POLYCARBONATE RESIN COMPOSITION

Abstract

A polycarbonate resin composition contains (A) a polycarbonate resin containing a structural unit that is represented by general formula (1) and (B) a silane coupling agent that is represented by general formula (2), wherein 0.06 part by mass or more of the silane coupling agent (B) is contained relative to 100 parts by mass of the polycarbonate resin (A).

Claims

1. A polycarbonate resin composition comprising a polycarbonate resin (A) comprising a structural unit represented by General formula (1) below and a silane coupling agent (B) represented by General formula (2) below, wherein the polycarbonate resin composition comprises 0.06 parts by mass or more of the silane coupling agent (B) per 100 parts by mass of the polycarbonate resin (A): ##STR00020## (in Formula (1), R.sub.1-R.sub.4 each independently represent hydrogen, fluorine, chlorine, bromine, iodine, or an optionally substituted C1-C20 alkyl group, C6-C12 aryl group, C2-C12 alkenyl group, C1-C5 alkoxy group, or C7-C17 aralkyl group, X represents a single bond, O, S, SO, SO.sub.2, CO, or a divalent group represented by any of General formulae (4)-(9) below), ##STR00021## (in General formula (4), R.sub.8-R.sub.17 each independently represent hydrogen or a C1-C3 alkyl group, where at least one of R.sub.8-R.sub.17 represents a C1-C3 alkyl group; and in General formulae (5) to (9), R.sub.18 and R.sub.19 each independently represent hydrogen, a halogen, an optionally substituted C1-C20 alkyl group, an optionally substituted C1-C5 alkoxy group, an optionally substituted C6-C12 aryl group, an optionally substituted C7-C17 aralkyl group, or an optionally substituted C2-C15 alkenyl group, or R.sub.18 and R.sub.19 bind with each other to form a C3-C20 carbon ring or a C1-C20 heterocyclic ring, R.sub.20 represents an optionally substituted C1-C9 alkylene group, c represents an integer from 0 to 20, and d represents an integer from 1 to 500); ##STR00022## (in General formula (2), R.sub.21 represents a C1-C4 alkylene group or a phenylene group, R.sub.22 each independently represent a C1-C4 alkyl group, R.sub.23 each independently represent a hydroxyl group or a C1-C4 alkyl group, Y represents an active group comprising an epoxy group, an isocyanate group, a vinyl group, a styryl group, an acryloyl group, a ureido group, an isocyanurate group, or a mercapto group, and m each independently represent an integer from 1-3).

2. The polycarbonate resin composition according to claim 1, wherein the terminal structure of the polycarbonate resin (A) is represented by General formula (3) below: ##STR00023## (in General formula (3), R.sub.5 each independently represent a C1-C8 alkyl group, which may be substituted by a hydroxyl group, and n represents an integer from 0 to 5).

3. The polycarbonate resin composition according to claim 1, wherein X in General formula (1) above represents O, S, or General formula (4) or (5) above.

4. The polycarbonate resin composition according to claim 1, wherein General formula (1) above represents one or more selected from the group consisting of Formulae (10) to (22) below. ##STR00024##

5. The polycarbonate resin composition according to claim 1, wherein the active group represented by Y in General formula (2) above has at least one of an epoxy group, an isocyanate group, and a vinyl group.

6. The polycarbonate resin composition according to claim 1, wherein the active group represented by Y in General formula (2) above comprises any of Formulae (i) to (ix) below: ##STR00025## (in General formulae (i) to (ix), * represents a bond point with R.sub.21 in General formula (2) above).

7. The polycarbonate resin composition according to claim 1, wherein the viscosity-average molecular weight of the polycarbonate resin (A) is 10,000-60,000.

8. The polycarbonate resin composition according to claim 1, comprising 10 parts by mass or less of the silane coupling agent (B) per 100 parts by mass of the polycarbonate resin (A).

9. A film or coating comprising the polycarbonate resin composition according to claim 1.

10. A paint composition comprising the polycarbonate resin composition according to claim 1.

11. The paint composition according to claim 10, further comprising a solvent component.

12. A resin solution comprising the resin composition according to claim 1 and a non-halogenated organic solvent.

13. A coating solution comprising the resin composition according to claim 1.

14. A printing ink comprising the resin composition according to claim 1.

15. A conductive paste comprising the resin composition according to claim 1.

16. An adhesive curable resin composition, which comprises the polycarbonate resin composition according to claim 1 and which does not comprise a solvent.

Description

EXAMPLES

[0177] Hereinafter, examples and comparative examples will be described. The properties of the resin compositions in the examples and comparative examples were measured as follows.

[0178] <Viscosity-Average Molecular Weight (Mv)>

[0179] The viscosity-average molecular weight of the resin was measured as follows. [0180] Measurement equipment: Ubbelohde capillary viscometer [0181] Solvent: Dichloromethane [0182] Concentration of resin solution: 0.5 grams/deciliter [0183] Measurement temperature: 25? C.

[0184] Measurement was performed under the above conditions to determine the intrinsic viscosity [?] deciliter/gram at a Huggins' constant of 0.45 and the viscosity-average molecular weight was calculated by the following formula.

