BLOCK POLYISOCYANATE COMPOSITION, RESIN COMPOSITION, RESIN FILM AND LAYERED BODY
20230151137 · 2023-05-18
Assignee
Inventors
- Masatsugu HIGASHI (Tokyo, JP)
- Tomoharu YOSHINUMA (Tokyo, JP)
- Masakazu Yamauchi (Tokyo, JP)
- Misa HORINOUCHI (Tokyo, JP)
- Kie Shinomiya (Tokyo, JP)
Cpc classification
C08G18/4277
CHEMISTRY; METALLURGY
C08G18/62
CHEMISTRY; METALLURGY
C08J2375/12
CHEMISTRY; METALLURGY
C08G18/1875
CHEMISTRY; METALLURGY
C08G18/6229
CHEMISTRY; METALLURGY
C08G18/10
CHEMISTRY; METALLURGY
C08G18/12
CHEMISTRY; METALLURGY
C08G18/8093
CHEMISTRY; METALLURGY
C08G18/755
CHEMISTRY; METALLURGY
C08G18/0823
CHEMISTRY; METALLURGY
C08G18/722
CHEMISTRY; METALLURGY
C08G18/0866
CHEMISTRY; METALLURGY
C08G18/8093
CHEMISTRY; METALLURGY
C08G18/12
CHEMISTRY; METALLURGY
C08G18/8096
CHEMISTRY; METALLURGY
C08G18/62
CHEMISTRY; METALLURGY
International classification
C08G18/42
CHEMISTRY; METALLURGY
Abstract
This blocked polyisocyanate composition contains a block polyisocyanate derived from one or more diisocyanates, an active hydrogen compound, and a blocking agent containing a malonic acid ester. The active hydrogen compound has a number-average molecular weight of 60 to 5,000 and an average of 1.6 to 2.4 functional groups.
Claims
1. A blocked polyisocyanate composition comprising a blocked polyisocyanate derived from at least one diisocyanate, an active hydrogen compound and a blocking agent comprising a malonic acid ester, wherein the active hydrogen compound has both a number-average molecular weight of 60 to 5,000 and an average number of functional groups of 1.6 to 2.4.
2. A blocked polyisocyanate composition comprising a blocked polyisocyanate derived from an active hydrogen compound, a polyisocyanate and a blocking agent comprising a malonic acid ester, wherein the active hydrogen compound has both a number-average molecular weight of 60 to 5,000 and an average number of functional groups of 1.6 to 2.4.
3. The blocked polyisocyanate composition according to claim 2, wherein the active hydrogen compound is a polyol A.
4. The blocked polyisocyanate composition according to claim 3, wherein the polyol A is at least one polyol selected from the group consisting of 1,4-butanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,4-cyclohexanedimethanol, glycerol, and polycaprolactone polyols derived therefrom with ε-caprolactone.
5. The blocked polyisocyanate composition according to claim 2, wherein an amount of a constitution unit derived from the active hydrogen compound relative to 100 parts by mass of a constitution unit derived from the polyisocyanate is 0.05 parts by mass to 10 parts by mass.
6. The blocked polyisocyanate composition according to claim 2, wherein the polyisocyanate has an average number of isocyanate groups of 3.5 or more, has an isocyanurate group, and, is a polyisocyanate derived from at least one diisocyanate selected from the group consisting of aliphatic diisocyanates and alicyclic diisocyanates.
7. The blocked polyisocyanate composition according to claim 2, wherein the polyisocyanate is derived from a diisocyanate and a polyol B having an average number of functional groups of 2.9 to 8.0.
8. The blocked polyisocyanate composition according to claim 2, wherein the blocked polyisocyanate comprises a constitution unit of general formula (I): ##STR00009## in the general formula (I), R.sup.11, R.sup.12 and R.sup.13 are each independently an alkyl group which may have at least one substituent selected from the group consisting of a hydroxy group and an amino group, a total carbon number of R.sup.11, R.sup.12 and R.sup.13 is 3 to 20, R.sup.14, R.sup.15 and R.sup.16 are each independently a hydrogen atom or an alkyl group which may have at least one substituent selected from the group consisting of a hydroxy group and an amino group, and a wavy line indicates a bond.
9. The blocked polyisocyanate composition according to claim 8, wherein in the general formula (I), the total carbon number of R.sup.11, R.sup.12 and R.sup.13 is 4 to 20.
10. The blocked polyisocyanate composition according to claim 8, comprising a constitution unit (I-1) in which, in the general formula (I), the total carbon number of R.sup.11, and R.sup.13 is 4 to 20 and R.sup.16 is a hydrogen atom, as the constitution unit of general formula (I).
11. The blocked polyisocyanate composition according to claim 8, comprising a constitution unit in which, in the general formula (I), R.sup.11, R.sup.12 and R.sup.13 are each independently an unsubstituted alkyl group and R.sup.14, R.sup.15 and R.sup.16 are each independently a hydrogen atom or an unsubstituted alkyl group, as the constitution unit of the general formula (I).
12. The blocked polyisocyanate composition according to claim 8, wherein a molar ratio of hydroxy groups contained in the polyol A to the constitution unit of the general formula (I) is 0.5/99.5 to 15/85.
13. The blocked polyisocyanate composition according to claim 2, wherein the blocked polyisocyanate partially comprises a constitution unit derived from a hydrophilic compound.
14. The blocked polyisocyanate composition according to claim 13, wherein the hydrophilic compound comprises at least one compound selected from the group consisting of nonionic compounds and anionic compounds.
15. The blocked polyisocyanate composition according to claim 2, wherein the blocking agent comprises a malonic acid ester having a secondary alkyl group.
16. A blocked polyisocyanate composition comprising a blocked polyisocyanate derived from a polyisocyanate and at least one blocking agent, wherein the blocked polyisocyanate comprises a constitution unit of general formula (I): ##STR00010## in the general formula (I), R.sup.11, R.sup.12 and R.sup.13 are each independently an alkyl group which may have at least one substituent selected from the group consisting of a hydroxy group and an amino group, a total carbon number of R.sup.11, R.sup.12 and R.sup.13 is 4 to 20, R.sup.14, R.sup.15 and R.sup.16 are each independently a hydrogen atom or an alkyl group which may have at least one substituent selected from the group consisting of a hydroxy group and an amino group, and a wavy line indicates a bond.
17. The blocked polyisocyanate composition according to claim 16, further comprising a constitution unit of general formula (II), wherein a molar ratio of the constitution unit of general formula (II) to the constitution unit of general formula (I) is 4/96 to 96/4, ##STR00011## in the general formula (II), R.sup.21, R.sup.22, R.sup.23 and R.sup.24 are each independently a hydrogen atom or an alkyl group which may have at least one substituent selected from the group consisting of a hydroxy group and an amino group, and a wavy line indicates a bond.
18. The blocked polyisocyanate composition according to claim 16, comprising a constitution unit (I-1) in which R.sup.16 is a hydrogen atom as the constitution unit of the general formula (I).
19. The blocked polyisocyanate composition according to claim 16, wherein in the general formula (I) R.sup.11, R.sup.12 and R.sup.13 are each independently a methyl group or an ethyl group.
20. The blocked polyisocyanate composition according to claim 16, wherein isocyanate groups of the polyisocyanate are partially modified by a nonionic compound.
21. The blocked polyisocyanate composition according to claim 16, wherein the polyisocyanate has an average number of isocyanate groups of 2 or more.
22. The blocked polyisocyanate composition according to claim 16, wherein the polyisocyanate is a polyisocyanate derived from at least one diisocyanate selected from the group consisting of aliphatic diisocyanates and alicyclic diisocyanates.
23. The blocked polyisocyanate composition according to claim 16, wherein the blocked polyisocyanate has an isocyanurate group.
24. A resin composition comprising: a blocked polyisocyanate composition of claim 2; and a polyvalent hydroxy compound.
25. A resin film formed by curing a resin composition of claim 24.
26. A layered body comprising at least two layers of a resin film of claim 25, constitutions of the at least two layers being different from each other, wherein each layer thickness of the layered body is 1 μm to 50 μm.
27. A preparation method of a blocked polyisocyanate composition of claim 2, comprising: first reacting a polyisocyanate composition and a blocking agent containing a malonic acid ester; and second reacting a blocked polyisocyanate composition obtained in the first reacting and an active hydrogen compound.
28. A resin composition comprising: a blocked polyisocyanate composition of claim 16; and a polyvalent hydroxy compound.
29. A resin film formed by curing a resin composition of claim 28.
30. A layered body comprising at least two layers of a resin film of claim 29, constitutions of the at least two layers being different from each other, wherein each layer thickness of the layered body is 1 μm to 50 μm.
Description
EXAMPLES
[0513] Hereinafter, although the present embodiment will be described further specifically based on examples and comparative examples, the present embodiment is not limited to the following examples.
<Test Items>
[0514] Physical properties of blocked polyisocyanate compositions obtained in examples and comparative examples were measured and evaluated by the following methods.
[Physical Property 1]
(Content Ratio of Isocyanate (NCO) Groups)
[0515] A polyisocyanate before being blocked with a blocking agent was used as a measurement sample to measure the NCO content ratio of the polyisocyanate.
[0516] First, 2 g to 3 g of the measurement sample was precisely weighed in a flask (W g). Then, 20 mL of toluene was added thereto, and the measurement sample was dissolved. Then, 20 mL of a toluene solution containing 2 N di-n-butylamine was added thereto, and mixed, and then the resultant mixture was left to stand for 15 minutes at room temperature. Then, 70 mL of isopropyl alcohol was added thereto and mixed. Then, the resultant solution was titrated with 1 N hydrochloric acid solution (factor F) using an indicator. The titration value V2 mL was obtained. The same titration operation was performed without the polyisocyanate sample, and the titration value V1 mL was obtained. Then, the content ratio (% by mass) of isocyanate (NCO) groups of the polyisocyanate was calculated by the following equation.
Content ratio (% by mass) of isocyanate (NCO) groups=(V1−V2)×F×42/(W×1000)×100
[Physical Property 2]
(Number-Average Molecular Weight and Weight-Average Molecular Weight)
[0517] The number-average molecular weight and the weight-average molecular weight are the number-average molecular weight and the weight-average molecular weight determined by gel permeation chromatography (GPC) analysis using the following device with reference to polystyrene standards.
[0518] A polyisocyanate before being blocked with a blocking agent was used as a measurement sample to determine the number-average molecular weight of the polyisocyanate.
[0519] A blocked polyisocyanate composition or a polyvalent hydroxy compound was directly used as a measurement sample of the weight-average molecular weight. Measurement conditions are shown below.
(Measurement Conditions)
[0520] Device: HLC-802A (manufactured by Tosoh Corporation)
[0521] Column: G1000HXL×1 column, G2000HXL×1 column, G3000HXL×1 column (all of these were manufactured by Tosoh Corporation.)
[0522] Carrier: Tetrahydrofuran
[0523] Detection method: Differential refractometer
[Physical Property 3]
(Average Number of Isocyanate Groups)
[0524] The average number of isocyanate groups of the polyisocyanate (average NCO number) was determined in accordance with the following equation. In the equation, “Mn” is the number-average molecular weight of a polyisocyanate before being blocked with a blocking agent and the value determined in the above-mentioned “physical property 2” was used. The term “NCO content ratio” means the content ratio of isocyanate groups in a polyisocyanate measured before being blocked with a blocking agent, and the value determined in the above-mentioned “physical property 1” was used.
Average number of isocyanate groups=(Mn×NCO content ratio×0.01)/42
[Physical Property 4]
(Amount of Solid Content in Blocked Polyisocyanate Composition)
[0525] The amount of solid content in the blocked polyisocyanate composition was determined as described below.
[0526] The weight of an aluminum plate having a bottom diameter of 38 mm was precisely measured. Then, approximately 1 g of a blocked polyisocyanate composition prepared in an example or comparative example was placed on the aluminum plate, and the weight thereof (W1) was precisely measured. Then, the thickness of the blocked polyisocyanate composition was adjusted to be uniform. Then, the blocked polyisocyanate composition placed on the aluminum plate was maintained at 105° C. in an oven for 1 hour. Then, when the temperature of the aluminum plate decreased to room temperature, the weight (W2) of the blocked polyisocyanate composition remaining on the aluminum plate was measured. Then, the amount of solid content (% by mass) in the blocked polyisocyanate composition was calculated in accordance with the following equation.
Amount (% by mass) of solid content in blocked polyisocyanate composition=W2/W1×100
[Physical Property 5]
(Hydroxy Group Value)
[0527] The hydroxy group value of the polyvalent hydroxy compound was measured by potentiometer titration and calculated. The hydroxy group value is a value relative to the solid content in the polyvalent hydroxy compound.