?=1.23?10.sup.?4?Mv.sup.0.83

[0185] <Adhesiveness to Base Material>

[0186] The polycarbonate resin composition was coated onto a stainless steel plate and glass base material (coating thickness: 60 ?m), air-dried, and then dried at 140? C. for 12 hours to produce a laminate having a layer of a coating film consisting of the polycarbonate resin composition.

[0187] The obtained laminate was subjected to an adhesion test employing the cross-cut (spaced at 1 mm) method for adhesion in accordance with JIS K5600-5-6, using a 24 mm wide cellophane tape (registered trademark) (adhesive strength 4.01 N/10 mm) manufactured by Nichiban Co., Ltd. that complies with the cross-cut test to evaluate the adhesiveness to the base material based on the JIS classification index, using a numerical scale of 0 (no peeling) to 5 (almost the entire surface was peeled off).

[0188] <Molecular Weight Stability>

[0189] The polycarbonate resin composition was dried on a PFA petri dish (petri dish made of an ethylene tetrafluoride-perfluoroalkoxy ethylene copolymer resin) at 140? C. for 12 hours to measure the Mw of the dried resin composition. Based on the Mw of the polycarbonate resin used in the resin composition and the Mw of the dried resin composition, those whose Mw decreased by 3,000 or more after drying were considered defective, and those whose Mw decreased by less than 3,000 were considered favorable.

[0190] Mw was measured as follows.

[0191] <Mass-Average Molecular Weight (Mw)>

[0192] Measurement Conditions for Gel Permeation Chromatography (GPC) Analysis

[0193] The mass-average molecular weights (Mw) of the polycarbonate resin and the polycarbonate resin composition were determined by gel permeation chromatography analysis performed under the conditions shown below. [0194] Equipment used: Alliance HPLC System manufactured by Waters Corporation [0195] Columns: Two Shodex 805L columns manufactured by Showa Denko K.K. [0196] Eluent: Chloroform [0197] Flow rate: 1.0 ml/min [0198] Sample: 0.25 w/v % chloroform solution sample [0199] Detection: UV detection at 254 nm

[0200] The GPC analysis described above gave mass-average molecular weights (Mw) in terms of polystyrene (PS).

[0201] <Examples of Polycarbonate Resin Synthesis>

[0202] (Synthesis of Polycarbonate Resin (A-1))

[0203] Into 530 ml of 9 w/w % aqueous sodium hydroxide solution and 200 ml of pure water, 90 g (0.34 mol) of 1,1-bis(4-hydroxyphenyl)cyclohexane (hereinafter abbreviated as BPZ: manufactured by Honshu Chemical Industry Co., Ltd.), 1.65 g (0.011 mol) of PTBP (p-tert-butylphenol), and 0.3 g of hydrosulfite were dissolved.

[0204] To this, 300 ml of methylene chloride was added, and while stirring, 46.5 g of phosgene was blown therein over about 30 minutes while keeping the temperature at 15-20? C.

[0205] After the phosgene blowing, 100 ml of 9 w/w % aqueous sodium hydroxide solution was added, and the reaction solution was emulsified by vigorous stirring. Then, 0.5 ml of triethylamine was added as a polymerization catalyst, and the mixture was stirred at 20-30? C. for about 40 minutes to allow polymerization.

[0206] After the polymerization, the reaction solution was separated into an aqueous phase and an organic phase, the organic phase was neutralized with phosphoric acid, and repeatedly rinsed with water until the conductivity of the wash liquid (aqueous phase) became 10 ?S/cm or less. The resulting polymer solution was dropped into warm water kept at 60? C. to remove the solvent by evaporation to obtain white powdery precipitate. The obtained precipitate was filtered and dried at 105? C. for 24 hours to use the resulting polycarbonate resin (A-1).

##STR00015##

[0207] (Synthesis of Polycarbonate Resin (A-2))

[0208] Polycarbonate resin (A-2) was used, which was obtained in the same manner as polycarbonate resin (A-1) except that the amount of PTBP was changed to 0.51 g.

[0209] (Synthesis of Polycarbonate Resin (A-3))

[0210] Polycarbonate resin (A-3) was used, which was obtained in the same manner as polycarbonate resin (A-1) except that 97 g of 1,1-bis(4-hydroxyphenyl)-1-phenylethane (hereinafter abbreviated as BPAP: manufactured by Honshu Chemical Industry Co., Ltd.) was used instead of BPZ and the amount of PTBP was changed to 1.93 g.

##STR00016##

[0211] (Synthesis of Polycarbonate Resin (A-4))

[0212] Polycarbonate resin (A-4) was used, which was obtained in the same manner as polycarbonate resin (A-1) except that 118 g of 1,1-bis(4-hydroxyphenyl)cyclododecane (hereinafter abbreviated as BPCD: manufactured by Honshu Chemical Industry Co., Ltd.) was used instead of BPZ and the amount of PTBP was changed to 1.42 g.