[Physical Property 6]
(Glass Transition Temperature Tg)
[0528] An organic solvent and the moisture content in a polyvalent hydroxy compound solution were evaporated under reduced pressure, and then the resultant was subjected to vacuum drying, followed by measuring the glass transition temperature of the resultant using a differential scanning calory (DSC) measurement device at a temperature increase rate of 5° C./minute.
[Physical Property 7]
(Molar Ratio of Hydroxy Groups Contained in Polyol A to Constitution Unit (I) (OH/Constitution Unit (I))
[0529] The molar ratio of the amount (mol) of hydroxy groups contained in polyol A in the blocked polyisocyanate composition relative to that of the constitution unit (I) was calculated from formulation amounts of the polyol A and a blocking agent.
[0530] The amount (mol) of hydroxy groups contained in polyol A was determined by a gas chromatography/mass spectrometry method (GC/MS method), and the amount (mol) of the constitution unit (I) was determined by .sup.13C-NMR, to determine the molar ratio thereof.
(Measurement Conditions)
(Amount (Mol) of Hydroxy Groups Contained in Polyol A)
[0531] 5-Times mol of 2-ethylhexanol relative to the molar amount of effective isocyanate groups in a blocked polyisocyanate composition was added to the blocked polyisocyanate composition, followed by heating the mixture at 120° C. for 5 hours. The heated reaction liquid was subjected to gas chromatography/mass spectrometry (GC/MS) to measure the generated polyol A component, and then the amount (mol) of hydroxy groups contained in polyol A in the blocked polyisocyanate composition was calculated.
[0532] Device: “Agilent 7890, 5977” manufactured by Agilent Technologies, Inc.
[0533] Column: “HP-5MS” (L 30 m, I.D 0.250 mm, Film 0.25 μm) manufactured by Agilent Technologies, Inc.
[0534] Carrier gas: Helium
[0535] Detection device: MSD
[0536] Ionization: EI
[0537] Inlet temperature: 320° C.
[0538] Transfer temperature: 320° C.
[0539] Oven temperature: 40° C. (maintained for 5 minutes).fwdarw.(temperature elevated at 20° C./minute).fwdarw.320° C. (maintained for 10 minutes)
[0540] Split ratio: 1/1000
[0541] Mass range: m/z 10 to 800
[0542] Injection volume: 0.5 kL
(Amount (Mol) of Constitution Unit (I))
[0543] The amount of the constitution unit (I) in the blocked polyisocyanate composition was determined by .sup.13C-NMR.
[0544] Device: “JEOL-ECZ500 (SC) (trade name) manufactured by JEOL Ltd.
[0545] Solvent: Deuterated chloroform
[0546] Cumulated number: 5120
[0547] Sample concentration: 50 wt/vol %
[0548] Chemical shift standard: Deuterated chloroform was set at 77.0 ppm.
[Physical Property 8] Molar Ratio of Constitution Unit (I-1) to Constitution Unit (I)
[0549] The molar ratio of constitution unit (I-1) to constitution unit (I) in a blocked polyisocyanate composition (constitution unit (I-1)/constitution unit (I)) was determined by the following method.
[0550] Specifically, the total molar amount of the constitution unit (I) (including the constitution unit (I-1)) and the molar amount of the constitution unit (I-1) were determined by a .sup.13C-NMR analysis using “JEOL-ECZ500 (SC) (trade name) manufactured by JEOL Ltd, and then the molar ratio was determined.
(Measurement Conditions)
[0551] Device: “JEOL-ECZ500 (SC) (trade name) manufactured by JEOL Ltd.
[0552] Solvent: Deuterated chloroform
[0553] Cumulated number: 5120
[0554] Sample concentration: 50 wt/vol %
[0555] Chemical shift standard: Deuterated chloroform was set at 77.0 ppm.
[Physical Property 9]
(Molar Ratio of Constitution Unit (II)/Constitution Unit (I))
[0556] The molar ratio of the constitution unit (II) to the constitution unit (I) (constitution unit (II)/constitution unit (I)) was determined by evaporating the solvent and other components at 50° C. or lower using an evaporator to dry the blocked polyisocyanate composition under reduced pressure, followed by measuring the constitution ratio of the constitution unit (II) to the constitution unit (I) by .sup.13C-NMR to determine the molar ratio of the constitution unit (II) to the constitution unit (I).
(Measurement Conditions)
[0557] Device: “JEOL-ECZ500 (SC) (trade name) manufactured by JEOL Ltd.
[0558] Solvent: Deuterated chloroform
[0559] Cumulated number: 5120
[0560] Sample concentration: 50 wt/vol %
[0561] Chemical shift standard: Deuterated chloroform was set at 77.0 ppm.
[Physical Property 10]
(Amount of Monoalcohol in Blocked Polyisocyanate)
[0562] The amount (% by mass) of monoalcohol in the blocked polyisocyanate was quantified by a gas chromatography analysis.
[0563] Device: GC-2014 manufactured by Shimadzu Corporation.
[0564] Column: Agilent J&W DB-1 (L 30 m, I.D 0.25 mm, Film 1.00 μm)
[0565] Carrier: Helium
[0566] Detection device: FID
[0567] Inlet temperature: 100° C.
[0568] Detection device temperature: 220° C.
[0569] Oven temperature: 40° C. (maintained for 5 minutes).fwdarw.(temperature elevated at 10° C./minute).fwdarw.150° C. (maintained for 5 minutes)
[0570] Injection volume: 0.3 μL
[Preparation 1-1 of Resin Composition]
[0571] A polyvalent hydroxy compound OHP1 and each blocked isocyanate composition were formulated such that the molar ratio of isocyanate groups to hydroxy groups (isocyanate groups/hydroxy groups) was 1, followed by further adding 2-propanol to the mixture to adjust the solid content to 35% by mass, thereby obtaining a resin composition.
[Preparation 1-2 of Resin Composition]
[0572] A polyvalent hydroxy compound OHP1 and each blocked isocyanate composition were formulated such that the molar ratio of isocyanate groups to hydroxy groups (isocyanate groups/hydroxy groups) was 1, followed by further adding butyl acetate to the mixture to adjust the solid content to 35% by mass, thereby obtaining a resin composition.
[Evaluation 1-1]
(Storage Stability)
[0573] The viscosity of each resin composition obtained in the “Preparation 1-1 of resin composition” at an initial stage, and the viscosity thereof after storage at 40° C. for 10 days were measured (viscometer: RE-85R manufactured by TOKI SANGYO CO., LTD.). The ratio of the viscosity after storage relative to the viscosity at an initial stage was calculated. The storage stability was evaluated in accordance with the following criteria based on the calculated ratio of the viscosity after storage relative to the viscosity at the initial stage. The storage stability was evaluated in accordance with the following criteria.
(Evaluation Criteria)
[0574] A: Ratio of viscosity after storage to viscosity at an initial stage was 2.0 or less.
[0575] B: Ratio of viscosity after storage to viscosity at an initial stage exceeded 2.0 and 3.0 or less.
[0576] C: Gelated
[Evaluation 1-2]
(Low-Temperature Curability: Gel Fraction)
[0577] Each resin composition obtained by the “Preparation 1-2 of resin composition” was coated on a polypropylene (PP) plate such that a dried film thickness became 40 μm, dried at 80° C. for 30 minutes by heating to form a resin film. The resultant resin film was stored at ordinary temperature (23° C.) for 1 week to measure the gel fraction. The gel fraction was determined as a percentage (% by mass) by dividing the mass of the undissolved portion when the resin film was immersed in acetone at 23° C. for 24 hours by the mass of the resin film before being immersed. In the case where the gel fraction was 82% by mass or more, the resultant resin film was evaluated as favorable.
[Evaluation 1-3]
(Koenig Hardness)
[0578] The resin composition obtained in the “Preparation 1-2 of resin composition” was coated on a glass plate such that the dried film thickness became 40 m, followed by heating to dry at 80° C. for 30 minutes to obtain a resin film. The Koenig hardness (times) of the resultant resin film was measured using a Koenig hardness meter (Pendulum Hardness tester manufactured by BYK Gardner) at 23° C. In the case where the Koenig hardness was 40 times or more, the resultant was evaluated as favorable.
[Evaluation 1-4]
(Strength: Maximum Tensile Stress)
[0579] Each resin composition obtained by the “Preparation 1-2 of resin composition” was coated on a polypropylene (PP) plate such that the dried coating film thickness became 40 m, followed by heating and drying at 80° C. for 30 minutes to obtain a resin film. The resultant resin film was cut into a size of a width of 10 mm and a length of 40 mm, and then set such that the distance between chucks became 20 mm, followed by conducting a tensile test at 23° C. at a speed of 20 mm/minute. The maximum point stress was measured as the maximum tensile stress. In the case where the maximum tensile stress was 10.0 MPa or more, the resultant resin film was evaluated as favorable.
[Evaluation 1-5]
(Solvent Resistance (Xylene Rubbing Test))
[0580] Each resultant aqueous resin composition was coated on a glass plate such that the dried coating film thickness became 40 μm, and then heated to dry at 85° C. for 30 minutes to obtain each resin film. Then, the resultant resin film was stored at ordinary temperature (23° C.) for one day, and then rubbed with a cotton swab immersed in xylene in a reciprocating motion repeatedly 20 times over a distance of 3 cm, followed by observing the state of the resultant resin film. The solvent resistance was evaluated from the state of the resultant resin film in accordance with the following evaluation criteria. In the case where the evaluation result was B or better, the resultant resin film was evaluated as favorable.
[0581] A: Almost no deterioration was confirmed.
[0582] B: Streaks were confirmed partially in the rubbed portion.
[0583] C: Streaks were confirmed in the rubbed portion, and film-thinning phenomena were confirmed.
[0584] D: There were places in which the resin film was dissolved completely in the rubbed portion.
Synthesis of Polyisocyanate
Synthesis Example 1-1
(Synthesis of Polyisocyanate P1-1)
[0585] 100 parts by mass of HDI and 5.3 parts by mass of polyester polyol (polycaprolactone triol) (“PLACCEL 303” (trade name) manufactured by DAICEL ChemTech, Inc., and having an average number of functional groups of 3, and a number-average molecular weight of 300) derived from a trivalent alcohol and ε-caprolactone were charged into a four-necked flask equipped with a thermometer, a stirrer blade and a reflux cooling tube in a nitrogen gas flow, and then the mixture was stirred while maintaining the temperature in the reactor at 89° C. for 1 hour to allow a urethane-forming reaction to proceed. Then, the temperature in the reactor was maintained at 63° C., and tetramethylammonium caprylate, which is an isocyanurate-forming catalyst, was added to the resultant, followed by adding a phosphoric acid when the yield reached 52% by mass to terminate the reaction. The reaction liquid was subjected to filtration, and then unreacted HDI was removed therefrom using a thin film evaporator to obtain an isocyanurate-type polyisocyanate (hereinafter, may be referred to as “polyisocyanate P1-1”).
[0586] The NCO content ratio of the resultant polyisocyanate P1-1 was 18.6% by mass, the number-average molecular weight thereof was 1220, and the average number of isocyanate groups was 5.4. The resultant polyisocyanate P1-1 was subjected to .sup.1H-NMR analysis to confirm the presence of an isocyanurate group.
Synthesis Example 1-2
(Synthesis of Polyisocyanate P1-2)
[0587] 81 parts by mass of HDI, 19 parts by mass of IPDI, and 3.35 parts by mass of trimethylolpropane (having an average number of functional groups of 3, and a molecular weight of 134), which is a trivalent alcohol, were charged into a four-necked flask equipped with a thermometer, a stirrer blade and a reflux cooling tube in a nitrogen gas flow, and then the mixture was stirred while maintaining the temperature in the reactor at 88° C. for 1 hour to allow a urethane-forming reaction to proceed. Then, the temperature in the reactor was maintained at 78° C., and 0.012 parts by mass of tetramethylammonium caprylate, which is an isocyanurate-forming catalyst, was added to the resultant, followed by adding a phosphoric acid when the yield reached 44% by mass to terminate the reaction. The reaction liquid was subjected to filtration, and then unreacted HDI and IPDI were removed therefrom using a thin film evaporator to obtain an isocyanurate-type polyisocyanate (hereinafter, may be referred to as “polyisocyanate P1-2”). The NCO content ratio of the resultant polyisocyanate P1-2 was 19.0% by mass, the number-average molecular weight thereof was 1170, and the average number of isocyanate groups was 5.3. The resultant polyisocyanate P1-2 was subjected to .sup.1H-NMR analysis to confirm the presence of an isocyanurate group.
Synthesis Example 1-3
(Synthesis of Polyisocyanate P1-3)
[0588] 70 parts by mass of HDI, 30 parts by mass of IPDI, and 2.9 parts by mass of trimethylolpropane (having an average number of functional groups of 3, and a molecular weight of 134), which is a trivalent alcohol, were charged into a four-necked flask equipped with a thermometer, a stirrer blade and a reflux cooling tube in a nitrogen gas flow, and then the mixture was stirred while maintaining the temperature in the reactor at 88° C. for 1 hour to allow a urethane-forming reaction to proceed. Then, the temperature in the reactor was maintained at 78° C., and 0.012 parts by mass of tetramethylammonium caprylate, which is an isocyanurate-forming catalyst, was added to the resultant, followed by adding a phosphoric acid when the yield reached 44% by mass to terminate the reaction. The reaction liquid was subjected to filtration, and then unreacted HDI and IPDI were removed therefrom using a thin film evaporator to obtain an isocyanurate-type polyisocyanate (hereinafter, may be referred to as “polyisocyanate P1-3”). The NCO content ratio of the resultant polyisocyanate P1-3 was 18.9% by mass, the number-average molecular weight thereof was 1130, and the average number of isocyanate groups was 5.1. The resultant polyisocyanate P1-3 was subjected to .sup.1H-NMR analysis to confirm the presence of an isocyanurate group.
Synthesis Example 1-4
(Synthesis of Polyisocyanate P1-4)
[0589] 100 parts by mass of HDI was charged into a four-necked flask equipped with a thermometer, a stirrer blade and a reflux cooling tube in a nitrogen gas flow, and 0.095 parts by mass of trimethylbenzylammonium hydroxide was added thereto while stirring and maintaining the temperature in the reactor at 60° C. 4.5 hours later, the reaction was terminated by adding 0.02 parts by mass of a phosphoric acid to the resultant when the conversion ratio reached 40% by mass. The reaction liquid was subjected to filtration, and then unreacted HDI was removed therefrom using a thin film evaporator to obtain an isocyanurate-type polyisocyanate (hereinafter, may be referred to as “polyisocyanate P1-4”). The NCO content ratio of the resultant polyisocyanate P1-4 was 22.0% by mass, the number-average molecular weight thereof was 655, and the average number of isocyanate groups was 3.43. The resultant polyisocyanate P1-4 was subjected to .sup.1H-NMR analysis to confirm the presence of an isocyanurate group.
Synthesis Example 1-5
(Synthesis of Polyisocyanate P1-5)
[0590] 600 parts by mass of HDI and 10.8 parts by mass of 1,3-butanediol, which is a divalent alcohol, were charged into a four-necked flask equipped with a thermometer, a stirrer blade and a reflux cooling tube in a nitrogen gas flow, followed by maintaining the temperature in the reactor at 90° C. for 1 hour while stirring the mixture to allow a urethane-forming reaction to proceed. Then, 0.03 parts by mass of tetetramethylammonium caprylate was added to the resultant as an isocyanurate-forming catalyst while maintaining the temperature in the reactor at 80° C., the refractive index of the reaction liquid was measured, and a phosphoric acid was added thereto to terminate the reaction when the yield reached 55%. The reaction liquid was subjected to filtration, and then unreacted HDI was removed therefrom using a thin film evaporator to obtain an isocyanurate-type polyisocyanate (hereinafter, may be referred to as “polyisocyanate P1-5”). The NCO content ratio of the resultant polyisocyanate P1-5 was 19.3% by mass, the number-average molecular weight thereof was 970, and the average number of isocyanate groups was 4.4. The resultant polyisocyanate P1-5 was subjected to .sup.1H-NMR analysis to confirm the presence of an isocyanurate group.
Preparation of Blocked Polyisocyanate Composition
Example 1-1
(Preparation of Blocked Polyisocyanate Composition BL-a1-1)
[0591] 100 parts by mass of the polyisocyanate P1-1 obtained in Synthesis Example 1-1, 0.59 parts by mass (0.50% by mol, relative to 100% by mol of isocyanate groups) of polycaprolactone diol (hereinafter, may be referred to as “C1”) (“PLACCEL 205UT” (trade name) manufactured by DAICEL ChemTech, Inc., and having a number-average molecular weight of 530, and an average number of functional groups of 2), 0.008 parts by mass of 2-ethylhexyl acid phosphate (“JP-508T” (trade name) manufactured by JOHOKU CHEMICAL CO., LTD.), and 54.2% by mass of dipropylene glycol dimethyl ether (DPDM) were mixed in a four-necked flask equipped with a thermometer, a stirrer blade and a reflux cooling tube in a nitrogen gas flow, to allow the reaction to proceed at 80° C. for 3 hours. The reaction liquid was cooled to 40° C., and then 50% by mol of diisopropyl malonate (hereinafter, may be referred to as “B1”) relative to 100% by mol of isocyanate groups and 50% by mol of di-tert-butyl malonate (hereinafter, may be referred to as “B2”) relative to 100% by mol of isocyanate groups were added thereto followed by further adding dipropylene glycol dimethyl ether (DPDM) thereto to adjust the solid content to 60% by mass. Then, 1.1 parts by mass of a methanol solution containing sodium methylate (28% by mass relative to the total mass of the solution) was added dropwise while conducting stirring, followed by adjusting an outer bath such that the solution temperature was 47° C. to allow the blocking reaction to proceed at 47° C. for 6 hours or more. The disappearance of the peak of isocyanate groups was confirmed by infrared spectroscopy (IR) to obtain a blocked polyisocyanate composition BL-a1-1. The solid content of the resultant blocked polyisocyanate composition BL-a1-1 was 60.0% by mass, and the weight-average molecular weight thereof was 2.1×10.sup.4.
[Examples 1-2 to 1-14, 1-17 to 1-21, 1-23, and 1-26 and Comparative Examples 1-1 and 1-2] (Preparation of Blocked Polyisocyanate Compositions BL-a1-2 to BL-a1-14, BL-a1-17 to BL-a1-21, BL-a1-23, BL-a1-26, BL-b1-1 and BL-b1-2)
[0592] Each blocked polyisocyanate composition was prepared by the same method as that of Example 1-1, except that the kind of the polyisocyanate, polyol and blocking agent, and the formulation amount thereof were changed to those shown in Tables 1 to 6.
Example 1-15
(Preparation of Blocked Polyisocyanate Composition BL-a1-15)
[0593] 100 parts by mass of the polyisocyanate P1-1 obtained in Synthesis Example 1-1, 50% by mol of diisopropyl malonate (B1) relative to 100% by mol of isocyanate groups and 50% by mol of di-tert-butyl malonate (B2) relative to 100% by mol of isocyanate groups were charged in a four-necked flask equipped with a thermometer, a stirrer blade and a reflux cooling tube in a nitrogen gas flow, followed by adding dipropylene glycol dimethyl ether (DPDM) thereto to adjust the solid content to 60% by mass. Then, 1.1 parts by mass of a methanol solution containing sodium methylate (28% by mass relative to the total mass of the solution) was added dropwise while conducting stirring, followed by adjusting an outer bath such that the solution temperature was 47° C. to allow the blocking reaction to proceed at 47° C. for 6 hours or more. Then, 0.59 parts by mass of polycaprolactone diol (C1) (“PLACCEL 205UT” (trade name) manufactured by DAICEL ChemTech, Inc., and having a number-average molecular weight of 530, and an average number of functional groups of 2) was added to the resultant, followed by adjusting an outer bath such that the solution temperature was 80° C. to allow the reaction to proceed for 2 hours, thereby obtaining a blocked polyisocyanate composition BL-a1-15. The solid content of the resultant blocked polyisocyanate composition BL-a1-15 was 60.1% by mass, and the weight-average molecular weight thereof was 1.8×10.sup.4.
Example 1-16
(Preparation of Blocked Polyisocyanate Composition BL-a1-16)
[0594] 100 parts by mass of the polyisocyanate P1-2 obtained in Synthesis Example 1-2, 0.59 parts by mass (0.50% by mol relative to 100% by mol of isocyanate groups) of polycaprolactone diol (C1) (“PLACCEL 205UT” (trade name) manufactured by DAICEL ChemTech, Inc., and having a number-average molecular weight of 530, and an average number of functional groups of 2), 0.5% by mol of methoxypolyethylene glycol (MPG-081, having 15 ethylene oxide repeating units, and manufactured by NIPPON NYUKAZAI CO., LTD.) relative to 100% by mol of isocyanate groups of the polyisocyanate P1-2, 0.008 parts by mass of 2-ethylhexyl acid phosphate (“JP-508T” (trade name) manufactured by JOHOKU CHEMICAL CO., LTD.) and 54.2 parts by mass of dipropylene glycol dimethyl ether (DPDM) were mixed in a four-necked flask equipped with a thermometer, a stirrer blade and a reflux cooling tube in a nitrogen gas flow, to allow the reaction to proceed at 80° C. for 4 hours. The reaction liquid was cooled to 40° C., and 70% by mol of diisopropyl malonate (B1) relative to 100% by mol of isocyanate groups, and 30% by mol of di-tert-butyl malonate (B2) relative to 100% by mol of isocyanate groups were charged therein, followed by further adding dipropylene glycol dimethyl ether (DPDM) thereto to adjust the solid content to 60% by mass. Then, 1.1 parts by mass of a methanol solution containing sodium methylate (28% by mass relative to the total mass of the solution) was added dropwise while conducting stirring, followed by adjusting an outer bath such that the solution temperature was 47° C. to allow the blocking reaction to proceed at 47° C. for 6 hours or more. The disappearance of the peak of isocyanate groups was confirmed by infrared spectroscopy (IR) to obtain a blocked polyisocyanate composition BL-a1-16. The solid content of the resultant blocked polyisocyanate composition BL-a1-16 was 60.0% by mass, and the weight-average molecular weight thereof was 2.0×10.sup.4.
Example 1-22
(Preparation of Blocked Polyisocyanate Composition BL-a1-22)
[0595] 100 parts by mass of the polyisocyanate P1-1 obtained in Synthesis Example 1-1, 5.9 parts by mass (0.50% by mol relative to 100% by mol of isocyanate groups) of polycaprolactone diol (C1) (“PLACCEL 205UT” (trade name) manufactured by DAICEL ChemTech, Inc., and having a number-average molecular weight of 530, and an average number of functional groups of 2), 0.008 parts by mass of 2-ethylhexyl acid phosphate (“JP-508T” (trade name) manufactured by JOHOKU CHEMICAL CO., LTD.), and 57.0 parts by mass of dipropylene glycol dimethyl ether (DPDM) were mixed in a four-necked flask equipped with a thermometer, a stirrer blade and a reflux cooling tube in a nitrogen gas flow to allow the reaction to proceed at 80° C. for 3 hours. The reaction liquid was cooled to 40° C., and diisopropyl malonate (B1) equimolar to isocyanate groups was charged thereinto, followed by further adding dipropylene glycol dimethyl ether (DPDM) to adjust the solid content to 60% by mass. Then, 1.1 parts by mass of a methanol solution containing sodium methylate (28% by mass relative to the total mass of the solution) was added dropwise while conducting stirring, followed by adjusting an outer bath such that the solution temperature was 47° C. to allow the blocking reaction to proceed at 47° C. for 6 hours or more, thereby obtaining an intermediate of a blocked polyisocyanate composition. Then, 200% by mol of tert-butanol relative to blocked isocyanate groups was added to the resultant to allow the reaction to proceed at 80° C. for 3 hours while removing generated isopropyl alcohol by conducting distillation under ordinary pressure. Then, isopropanol and tert-butanol were distilled away at 60° C. under reduced pressure (50 kPa), and finally dipropylene glycol dimethyl ether (DPDM) was added to the resultant to adjust the solid content to 60% by mass, thereby obtaining a blocked polyisocyanate composition BL-a1-22. The solid content of the resultant blocked polyisocyanate composition BL-a1-22 was 60.0% by mass, and the weight-average molecular weight thereof was 9.0×10.sup.3.
Example 1-24
(Preparation of Blocked Polyisocyanate Composition BL-a1-24)
[0596] 100 parts by mass of the polyisocyanate P1-1 obtained in Synthesis Example 1-1, 5.9 parts by mass (0.50% by mol relative to 100% by mol of isocyanate groups) of polycaprolactone diol (C1) (“PLACCEL 205UT” (trade name) manufactured by DAICEL ChemTech, Inc., and having a number-average molecular weight of 530, and an average number of functional groups of 2), 0.008 parts by mass of 2-ethylhexyl acid phosphate (“JP-508T” (trade name) manufactured by JOHOKU CHEMICAL CO., LTD.), and 57.0 parts by mass of dipropylene glycol dimethyl ether (DPDM) were mixed into a four-necked flask equipped with a thermometer, a stirrer blade and a reflux cooling tube in a nitrogen gas flow, to allow the reaction to proceed at 80° C. for 3 hours. The reaction liquid was cooled to 40° C., and diisopropyl malonate (B1) equimolar to isocyanate groups was charged thereinto, followed by further adding dipropylene glycol dimethyl ether (DPDM) to adjust the solid content to 60% by mass. Then, 1.1 parts by mass of a methanol solution containing sodium methylate (28% by mass relative to the total mass of the solution) was added dropwise while conducting stirring, followed by adjusting an outer bath such that the solution temperature was 47° C. to allow the blocking reaction to proceed at 47° C. for 6 hours or more, thereby obtaining an intermediate of a blocked polyisocyanate composition. Then, 200% by mol of 2-methyl-2-butanol relative to blocked isocyanate groups was added to the resultant to allow the reaction to proceed at 110° C. for 5 hours while removing generated isopropyl alcohol by conducting distillation under ordinary pressure. Then, isopropanol and 2-methyl-2-butanol were distilled away at 60° C. under reduced pressure (50 kPa), and finally dipropylene glycol dimethyl ether (DPDM) was added to the resultant to adjust the solid content to 60% by mass, thereby obtaining a blocked polyisocyanate composition BL-a1-24. The solid content of the resultant blocked polyisocyanate composition BL-a1-24 was 60.0% by mass, and the weight-average molecular weight thereof was 9.0×10.sup.3.
Example 1-25
(Preparation of Blocked Polyisocyanate Composition BL-a1-25)
[0597] 100 parts by mass of the polyisocyanate P1-1 obtained in Synthesis Example 1-1 and diisopropyl malonate (B1) equimolar to isocyanate groups were charged into a four-necked flask equipped with a thermometer, a stirrer blade and a reflux cooling tube in a nitrogen gas flow, followed by adding dipropylene glycol dimethyl ether (DPDM) thereto to adjust the solid content to 60% by mass. Then, 1.1 parts by mass of a methanol solution containing sodium methylate (28% by mass relative to the total mass of the solution) was added dropwise while conducting stirring, followed by adjusting an outer bath such that the solution temperature was 47° C. to allow the blocking reaction to proceed at 47° C. for 6 hours or more. Then, 5.9 parts by mass of polycaprolactone diol (C1) (“PLACCEL 205UT” (trade name) manufactured by DAICEL ChemTech, Inc., and having a number-average molecular weight of 530, and an average number of functional groups of 2) was added to the resultant, followed by adjusting an outer bath such that the solution temperature was 80° C. to allow the reaction to proceed for 2 hours. Then, 200% by mol of 2-methyl-2-butanol relative to blocked isocyanate groups was added to the resultant to allow the reaction to proceed at 110° C. for 5 hours while removing generated isopropyl alcohol by conducting distillation under ordinary pressure. Then, isopropanol and 2-methyl-2-butanol were distilled away at 60° C. under reduced pressure (50 kPa), and finally dipropylene glycol dimethyl ether (DPDM) was added to the resultant to adjust the solid content to 60% by mass, thereby obtaining a blocked polyisocyanate composition BL-a1-25. The solid content of the resultant blocked polyisocyanate composition BL-a1-25 was 60.0% by mass, and the weight-average molecular weight thereof was 9.0×10.sup.3.
Preparation of Polyvalent Hydroxy Compound
Preparation Example 1
(Preparation of Polyvalent Hydroxy Compound OHP1)
[0598] 29 parts by mass of propylene glycol monomethyl ether was charged into a four-necked flask equipped with a stirrer, a thermometer, a cooling tube, and a nitrogen gas inlet, and the temperature was increased to 110° C. in a nitrogen gas flow. When the temperature reached 110° C., the supply of nitrogen gas was stopped, and then a mixture composed of 22.3 parts by mass of 2-hydroxyethyl methacrylate, 8.0 parts by mass of methyl methacrylate, 26.1 parts by mass of butyl acrylate, 42.3 parts by mass of styrene, 1.3 parts by mass of acrylic acid, and 1.9 parts by mass of 2,2′-azobis(isobutyronitrile) was added dropwise over 5.5 hours. Then, the resultant was stirred at 115° C. for 3 hours while flowing nitrogen gas, and then cooled to 30° C., followed by removing the solvent by an evaporator. Then, butyl acetate was added to the resultant to obtain a solution of a polyvalent hydroxy compound OHPT, which was an acrylic polyol-based resin having a solid content of 60% by mass. The weight-average molecular weight Mw of the polyvalent hydroxy compound OHP1 was 2.73×10.sup.4, the hydroxy group value thereof was 139 mgKOH/g, and the glass transition temperature Tg was 29.8° C.
[0599] In the following Tables 1 to 6, abbreviations show the following compounds.
(Polyol A)
[0600] C1: Polycaprolactone diol (“PLACCEL 205UT” (trade name) manufactured by DAICEL ChemTech, Inc., and having a number-average molecular weight of 530, and an average number of functional groups of 2).
[0601] C2: Polycaprolactone diol (“PLACCEL 220CPT” (trade name) manufactured by DAICEL ChemTech, Inc., and having a number-average molecular weight of 2000, and an average number of functional groups of 2).
[0602] C3: Polycaprolactone diol (“PLACCEL 240CP” (trade name) manufactured by DAICEL ChemTech, Inc., and having a number-average molecular weight of 4000 and an average number of functional groups of 2).
[0603] C4: 1,4-Butane diol (having a molecular weight of 90.12, and two hydroxy groups).
[0604] C5: 1,3-Butanediol (having a molecular weight of 90.12, and two hydroxy groups).
(Blocking Agent)
[0605] B1: Diisopropyl malonate
[0606] B2: Di-tert-butyl malonate
[0607] B3: Di(2-methyl-2-butyl) malonate
TABLE-US-00001 TABLE 1 Ex- Ex- Ex- Ex- Ex- ample ample ample ample ample 1-1 1-2 1-3 1-4 1-5 Blocked polyisocyanate BL- BL- BL- BL- BL- composition a1-1 a1-2 a1-3 a1-4 a1-5 Consti- Polyiso- Type P1-1 P1-1 P1-1 P1-1 P1-1 tution cyanate Formu- 100 100 100 100 100 lation amount (parts by mass) Polyol Type Cl C1 C1 C1 C2 A Formu- 0.59 1.18 3.54 5.9 2.19 lation amount (parts by mass) Blocking Type B1 B1 B1 B1 B1 agent B2 B2 B2 B2 B2 — — — — — Molar 50/50 50/50 50/50 50/50 50/50 ratio (B1)/ (B2) Molar — — — — — ratio (B1)/ (B3) Consti- Total 3 3 3 3 3 tution carbon unit (1) number of R.sup.11, R.sup.12, and R.sup.13 Molar ratio 0% 0% 0% 0% 0% (Constitution unit (1-1)/ Constitution unit (I)) Amount % by 0% 0% 0% 0% 0% of mass alcohol
TABLE-US-00002 TABLE 2 Ex- Ex- Ex- Ex- Ex- ample ample ample ample ample 1-6 1-7 1-8 1-9 1-10 Blocked polyisocyanate BL- BL- BL- BL- BL- composition a1-6 a1-7 a1-8 a1-9 a1-10 Con- Polyiso- Type P1-1 P1-1 P1-1 P1-1 P1-1 sti- cyanate Formu- 100 100 100 100 100 tu- lation tion amount (parts by mass) Polyol A Type C2 C3 C4 C4 C1 Formu- 4.39 4.42 0.3 0.2 0.59 lation amount (parts by mass) Blocking Type B1 B1 B1 B1 B1 agent B2 B2 B2 B2 B2 — — — — — Molar ratio 50/50 50/50 50/50 50/50 70/30 (B1)/(B2) Molar ratio — — — — — (B1)/(B3) Consti- Total 3 3 3 3 3 tution carbon unit (I) number of R.sup.11, R.sup.12, and R.sup.13 Molar ratio 0% 0% 0% 0% 0% (Constitution unit (I-1)/ Constitution unit (I)) Amount % by 0% 0% 0% 0% 0% of mass alcohol
TABLE-US-00003 TABLE 3 Ex- Ex- Ex- Ex- Ex- ample ample ample ample ample 1-11 1-12 1-13 1-14 1-15 Blocked polyisocyanate BL- BL- BL- BL- BL- composition a1-11 a1-12 a1-13 a1-14 a1-15 Con- Polyiso- Type P1-1 P1-1 P1-2 P1-3 P1-1 sti- cyanate Formu- 100 100 100 100 100 tu- lation tion amount (parts by mass) Polyol A Type C1 C1 C1 C1 C1 Formu- 1.18 1.18 1.21 1.2 0.59 lation amount (parts by mass) Blocking Type B1 B1 B1 B1 B1 agent B2 B2 B2 B2 B2 — — — — — Molar ratio 70/30 70/30 92/8 70/30 50/50 (B1)/(B2) Molar ratio — — — — — (B1)/(B3) Consti- Total 3 3 3 3 3 tution carbon unit (I) number of R.sup.11, R.sup.12, and R.sup.13 Molar ratio 0% 0% 0% 0% 0% (Constitution unit (I-1)/ Constitution unit (I)) Amount % by 0% 0% 0% 0% 0% of mass alcohol
TABLE-US-00004 TABLE 4 Ex- Ex- Ex- Ex- Ex- ample ample ample ample ample 1-16 1-17 1-18 1-19 1-20 Blocked polyisocyanate BL- BL- BL- BL- BL- composition a1-16 a1-17 a1-18 a1-19 a1-20 Con- Polyiso- Type P1-2 P1-1 P1-1 P1-1 P1-1 sti- cyanate Formu- 100 100 100 100 100 tu- lation tion amount (parts by mass) Polyol A Type C1 C1 C1 C1 C1 Formu- 0.59 5.9 5.9 9.5 0.59 lation amount (parts by mass) Blocking Type B1 B1 B1 B1 B1 agent B2 B2 B2 B2 B2 — — — — — Molar ratio 70/30 20/80 40/60 50/50 97.2/ (B1)/(B2) 2.8 Molar ratio — — — — — (B1)/(B3) Consti- Total carbon 3 3 3 3 3 tution number of unit (I) R.sup.11, R.sup.12, and R.sup.13 Molar ratio 0% 0% 0% 0% 0% (Constitution unit (I-1)/ Constitution unit (I)) Amount % by 0% 0% 0% 0% 0% of mass alcohol
TABLE-US-00005 TABLE 5 Ex- Ex- Ex- Ex- Ex- ample ample ample ample ample 1-21 1-22 1-23 1-24 1-25 Blocked polyisocyanate BL- BL- BL- BL- BL- composition a1-21 a1-22 a1-23 a1-24 a1-25 Con- Polyiso- Type P1-1 P1-1 P1-1 P1-1 P1-1 sti- cyanate Formu- 100 100 100 100 100 tu- lation tion amount (parts by mass) Polyol A Type C1 C1 C1 C1 C1 Formu- 0.59 5.9 5.9 5.9 5.9 lation amount (parts by mass) Blocking Type B1 B1 B1 B1 B1 agent B2 — — — — — — B3 — — Molar ratio 98.6/ 100/0 — 100/0 100/0 (B1)/(B2) 1.4 Molar ratio — — 40/60 — — (B1)/(B3) Consti Total carbon 3 3 4 4 4 tution number of unit (I) R.sup.11, R.sup.12, and R.sup.13 Molar ratio 0% 80% 0% 80% 80% (Constitution unit (I-1)/ Constitution unit (I)) Amount % by 0% 3% 0% 3% 3% of mass alcohol
TABLE-US-00006 TABLE 6 Comparative Comparative Example 1-26 Example 1-1 Example 1-2 Blocked polyisocyanate composition BL-a1-26 BL-b1-1 BL-b1-2 Constitution Polyisocyanate Type P1-5 P1-1 P1-4 Formulation amount 100 100 100 (parts by mass) Polyol A Type C5 Unmodified Unmodified Formulation amount 3.25 — — (parts by mass) Blocking Type B1 — — agent B2 B2 B2 — — — Molar ratio (B1)/(B2) 40/60 0/100 0/100 Molar ratio (B1)/(B3) — — — Constitution unit Total carbon number of 3 3 3 (I) R.sup.11, R.sup.12, and R.sup.13 Molar ratio 0% 0% 0% (Constitution unit (I-1)/ Constitution unit (I)) Amount of alcohol % by mass 0% 0% 0%
TABLE-US-00007 TABLE 7 Ex- Ex- Ex- Ex- Ex- ample ample ample ample ample 1-1 1-2 1-3 1-4 1-5 Phy- Average 5.4 5.4 5.4 5.4 5.4 sical NCO pro- number per- of ties polyiso- cyanate Number- 530 530 530 530 2000 average molecular weight of polyol A Average 2 2 2 2 2 number of functional groups of polyol A Molar 1.0/ 2.0/ 5.9/ 9.6/ 1.0/ ratio 99.0 98.0 94.1 90.4 99.0 (OH/ Consti- tution unit (I)) Solid 60 60 60 60 60 content (% by mass) Weight- 1.8 × 2.0 × 2.5 × 3.0 × 2.4 × average 10.sup.4 10.sup.4 10.sup.4 10.sup.4 10.sup.4 molecular weight Eval- Storage A A A A A uation stability Low- 89.3 89.2 88.9 88.5 89.6 temper- ature curability (gel fraction: % by mass) Solvent B B B A B resistance Koenig 68 67 65 63 67 hardness (times) Maxi- 28.5 28.3 27.5 25.5 28.8 mum tensile stress (MPa)
TABLE-US-00008 TABLE 8 Ex- Ex- Ex- Ex- Ex- ample ample ample ample ample 1-6 1-7 1-8 1-9 1-10 Phy- Average 5.4 5.4 5.4 5.4 5.4 sical NCO pro- number per- of poly- ties isocyanate Number- 2000 4000 90 90 530 average molecular weight of polyol A Average 2 2 2 2 2 number of functional groups of polyol A Molar ratio 2.0/ 1.0/ 3.0/ 2.0/ 1.7/ (OH/ 98.0 99.0 97.0 98.0 98.3 Constitution unit (I)) Solid 60 60 60 60 60 content (% by mass) Weight- 2.6 × 2.5 × 1.9 × 1.8 × 2.2 × average 10.sup.4 10.sup.4 10.sup.4 10.sup.4 10.sup.4 molecular weight Eval- Storage A A A A A uation stability 89.7 89.5 88.3 88.4 89.1 Low- temperature curability (gel fraction: % by mass) Solvent B B B B B resistance Koenig 66 66 67 68 67 hardness (times) Maximum 28.6 27.6 26.8 27 28.2 tensile stress (MPa)
TABLE-US-00009 TABLE 9 Ex- Ex- Ex- Ex- Ex- ample ample ample ample ample 1-11 1-12 1-13 1-14 1-15 Phy- Average 5.4 5.4 5.3 5.1 5.4 sical NCO pro- number of per- polyiso- ties cyanate Number- 530 530 530 530 530 average molecular weight of polyol A Average 2 2 2 2 2 number of functional groups of polyol A Molar ratio 3.3/ 11.3/ 3.3/ 3.3/ 1.0/ (OH/ 96.7 88.7 96.7 96.7 99.0 Constitution unit (I)) Solid 60 60 60 60 60 content (% by mass) Weight- 2.3 × 2.5 × 1.9 × 1.8 × 1.7 × average 10.sup.4 10.sup.4 10.sup.4 10.sup.4 10.sup.4 molecular weight Eval- Storage A A A A A uation stability Low- 89.2 87.4 89 88.6 88.9 temper- ature curability (gel fraction: % by mass) Solvent B B B B B resistance Koenig 67 65 86 88 68 hardness (times) Maximum 27.8 26.3 31.6 30.5 27.8 tensile stress (MPa)
TABLE-US-00010 TABLE 10 Ex- Ex- Ex- Ex- Ex- ample ample ample ample ample 1-16 1-17 1-18 1-19 1-20 Phy- Average 5.3 5.4 5.4 5.4 5.4 sical NCO pro- number of per- polyiso- ties cyanate Number- 530 530 530 530 530 average molecular weight of polyol A Average 2 2 2 2 2 number of functional groups of polyol A Molar ratio 1.7/ 6.2/ 8.1/ 15/ 15.3/ (OH/ 98.3 93.8 91.9 85.0 84.7 Constitution unit (I)) Solid 60 60 60 60 60 content (% by mass) Weight- 2.0 × 3.0 × 3.0 × 3.5 × 1.8 × average 10.sup.4 10.sup.4 10.sup.4 10.sup.4 10.sup.4 molecular weight Eval- Storage A A A A A uation stability Low- 89.2 88.9 87.1 89.1 75.2 temper- ature curability (gel fraction: % by mass) Solvent B A A B c resistance Koenig 91 72 65 57 21 hardness (times) Maximum 31.8 29.3 27.7 16.2 7.3 tensile stress (MPa)
TABLE-US-00011 TABLE 11 Ex- Ex- Ex- Ex- Ex- ample ample ample ample ample 1-21 1-22 1-23 1-24 1-25 Phy- Average 5.4 5.4 5.4 5.4 5.4 sical NCO pro- number of per- polyiso- ties cyanate Number- 530 530 530 530 530 average molecular weight of polyol A Average 2 2 2 2 2 number of functional groups of polyol A Molar ratio 26.5/ 8.9/ 8.1/ 8.9/ 8.9/ (OH/ 73.5 91.1 91.9 91.1 91.1 Constitution unit (I)) Solid 60 60 60 60 60 content (% by mass) Weight- 1.8 × 9.0 × 3.0 × 9.0 × 9.0 × average 10.sup.4 10.sup.3 10.sup.4 10.sup.3 10.sup.3 molecular weight Eval- Storage A A A A A uation stability Low- 74.3 91.1 92.1 91.9 91.8 temper- ature curability (gel fraction: % by mass) Solvent C A A A A resistance Koenig 19 73 75 80 81 hardness (times) Maximum 6.2 32.1 35.5 37.2 36.5 tensile stress (MPa)
TABLE-US-00012 TABLE 12 Comparative Comparative Example 1-26 Example 1-1 Example 1-2 Physical Average NCO number of 4.4 5.4 3.43 properties polyisocyanate Number-average molecular 90 — — weight of polyol A Average number of functional 2 — 2 groups of polyol A Molar ratio (OH/Constitution 23/77 0/100 0/100 unit (I)) Solid content (% by mass) 60 60 60 Weight-average molecular 1.2 × 10.sup.4 8.5 × 10.sup.3 2.4 × 10.sup.3 weight Evaluation Storage stability A A Low-temperature curability 85.4 80.9 62.3 (gel fraction: % by mass) Solvent resistance C D D Koenig hardness 45 33 4 (times) Maximum tensile stress 24.3 9.7 2.1 (MPa)
[0608] As shown in the tables, the blocked polyisocyanate compositions BL-a1-1 to BL-a1-16 (Examples 1-1 to 1-16) exhibited favorable storage stability of the resultant resin composition, and excellent curability at a low temperature of about 80° C., hardness and strength of the resultant coating film.
[0609] When the blocked polyisocyanate compositions BL-a1-1 to BL-a1-4 (Examples 1-1 to 1-4) in which the formulation amount of the polyol A was different from each other were compared, there was a tendency that the decrease in the formulation amount of the polyol A improved the curability at a low temperature of about 80° C., the hardness and the strength when made into a coating film.
[0610] When the blocked polyisocyanate compositions BL-a1-2, BL-a1-11 and BL-a1-12 (Examples 1-2, 1-11 and 1-12) in which the molar ratio of the blocking agent B1 to the blocking agent B2 was different from each other were compared, there was a tendency that the molar ratio B1/B2 of 70/30 or less made the curability at a low temperature of about 80° C. and the hardness of the resultant coating film more excellent, and the molar ratio B1/B2 of 50/50 made the strength of the resultant coating film particularly excellent.
[0611] When the blocked polyisocyanate compositions BL-a1-11, BL-a1-13 and BL-a1-14 (Examples 1-11, 1-13 and 1-14) in which the type of the polyisocyanate used was different from each other were compared, there was a tendency that a decrease in the average number of isocyanate groups of the polyisocyanate improved the hardness when made into a coating film, whilst an increase in the average number of isocyanate groups of the polyisocyanate improved the curability at a low temperature of about 80° C.
[0612] Although the blocked polyisocyanate compositions BL-b1-1 and BL-b1-2 (Comparative Examples 1-1 and 1-2) obtained without conducting modification with the polyol A exhibited a favorable storage stability of the resultant resin composition, the curability at a low temperature of about 80° C., the hardness, the strength and the solvent resistance when made into a coating film were deteriorated.
[Preparation of Aqueous Resin Composition]
[0613] An acrylic polyol (“Setaqua (registered trademarks) 6515” (trade name) manufactured by Nuplex, OH (% by mol) (on solids)=3.3, Acid value (mg KOH/g)=9.9, solid content: 45% by mass) as an aqueous main agent and each blocked polyisocyanate composition were mixed such that the molar ratio of isocyanate groups to hydroxy groups (isocyanate group/hydroxy group) was 0.80. Ion-exchanged water was added to the mixture, followed by adding a minute amount of dimethylaminoethanol thereto to adjust pH to approximately 8.0 to 8.5 and the solid content to 45% by mass. Then, the resultant solution was stirred using a homodisper at 1,000 rpm for 15 minutes, and then defoamed to obtain each aqueous resin composition.
[Evaluation 2-1]
(Low-Temperature Curability)
[0614] Each resultant resin composition was coated on a polypropylene (PP) plate such that a dried film thickness became 40 μm, then dried at 85° C. for 30 minutes by heating to form a resin film. The resultant resin film was stored at ordinary temperature (23° C.) for 1 week to measure the gel fraction. The gel fraction was determined as a percentage (% by mass) by dividing the mass of the undissolved portion when the resin film was immersed in acetone at 23° C. for 24 hours by the mass of the resin film before being immersed. The low-temperature curability was evaluated based on the resultant gel fraction in accordance with the following evaluation criteria. In the case where the evaluation result was C or better, the low-temperature curability was evaluated as favorable.
(Evaluation Criteria)
[0615] A: Gel fraction at an initial stage was 85% by mass or more.
[0616] B: Gel fraction at an initial stage was 82% by mass to less than 85% by mass.
[0617] C: Gel fraction at an initial stage was 78% by mass to less than 82% by mass.
[0618] D: Gel fraction at an initial stage was 70% by mass to less than 78% by mass.
[0619] E: Gel fraction at an initial stage was less than 70% by mass.
[Evaluation 2-2]
(Storage Stability)
[0620] 20 g of each resultant aqueous resin composition was stored at 40° C. for 3 days, to measure the gel fraction before storage (gel fraction at an initial stage) and the gel fraction after storage. The gel fraction was determined by the method described in “Evaluation 2-1”. The gel fraction retention rate was calculated by the following equation.
Gel fraction retention rate (%)=(Gel fraction after storage)/(Gel fraction at an initial stage)×100
[0621] The storage stability was evaluated based on the resultant gel fraction retention rate in accordance with the following evaluation criteria. In the case where the evaluation result was D or better, the storage stability was evaluated as favorable.
(Evaluation Criteria)
[0622] A: Gel fraction retention rate was 90% or more.
[0623] B: Gel fraction retention rate was 80% to less than 90%.
[0624] C: Gel fraction retention rate was 73% to less than 80%.
[0625] D: Gel fraction retention rate was 67% to less than 73%.
[0626] E: Gel fraction retention rate was 60% to less than 67%.
[0627] F: Gel fraction retention rate was less than 60%.
[Evaluation 2-3]
(Koenig Hardness)
[0628] Each resin film was formed on a glass plate by the same method as described in the “Evaluation 2-1”. The Koenig hardness (times) of the resultant resin film was measured using a Koenig hardness meter (Pendulum Hardness tester manufactured by BYK Gardner) at 23° C. The Koenig hardness was evaluated based on the measured Koenig hardness value in accordance with the following evaluation criteria. In the case where the evaluation result was B or better, the Koenig hardness was evaluated as favorable.
(Evaluation Criteria)
[0629] A: 30 Times or more.
[0630] B: 25 Times to 29 times.
[0631] C: 20 Times to 24 times.
[0632] D: 19 Times or less.
[Evaluation 2-4]
(Solvent Resistance (Ethanol Rubbing Test))
[0633] Each resultant aqueous resin composition was coated on a glass plate such that the dried coating film thickness became 40 μm, and then heated to dry at 85° C. for 30 minutes to obtain each resin film. Then, the resultant resin film was stored at ordinary temperature (23° C.) for one day, and then rubbed with a cotton swab immersed in xylene in a reciprocating motion repeatedly 20 times over a distance of 3 cm, followed by observing the state of the resultant resin film. The solvent resistance was evaluated based on the state of the resultant resin film in accordance with the following evaluation criteria. In the case where the evaluation result was B or better, the solvent resistance was evaluated
(Evaluation Criteria)
[0634] A: Almost no deterioration was confirmed.
[0635] B: Streaks were confirmed partially in the rubbed portion.
[0636] C: Streaks were confirmed in the rubbed portion, and film-thinning phenomena were confirmed.
[0637] D: There were places in which the resin film was dissolved completely in the rubbed portion.
Synthesis of Polyisocyanate
Synthesis Example 2-1
(Synthesis of Polyisocyanate P2-1)
[0638] 100 parts by mass of HDI and 5.2 parts by mass of polyester polyol derived from trivalent alcohol and ε-caprolactone (“PLACCEL 303” (trade name) manufactured by DAICEL ChemTech, Inc., and having an average number of functional groups of 3, and a number-average molecular weight of 300) were charged into a four-necked flask equipped with a thermometer, a stirrer blade and a reflux cooling tube in a nitrogen gas flow, and then the mixture was stirred while maintaining the temperature in the reactor at 88° C. for 1 hour to allow a urethane-forming reaction to proceed. Then, the temperature in the reactor was maintained at 62° C., and tetramethylammonium caprylate, which is an isocyanurate-forming catalyst, was added to the resultant, followed by adding a phosphoric acid when the yield reached 51% by mass to terminate the reaction. The reaction liquid was subjected to filtration, and then unreacted HDI was removed therefrom using a thin film evaporator to obtain an isocyanurate-type polyisocyanate (hereinafter, may be referred to as “polyisocyanate P2-1”). The NCO content ratio of the resultant polyisocyanate P2-1 was 18.8% by mass, the number-average molecular weight thereof was 1180, and the average number of isocyanate groups was 5.3. The resultant polyisocyanate P2-1 was subjected to .sup.1H-NMR analysis to confirm the presence of an isocyanurate group.
Synthesis Example 2-2
(Synthesis of Polyisocyanate P2-1)
[0639] 100 parts by mass of HDI was charged into a four-necked flask equipped with a thermometer, a stirrer blade and a reflux cooling tube in a nitrogen gas flow, the temperature in the reactor was maintained at 60° C., and tetramethylammonium caprylate, which is an isocyanurate-forming catalyst, was added thereto, followed by adding a phosphoric acid when the yield reached 38% by mass to terminate the reaction. The reaction liquid was subjected to filtration, and then unreacted HDI was removed therefrom using a thin film evaporator to obtain an isocyanurate-type polyisocyanate (hereinafter, may be referred to as “polyisocyanate P2-2”). The NCO content ratio of the resultant polyisocyanate P2-2 was 22.2% by mass, the number-average molecular weight thereof was 650, and the average number of isocyanate groups was 3.4. The resultant polyisocyanate P2-2 was subjected to .sup.1H-NMR analysis to confirm the presence of an isocyanurate group.
Synthesis Example 2-3
(Synthesis of Polyisocyanate P2-3)
[0640] 100 parts by mass of polyisocyanate P2-1, 13 parts by mass of dipropylene glycol dimethyl ether (DPDM), 15 parts by mass (5% by mol relative to 100% by mol of isocyanate groups of the polyisocyanate P1-2) of methoxypolyethylene glycol (MPG-081, having 15 ethylene oxide repeating units, and manufactured by NIPPON NYUKAZAI CO., LTD.), 0.08 parts by mass of 2-ethylhexyl acid phosphate (JP-508T manufactured by JOHOKU CHEMICAL CO., LTD.) and dipropylene glycol dimethyl ether (DPDM) were mixed in a four-necked flask equipped with a thermometer, a stirrer blade and a reflux cooling tube in a nitrogen gas flow, and the mixture was stirred at 120° C. for 2 hours to obtain a polyisocyanate P2-3. The NCO content ratio of the resultant polyisocyanate P2-3 was 14.0% by mass, and the average number of isocyanate groups was 5.0.
Synthesis Example 2-4
(Synthesis of Polyisocyanate P2-4)
[0641] 100 parts by mass of polyisocyanate P2-2, 13 parts by mass of dipropylene glycol dimethyl ether (DPDM), 18 parts by mass (5% by mol relative to 100% by mol of isocyanate groups of the polyisocyanate P2-2) of methoxypolyethylene glycol (MPG-081, having 15 ethylene oxide repeating units, and manufactured by NIPPON NYUKAZAI CO., LTD.), 0.08 parts by mass of 2-ethylhexyl acid phosphate (JP-508T manufactured by JOHOKU CHEMICAL CO., LTD.), and dipropylene glycol dimethyl ether (DPDM) were mixed in a four-necked flask equipped with a thermometer, a stirrer blade and a reflux cooling tube in a nitrogen gas flow, and the mixture was stirred at 120° C. for 2 hours to obtain a polyisocyanate P2-4. The NCO content ratio of the resultant polyisocyanate P2-4 was 16.2% by mass, and the average number of isocyanate groups was 3.2.
Preparation of Blocked Polyisocyanate Composition
Example 2-1
(Preparation of Blocked Polyisocyanate Composition BL-a2-1)
[0642] 100 parts by mass of the polyisocyanate P2-3 obtained in the Synthesis Example 2-3, 43.9 parts by mass (70% by mol relative to 100% by mol of NCO groups) of diisopropyl malonate, and 23.0 parts by mass (30% by mol relative to 100% by mol of NCO groups) of (2-methyl-2-pentyl)isopropyl malonate were charged into a four-necked flask equipped with a thermometer, a stirrer blade and a reflux cooling tube in a nitrogen gas flow, followed by further adding dipropylene glycol dimethyl ether (DPDM) thereto to adjust the solid content to 60% by mass. Then, 1.0 part by mass of a methanol solution containing sodium methylate (28% by mass relative to the total mass of the solution) was added dropwise while conducting stirring, followed by adjusting an outer bath such that the solution temperature was 55° C. to allow the blocking reaction to proceed at 55° C. for 5 hours, thereby obtaining a blocked polyisocyanate composition BL-a2-1 having a solid content of 60% by mass.
Example 2-2
(Preparation of Blocked Polyisocyanate Composition BL-a2-2)
[0643] 100 parts by mass of the polyisocyanate P2-3 obtained in the Synthesis Example 2-3, 43.9 parts by mass (70% by mol relative to 100% by mol of NCO groups) of diisopropyl malonate, and 21.6 parts by mass (30% by mol relative to 100% by mol of NCO groups) of (2-methyl-2-butyl)isopropyl malonate were charged into a four-necked flask equipped with a thermometer, a stirrer blade and a reflux cooling tube in a nitrogen gas flow, followed by further adding dipropylene glycol dimethyl ether (DPDM) thereto to adjust the solid content to 60% by mass. Then, 1.0 part by mass of a methanol solution containing sodium methylate (28% by mass relative to the total mass of the solution) was added dropwise while conducting stirring, followed by adjusting an outer bath such that the solution temperature was 55° C. to allow the blocking reaction to proceed at 55° C. for 5 hours, thereby obtaining a blocked polyisocyanate composition BL-a2-2 having a solid content of 60% by mass.
Example 2-3
(Preparation of Blocked Polyisocyanate Composition BL-a2-3)
[0644] 100 parts by mass of the polyisocyanate P2-3 obtained in the Synthesis Example 2-3, and 63.9 parts by mass (102% by mol relative to 100% by mol of NCO groups) of diisopropyl malonate were charged into a four-necked flask equipped with a thermometer, a stirrer blade and a reflux cooling tube in a nitrogen gas flow, followed by further adding dipropylene glycol dimethyl ether (DPDM) thereto to adjust the solid content to 60% by mass. Then, 1.0 part by mass of a methanol solution containing sodium methylate (28% by mass relative to the total mass of the solution) was added dropwise while conducting stirring, followed by adjusting an outer bath such that the solution temperature was 55° C. to allow the blocking reaction to proceed at 55° C. for 5 hours, thereby obtaining an intermediate of a blocked polyisocyanate composition, the solid content of the intermediate being 60% by mass. Then, 30 parts by mass (100% by mol relative to blocked isocyanate groups) of 2-methyl-2-butanol was added to the resultant to allow the reaction to proceed at 80° C. for 3 hours while removing generated isopropyl alcohol by conducting distillation under ordinary pressure. Then, isopropanol and 2-methyl-2-butanol were distilled away at 60° C. under reduced pressure (50 kPa), and finally dipropylene glycol dimethyl ether (DPDM) was added to the resultant to adjust the solid content to 60% by mass, thereby obtaining a blocked polyisocyanate composition BL-a2-3.
Example 2-4
(Preparation of Blocked Polyisocyanate Composition BL-a2-4)
[0645] 100 parts by mass of the polyisocyanate P2-3 obtained in the Synthesis Example 2-3, and 63.9 parts by mass (102% by mol relative to 100% by mol of NCO groups) of diisopropyl malonate were charged into a four-necked flask equipped with a thermometer, a stirrer blade and a reflux cooling tube in a nitrogen gas flow, followed by further adding dipropylene glycol dimethyl ether (DPDM) thereto to adjust the solid content to 60% by mass. Then, 1.0 part by mass of a methanol solution containing sodium methylate (28% by mass relative to the total mass of the solution) was added dropwise while conducting stirring, followed by adjusting an outer bath such that the solution temperature was 55° C. to allow the blocking reaction to proceed at 55° C. for 5 hours, thereby obtaining an intermediate of a blocked polyisocyanate composition, the solid content of the intermediate being 60% by mass. Then, 15 parts by mass (50% by mol relative to blocked isocyanate groups) of 2-methyl-2-butanol was added to the resultant to allow the reaction to proceed at 80° C. for 3 hours while removing generated isopropyl alcohol by conducting distillation under ordinary pressure. Then, isopropanol and 2-methyl-2-butanol were distilled away at 60° C. under reduced pressure (50 kPa), and finally dipropylene glycol dimethyl ether (DPDM) was added to the resultant to adjust the solid content to 60% by mass, thereby obtaining a blocked polyisocyanate composition BL-a2-4.
Example 2-5
(Preparation of Blocked Polyisocyanate Composition BL-a2-5)
[0646] 100 parts by mass of the polyisocyanate P2-3 obtained in the Synthesis Example 2-3, 31.3 parts by mass (50% by mol relative to 100% by mol of NCO groups) of diisopropyl malonate and 34.0 parts by mass (50% by mol relative to 100% by mol of NCO groups) of (2-methyl-2-butyl)isopropyl malonate were charged into a four-necked flask equipped with a thermometer, a stirrer blade and a reflux cooling tube in a nitrogen gas flow, followed by further adding dipropylene glycol dimethyl ether (DPDM) thereto to adjust the solid content to 60% by mass. Then, 1.0 part by mass of a methanol solution containing sodium methylate (28% by mass relative to the total mass of the solution) was added dropwise while conducting stirring, followed by adjusting an outer bath such that the solution temperature was 55° C. to allow the blocking reaction to proceed at 55° C. for 5 hours, thereby obtaining a blocked polyisocyanate composition BL-a2-5 having a solid content of 60% by mass.
Example 2-6
(Preparation of Blocked Polyisocyanate Composition BL-a2-6)
[0647] 100 parts by mass of the polyisocyanate P2-3 obtained in the Synthesis Example 2-3, 60.2 parts by mass (96% by mol relative to 100% by mol of NCO groups) of diisopropyl malonate and 2.9 parts by mass (4% by mol relative to 100% by mol of NCO groups) of (2-methyl-2-butyl)isopropyl malonate were charged into a four-necked flask equipped with a thermometer, a stirrer blade and a reflux cooling tube in a nitrogen gas flow, followed by further adding dipropylene glycol dimethyl ether (DPDM) thereto to adjust the solid content to 60% by mass. Then, 1.0 part by mass of a methanol solution containing sodium methylate (28% by mass relative to the total mass of the solution) was added dropwise while conducting stirring, followed by adjusting an outer bath such that the solution temperature was 55° C. to allow the blocking reaction to proceed at 55° C. for 5 hours, thereby obtaining a blocked polyisocyanate composition BL-a2-6 having a solid content of 60% by mass.
Example 2-7
(Preparation of Blocked Polyisocyanate Composition BL-a2-7)
[0648] 100 parts by mass of the polyisocyanate P2-3 obtained in the Synthesis Example 2-3 and 54.4 parts by mass (102% by mol relative to 100% by mol of NCO groups) of diethyl malonate were charged into a four-necked flask equipped with a thermometer, a stirrer blade and a reflux cooling tube in a nitrogen gas flow, followed by further adding dipropylene glycol dimethyl ether (DPDM) thereto to adjust the solid content to 60% by mass. Then, 1.0 part by mass of a methanol solution containing sodium methylate (28% by mass relative to the total mass of the solution) was added dropwise while conducting stirring, followed by adjusting an outer bath such that the solution temperature was 55° C. to allow the blocking reaction to proceed at 55° C. for 5 hours, thereby obtaining an intermediate of a blocked polyisocyanate composition, the solid content of the intermediate being 60% by mass. Then, 30 parts by mass (100% by mol relative to blocked isocyanate groups) of 2-methyl-2-butanol was added to the resultant to allow the reaction to proceed at 80° C. for 5 hours while removing generated ethanol by conducting distillation under ordinary pressure. Then, ethanol and 2-methyl-2-butanol were distilled away at 60° C. under reduced pressure (50 kPa), and finally dipropylene glycol dimethyl ether (DPDM) was added to the resultant to adjust the solid content to 60% by mass, thereby obtaining a blocked polyisocyanate composition BL-a2-7.
Example 2-8
(Preparation of Blocked Polyisocyanate Composition BL-a2-8)
[0649] 100 parts by mass of the polyisocyanate P2-3 obtained in the Synthesis Example 2-3 and 63.9 parts by mass (102% by mol relative to 100% by mol of NCO groups) of diisopropyl malonate were charged into a four-necked flask equipped with a thermometer, a stirrer blade and a reflux cooling tube in a nitrogen gas flow, followed by further adding dipropylene glycol dimethyl ether (DPDM) thereto to adjust the solid content to 60% by mass. Then, 1.0 part by mass of a methanol solution containing sodium methylate (28% by mass relative to the total mass of the solution) was added dropwise while conducting stirring, followed by adjusting an outer bath such that the solution temperature was 55° C. to allow the blocking reaction to proceed at 55° C. for 5 hours, thereby obtaining an intermediate of a blocked polyisocyanate composition, the solid content of the intermediate being 60% by mass. Then, 34.8 parts by mass (100% by mol relative to blocked isocyanate groups) of 3-methyl-3-pentanol was added to the resultant to allow the reaction to proceed at 80° C. for 3 hours while removing generated isopropyl alcohol by conducting distillation under ordinary pressure. Then, isopropanol, and 3-methyl-3-pentanol were distilled away at 60° C. under reduced pressure (50 kPa), and finally dipropylene glycol dimethyl ether (DPDM) was added to the resultant to adjust the solid content to 60% by mass, thereby obtaining a blocked polyisocyanate composition BL-a2-8.
Example 2-9
(Preparation of Blocked Polyisocyanate Composition BL-a2-9)
[0650] 100 parts by mass of the polyisocyanate P2-4 obtained in the Synthesis Example 2-4 and 73.9 parts by mass (102% by mol relative to 100% by mol of NCO groups) of diisopropyl malonate were charged into a four-necked flask equipped with a thermometer, a stirrer blade and a reflux cooling tube in a nitrogen gas flow, followed by further adding dipropylene glycol dimethyl ether (DPDM) thereto to adjust the solid content to 60% by mass. Then, 1.0 part by mass of a methanol solution containing sodium methylate (28% by mass relative to the total mass of the solution) was added dropwise while conducting stirring, followed by adjusting an outer bath such that the solution temperature was 55° C. to allow the blocking reaction to proceed at 55° C. for 5 hours, thereby obtaining an intermediate of a blocked polyisocyanate composition, the solid content of the intermediate being 60% by mass. Then, 40.2 parts by mass (100% by mol relative to blocked isocyanate groups) of 3-methyl-3-pentanol was added to the resultant to allow the reaction to proceed at 80° C. for 3 hours while removing generated isopropyl alcohol by conducting distillation under ordinary pressure. Then, isopropanol, and 3-methyl-3-pentanol were distilled away at 60° C. under reduced pressure (50 kPa), and finally dipropylene glycol dimethyl ether (DPDM) was added to the resultant to adjust the solid content to 60% by mass, thereby obtaining a blocked polyisocyanate composition BL-a2-9.
Example 2-10
(Preparation of Blocked Polyisocyanate Composition BL-a2-10)
[0651] 100 parts by mass of the polyisocyanate P2-3 obtained in the Synthesis Example 2-3 and 63.9 parts by mass (102% by mol relative to 100% by mol of NCO groups) of diisopropyl malonate were charged into a four-necked flask equipped with a thermometer, a stirrer blade and a reflux cooling tube in a nitrogen gas flow, followed by further adding dipropylene glycol dimethyl ether (DPDM) thereto to adjust the solid content to 60% by mass. Then, 1.0 part by mass of a methanol solution containing sodium methylate (28% by mass relative to the total mass of the solution) was added dropwise while conducting stirring, followed by adjusting an outer bath such that the solution temperature was 55° C. to allow the blocking reaction to proceed at 55° C. for 5 hours, thereby obtaining an intermediate of a blocked polyisocyanate composition, the solid content of the intermediate being 60% by mass. Then, 43.3 parts by mass (100% by mol relative to blocked isocyanate groups) of 3-ethyl-3-hexanol was added to the resultant to allow the reaction to proceed at 80° C. for 3 hours while removing generated isopropyl alcohol by conducting distillation under ordinary pressure. Then, isopropanol and 3-ethyl-3-hexanol were distilled away at 60° C. under reduced pressure (30 kPa), and finally dipropylene glycol dimethyl ether (DPDM) was added to the resultant to adjust the solid content to 60% by mass, thereby obtaining a blocked polyisocyanate composition BL-a2-10.
Example 2-11
(Preparation of Blocked Polyisocyanate Composition BL-a2-11)
[0652] 100 parts by mass of the polyisocyanate P2-3 obtained in the Synthesis Example 2-3, 12.5 parts by mass (20% by mol relative to 100% by mol of NCO groups) of diisopropyl malonate and 57.5 parts by mass (80% by mol relative to 100% by mol of NCO groups) of (2-methyl-2-butyl)isopropyl malonate were charged into a four-necked flask equipped with a thermometer, a stirrer blade and a reflux cooling tube in a nitrogen gas flow, followed by further adding dipropylene glycol dimethyl ether (DPDM) thereto to adjust the solid content to 60% by mass. Then, 1.0 part by mass of a methanol solution containing sodium methylate (28% by mass relative to the total mass of the solution) was added dropwise while conducting stirring, followed by adjusting an outer bath such that the solution temperature was 55° C. to allow the blocking reaction to proceed at 55° C. for 5 hours, thereby obtaining a blocked polyisocyanate composition BL-a2-11 having a solid content of 60% by mass.
Example 2-12
(Preparation of Blocked Polyisocyanate Composition BL-a2-12)
[0653] 100 parts by mass of the polyisocyanate P2-3 obtained in the Synthesis Example 2-3 and 63.9 parts by mass (102% by mol relative to 100% by mol of NCO groups) of diisopropyl malonate were charged into a four-necked flask equipped with a thermometer, a stirrer blade and a reflux cooling tube in a nitrogen gas flow, followed by further adding dipropylene glycol dimethyl ether (DPDM) thereto to adjust the solid content to 60% by mass. Then, 1.0 part by mass of a methanol solution containing sodium methylate (28% by mass relative to the total mass of the solution) was added dropwise while conducting stirring, followed by adjusting an outer bath such that the solution temperature was 55° C. to allow the blocking reaction to proceed at 55° C. for 5 hours, thereby obtaining an intermediate of a blocked polyisocyanate composition, the solid content of the intermediate being 60% by mass. Then, 75 parts by mass (250% by mol relative to blocked isocyanate groups) of 2-methyl-2-butanol was added to the resultant to allow the reaction to proceed at 80° C. for 3 hours while removing generated isopropyl alcohol by conducting distillation under ordinary pressure. Then, isopropanol and 2-methyl-2-butanol were distilled away at 60° C. under reduced pressure (50 kPa), and finally dipropylene glycol dimethyl ether (DPDM) was added to the resultant to adjust the solid content to 60% by mass, thereby obtaining a blocked polyisocyanate composition BL-a2-12.
Example 2-13
(Preparation of Blocked Polyisocyanate Composition BL-a2-13)
[0654] 100 parts by mass of the polyisocyanate P2-3 obtained in the Synthesis Example 2-3, 43.9 parts by mass (70% by mol relative to 100% by mol of NCO groups) of diisopropyl malonate and 24.4 parts by mass (30% by mol relative to 100% by mol of NCO groups) of di(2-methyl-2-butyl) malonate were charged into a four-necked flask equipped with a thermometer, a stirrer blade and a reflux cooling tube in a nitrogen gas flow, followed by further adding dipropylene glycol dimethyl ether (DPDM) thereto to adjust the solid content to 60% by mass. Then, 1.0 part by mass of a methanol solution containing sodium methylate (28% by mass relative to the total mass of the solution) was added dropwise while conducting stirring, followed by adjusting an outer bath such that the solution temperature was 55° C. to allow the blocking reaction to proceed at 55° C. for 5 hours, thereby obtaining a blocked polyisocyanate composition BL-a2-13 having a solid content of 60% by mass.
Comparative Example 2-1
Preparation of Blocked Polyisocyanate Composition BL-b2-1
[0655] 100 parts by mass of the polyisocyanate P2-3 obtained in the Synthesis Example 2-3, 43.9 parts by mass (70% by mol relative to 100% by mol of NCO groups) of diisopropyl malonate and 50.5 parts by mass (30% by mol relative to 100% by mol of NCO groups) of di-tert-butyl malonate were charged into a four-necked flask equipped with a thermometer, a stirrer blade and a reflux cooling tube in a nitrogen gas flow, followed by further adding dipropylene glycol dimethyl ether (DPDM) thereto to adjust the solid content to 60% by mass. Then, 1.0 part by mass of a methanol solution containing sodium methylate (28% by mass relative to the total mass of the solution) was added dropwise while conducting stirring, followed by adjusting an outer bath such that the solution temperature was 55° C. to allow the blocking reaction to proceed at 55° C. for 5 hours, thereby obtaining a blocked polyisocyanate composition BL-b2-1 having a solid content of 60% by mass.
Comparative Example 2-2
(Preparation of Blocked Polyisocyanate Composition BL-b2-2)
[0656] 100 parts by mass of the polyisocyanate P2-3 obtained in the Synthesis Example 2-3 and 63.9 parts by mass (102% by mol relative to 100% by mol of NCO groups) of diisopropyl malonate were charged into a four-necked flask equipped with a thermometer, a stirrer blade and a reflux cooling tube in a nitrogen gas flow, followed by further adding dipropylene glycol dimethyl ether (DPDM) thereto to adjust the solid content to 60% by mass. Then, 1.0 part by mass of a methanol solution containing sodium methylate (28% by mass relative to the total mass of the solution) was added dropwise while conducting stirring, followed by adjusting an outer bath such that the solution temperature was 55° C. to allow the blocking reaction to proceed at 55° C. for 5 hours, thereby obtaining a blocked polyisocyanate composition BL-b2-2 having a solid content of 60% by mass.
Comparative Example 2-3
(Preparation of Blocked Polyisocyanate Composition BL-b2-3)
[0657] 100 parts by mass of the polyisocyanate P2-3 obtained in the Synthesis Example 2-3 and 54.3 parts by mass (102% by mol relative to 100% by mol of NCO groups) of diethyl malonate were charged into a four-necked flask equipped with a thermometer, a stirrer blade and a reflux cooling tube in a nitrogen gas flow, followed by further adding dipropylene glycol dimethyl ether (DPDM) thereto to adjust the solid content to 60% by mass. Then, 1.0 part by mass of a methanol solution containing sodium methylate (28% by mass relative to the total mass of the solution) was added dropwise while conducting stirring, followed by adjusting an outer bath such that the solution temperature was 55° C. to allow the blocking reaction to proceed at 55° C. for 5 hours, thereby obtaining a blocked polyisocyanate composition BL-b2-3 having a solid content of 60% by mass.
Comparative Example 2-4
(Preparation of Blocked Polyisocyanate Composition BL-b2-4)
[0658] 100 parts by mass of the polyisocyanate P2-3 obtained in the Synthesis Example 2-3 and 63.9 parts by mass (102% by mol relative to 100% by mol of NCO groups) of diisopropyl malonate were charged into a four-necked flask equipped with a thermometer, a stirrer blade and a reflux cooling tube in a nitrogen gas flow, followed by further adding dipropylene glycol dimethyl ether (DPDM) thereto to adjust the solid content to 60% by mass. Then, 1.0 part by mass of a methanol solution containing sodium methylate (28% by mass relative to the total mass of the solution) was added dropwise while conducting stirring, followed by adjusting an outer bath such that the solution temperature was 55° C. to allow the blocking reaction to proceed at 55° C. for 5 hours, thereby obtaining an intermediate of a blocked polyisocyanate composition, the solid content of the intermediate being 60% by mass. Then, 49.3 parts by mass (150% by mol relative to blocked isocyanate groups) was added to the resultant to allow the reaction to proceed at 80° C. for 5 hours under reflux. Then, isopropanol and tert-butanol were distilled away at 60° C. under reduced pressure (50 kPa), and finally dipropylene glycol dimethyl ether (DPDM) was added to the resultant to adjust the solid content to 60% by mass, thereby obtaining a blocked polyisocyanate composition BL-b2-4.
Comparative Example 2-5
(Preparation of Blocked Polyisocyanate Composition BL-b2-5)
[0659] 100 parts by mass of the polyisocyanate P2-3 obtained in the Synthesis Example 2-3 and 73.4 parts by mass (102% by mol relative to 100% by mol of NCO groups) of di-tert-butyl malonate were charged into a four-necked flask equipped with a thermometer, a stirrer blade and a reflux cooling tube in a nitrogen gas flow, followed by further adding dipropylene glycol dimethyl ether (DPDM) thereto to adjust the solid content to 60% by mass. Then, 1.0 part by mass of a methanol solution containing sodium methylate (28% by mass relative to the total mass of the solution) was added dropwise while conducting stirring, followed by adjusting an outer bath such that the solution temperature was 55° C. to allow the blocking reaction to proceed at 55° C. for 5 hours, thereby obtaining a blocked polyisocyanate composition BL-b2-5 having a solid content of 60% by mass.
[0660] Measurement results and evaluation results obtained by the above-mentioned methods relating to physical properties of the blocked polyisocyanate compositions obtained in Examples and Comparative Examples are shown in the following tables.
TABLE-US-00013 TABLE 13 Ex- Ex- Ex- Ex- Ex- ample ample ample ample ample Blocked 2-1 2-2 2-3 2-4 2-5 polyisocyanate BL- BL- BL- BL- BL- composition a2-1 a2-2 a2-3 a2-4 a2-5 Con- Polyiso- P2-3 P2-3 P2-3 P2-3 P2-3 sti- cyanate tu- Consti- R.sup.11 Propyl Ethyl Ethyl Ethyl Ethyl tion tution group group group group group unit (I) R.sup.12 Methyl Methyl Methyl Methyl Methyl group group group group group R.sup.13 Methyl Methyl Methyl Methyl Methyl group group group group group R.sup.14 H H H H H R.sup.15 Methyl Methyl Methyl Methyl Methyl group group group group group R.sup.16 Methyl Methyl Methyl Methyl Methyl group group group group group Consti- R.sup.21 Methyl Methyl Methyl Methyl Methyl tution group group group group group unit (II) R.sup.22 Methyl Methyl Methyl Methyl Methyl group group group group group R.sup.23 Methyl Methyl Methyl Methyl Methyl group group group group group R.sup.24 Methyl Methyl Methyl Methyl Methyl group group group group group Molar ratio 70/30 70/30 80/20 90/10 50/50 (Constitution unit (II)/ Constitution unit (I)) Molar ratio 100% 100% 95% 98% 100% (Constitution unit (I-1)/ Constitution unit (I)) Amount of 0% 0% 3% 0.1% 0% alcohol (% by mass)
TABLE-US-00014 TABLE 14 Ex- Ex- Ex- Ex- Ex- ample ample ample ample ample Blocked 2-6 2-7 2-8 2-9 2-10 polyisocyanate BL- BL- BL- BL- BL-a2- composition a2-6 a2-7 a2-8 a2-9 10 Con- Polyisocyanate P2-3 P2-3 P2-3 P2-4 P2-3 sti- Consti- R.sup.11 Ethyl Ethyl Ethyl Ethyl Propyl tu- tution group group group group group tion unit (I) R.sup.12 Methyl Methyl Ethyl Ethyl Ethyl group group group group group R.sup.13 Methyl Methyl Methyl Methyl Ethyl group group group group group R.sup.14 H H H H H R.sup.15 Methyl H Methyl Methyl Methyl group group group group R.sup.16 Methyl Methyl Methyl Methyl Methyl group group group group group Consti- R.sup.21 Methyl H Methyl Methyl Methyl tution group group group group unit (II) R.sup.22 Methyl Methyl Methyl Methyl Methyl group group group group group R.sup.23 Methyl H Methyl Methyl Methyl group group group group R.sup.24 Methyl Methyl Methyl Methyl Methyl group group group group group Molar ratio 96/4 80/20 80/20 80/20 80/20 (Constitution unit (II)/ Constitution unit (I)) Molar ratio 100% 96% 95% 95% 95% (Constitution unit (I-1)/ Constitution unit (I)) Amount of 0% 3% 15% 15% 15% alcohol (% by mass)
TABLE-US-00015 TABLE 15 Example 2-11 Example 2-12 Example 2-13 Blocked polyisocyanate composition BL-a2-11 BL-a2-12 BL-a2-13 Constitution Polyisocyanate P2-3 P2-3 P2-3 Constitution R.sup.11 Ethyl group Ethyl group Ethyl group unit (I) R.sup.12 Methyl group Methyl group Methyl group R.sup.13 Methyl group Methyl group Methyl group R.sup.14 H H Ethyl group R.sup.15 Methyl group Methyl group Methyl group R.sup.16 Methyl group Methyl group Methyl group Constitution R.sup.21 Methyl group Methyl group Methyl group unit (II) R.sup.22 Methyl group Methyl group Methyl group R.sup.23 Methyl group Methyl group Methyl group R.sup.24 Methyl group Methyl group Methyl group Molar ratio 20/80 35/65 70/30 (Constitution unit (II)/ Constitution unit (I)) Molar ratio 100% 85% 0% (Constitution unit (I-1)/ Constitution unit (I)) Amount of alcohol 0% 12% 0% (% by mass)
TABLE-US-00016 TABLE 16 C. C. C. C. C. Ex- Ex- Ex- Ex- Ex- ample ample ample ample ample Blocked 2-1 2-2 2-3 2-4 2-5 polyisocyanate BL- BL- BL- BL- BL- composition b2-1 b2-2 b2-3 b2-4 b2-5 Con- Polyisocyanate P2-3 P2-3 P2-3 P2-3 P2-3 sti- Consti- R.sup.11 Methyl — — Methyl Methyl tu- tution group group group tion unit (I) R.sup.12 Methyl — — Methyl group group group R.sup.13 Methyl — — Methyl Methyl group group group R.sup.14 Methyl — — H Methyl group group R.sup.15 Methyl — — Methyl Methyl group group group R.sup.16 Methyl — — Methyl Methyl group group group R.sup.21 Methyl Methyl H Methyl — group group group R.sup.22 Methyl Methyl Methyl Methyl — group group group group R.sup.23 Methyl Methyl H Methyl — group group group R.sup.24 Methyl Methyl Methyl Methyl — group group group group Molar ratio 70/30 100/0 100/0 70/30 0/00 (Constitution unit (II)/ Constitution unit (I)) Molar ratio 0% 93% 0% (Constitution unit (I-1)/ Constitution unit (I)) Amount of 0% 0% 0% 8% 0% alcohol (% by mass)
C. Example: Comparative Example
[0661]
TABLE-US-00017 TABLE 17 Ex- Ex- Ex- Ex- Ex- ample ample ample ample ample 2-1 2-2 2-3 2-4 2-5 Physical Average 5.0 5.0 5.0 5.0 5.0 properties NCO number Solid 60 60 60 60 60 content (% by mass) Evaluation Low- A A B C A temperature curability Koenig A A A B A hardness Storage B B A A C stability Solvent A A A A A resistance
TABLE-US-00018 TABLE 18 Ex- Ex- Ex- Ex- Ex- ample ample ample ample ample 2-6 2-7 2-8 2-9 2-10 Physical Average 5.0 5.0 5.0 3.2 5.0 properties NCO number Solid 60 60 60 60 60 content (% by mass) Evaluation Low- C C B C C temperature curability Koenig B B A B B hardness Storage A A A A A stability Solvent A A A B B resistance
TABLE-US-00019 TABLE 19 Example 2-11 Example 2-12 Example 2-13 Physical Average NCO number 5.0 5.0 5.0 properties Solid content 60 60 60 (% by mass) Evaluation Low- temperature A A A curability Koenig hardness A A A Storage stability D C D Solvent resistance A A A
TABLE-US-00020 TABLE 20 C. Ex- C. Ex- C. Ex- C. Ex- C. Ex- ample ample ample ample ample 2-1 2-2 2-3 2-4 2-5 Physical Average 5.0 5.0 5.0 5.0 5.0 properties NCO number Solid 60 60 60 60 60 content (% by mass) Evaluation Low- A D E A A temperature curability Koenig A C D B A hardness Storage E A A E F stability Solvent A C D A A resistance
C. Example: Comparative Example
[0662] As shown in Tables 13 to 20, the blocked polyisocyanate compositions BL-a2-1 to BL-a2-10 (Examples 2-1 to 2-10) in which the total carbon number of R.sup.11, R.sup.12 and R.sup.13 in the constitution unit (I) was 4 or more exhibited favorable storage stability of the resultant resin compositions and favorable solvent resistance of the resultant resin films, particularly.
[0663] When the blocked polyisocyanate compositions BL-a2-2 to BL-a2-6 (Examples 2-2 to 2-6) in which the molar ratios of the constitution unit (II)/the constitution unit (I) were different from each other were compared, there was a tendency that a decrease in the molar ratio of the constitution unit (II)/the constitution unit (I) improved the low-temperature curability and the Koenig hardness of the resultant resin film. In contrast, there was a tendency that an increase in the molar ratio of the constitution unit (II)/the constitution unit (I) improved the storage stability.
[0664] When the blocked polyisocyanate compositions BL-a2-3 and BL-a2-10 (Examples 2-3 and 2-10) in which alkyl groups as R.sup.11, R.sup.12 and R.sup.13 in the constitution unit (I) were different from each other were compared, the blocked polyisocyanate composition BL-a2-3 in which the total carbon number of R.sup.11, R.sup.12 and R.sup.13 was 4 tended to exhibit more excellent low-temperature curability, Koenig hardness and solvent resistance of the resultant resin film.
[0665] When the blocked polyisocyanate compositions BL-a2-3 and BL-a2-7 (Examples 2-3 and 2-7) in which the type of the blocking agent causing the constitution unit (II) was different from each other were compared, the blocked polyisocyanate composition BL-a2-3 in which diisopropyl malonate was used tended to exhibit more excellent low-temperature curability and Koenig hardness of the resultant resin film than the blocked polyisocyanate composition BL-a2-7 in which diethyl malonate was used.
[0666] When the blocked polyisocyanate compositions BL-a2-8 and BL-a2-9 (Examples 2-8 and 2-9) in which the type of the polyisocyanate used in the blocking reaction was different from each other were compared, the blocked polyisocyanate composition BL-a2-8 in which a polyisocyanate having a larger average number of isocyanate groups was used tended to exhibit more excellent low-temperature curability and Koenig hardness of the resultant resin film.
[0667] In contrast, although the blocked polyisocyanate composition BL-b2-1 (Comparative Example 2-1), the blocked polyisocyanate composition BL-b2-4 (Comparative Example 2-4) and the blocked polyisocyanate composition BL-b2-5 (Comparative Example 2-5) in which the total carbon number of R.sup.11, R.sup.12 and R.sup.13 in the constitution unit (I) was 3 exhibited favorable low-temperature curability, Koenig hardness and solvent resistance of the resultant resin film, the storage stability when made into an aqueous resin composition was deteriorated.
[0668] Although the blocked polyisocyanate composition BL-b2-2 (Comparative Example 2-2) and the blocked polyisocyanate BL-b2-3 (Comparative Example 2-3) in which no constitution unit (I) was contained exhibited favorable storage stability when made into an aqueous resin composition, the low-temperature curability, the Koenig hardness, and the solvent resistance of the resultant resin film were deteriorated.
INDUSTRIAL APPLICABILITY
[0669] The blocked polyisocyanate composition according to the present embodiment makes it possible to provide a blocked polyisocyanate composition which exhibits favorable storage stability of the resultant resin composition as well as excellent curability at a low temperature of about 80° C., hardness and strength when made into a coating film.