##STR00017##

[0213] (Synthesis of Polycarbonate Resin (A-5))

[0214] Into 530 ml of 9 w/w % aqueous sodium hydroxide solution and 200 ml of pure water, 51.5 g (0.20 mol) of 2,2-bis(4-hydroxy-3-methylphenyl)propane (hereinafter abbreviated as BPC: manufactured by Honshu Chemical Industry Co., Ltd.), 30.5 g (0.13 mol) of 2,2-bis(4-hydroxyphenyl)propane (hereinafter abbreviated as BPA; manufactured by Mitsubishi Chemical Corporation), 1.56 g (0.010 mol) of PTBP, and 0.3 g of hydrosulfite were dissolved.

[0215] To this, 200 ml of methylene chloride was added and, while stirring, 0.08 g of benzyltriethylammonium chloride (hereinafter abbreviated as TEBAC) was added. Then, while keeping the temperature at 15-20? C., 46.5 g of phosgene was blown therein over about 30 minutes.

[0216] After the phosgene blowing, 100 ml of 9 w/w % aqueous sodium hydroxide solution was added, and the reaction solution was emulsified by vigorous stirring. Then, 0.5 ml of triethylamine was added as a polymerization catalyst, and the mixture was stirred at 20-30? C. for about 40 minutes to allow polymerization.

[0217] After the polymerization, the reaction solution was separated into an aqueous phase and an organic phase, the organic phase was neutralized with phosphoric acid, and repeatedly rinsed with water until the conductivity of the wash liquid (aqueous phase) became 10 ?S/cm or less. The resulting polymer solution was dropped into warm water kept at 60? C. to remove the solvent by evaporation to obtain white powdery precipitate. The obtained precipitate was filtered and dried at 105? C. for 24 hours to use the resulting polycarbonate resin (A-5).

##STR00018##

[0218] (Synthesis of Polycarbonate Resin (A-6))

[0219] Polycarbonate resin (A-6) was used, which was obtained in the same manner as polycarbonate resin (A-1) except that 48.7 g of BPAP and 45.3 g (0.17 mol) of 2,2-bis(4-hydroxyphenyl)-4-methylpentane (hereinafter abbreviated as MIBK: manufactured by Honshu Chemical Industry Co., Ltd.) were used instead of BPZ and the amount of PTBP was changed to 1.68 g.

##STR00019##

[0220] (Synthesis of Polycarbonate Resin (A-7))

[0221] Polycarbonate resin (A-7) was used, which was obtained in the same manner as polycarbonate resin (A-5) except that the amounts of BPC and BPA were changed to 50.8 g and 30.2 g, respectively, 2.03 g (0.20 mol) of p-hydroxyphenethyl alcohol (hereinafter abbreviated as PHEP; manufactured by Otsuka Chemical Co. Ltd.) was also used, and PTBP was not used.

[0222] (Synthesis of Polycarbonate Resin (A-8))

[0223] Polycarbonate resin (A-8) was used, which was obtained in the same manner as polycarbonate resin (A-7) except that 78.6 g (0.23 mol) of 2,2-bis(4-hydroxyphenyl)hexafluoropropane (hereinafter abbreviated as BPAF: manufactured by Central Glass Co., Ltd.) was used instead of BPC and the amounts of BPA and PHEP were changed to 22.9 g and 0.92 g, respectively.

[0224] The compositions and physical properties of the polycarbonate resins (A-1) to (A-8) are shown in Table 1.

TABLE-US-00001 TABLE 1 Main Terminal skeleton structure Mv Mw A-1 PCZ PTBP 21,200 58,800 A-2 PCZ PTBP 51,000 166,700 A-3 BPAP PTBP 20,600 55,900 A-4 BPCD PTBP 18,300 62,000 A-5 BPC/BPA PTBP 26,000 60,750 A-6 MIBK/ PTBP 23,900 64,000 BPAP A-7 BPC/BPA PHEP 25,500 56,400 A-8 BPAF/BPA PHEP 27,300 95,000

Example 1

[0225] A resin composition of 10 parts by mass of polycarbonate resin (A-1) and 0.05 parts by mass of silane coupling agent (B-1) (0.5 parts by mass per 100 parts by mass of polycarbonate resin) was dissolved in 55 parts by mass of toluene to prepare a solution of the polycarbonate resin composition.

Examples 2-15, Comparative Examples 1-5

[0226] Solutions of polycarbonate resin compositions were prepared in the same manner as in Example 1 except that the type of the polycarbonate resin or the parts by mass of the silane coupling agent was changed as shown in Table 2.

[0227] The compositions and evaluation results of the polycarbonate resin compositions of Examples 1-15 and Comparative examples 1-5 are shown in Table 2.

TABLE-US-00002 TABLE 2 Polycarbonate resin Silane coupling agent Adhesiveness to Molecular weight (A) (B) base material stability Type Parts by mass Type Parts by mass Stainless steel Glass Mw Evaluation Example 1 A-1 100 B-1 0.5 0 0 58,800 Favorable Example 2 A-1 100 B-1 0.1 1 0 58,800 Favorable Example 3 A-1 100 B-1 2.0 0 0 59,100 Favorable Example 4 A-2 100 B-1 0.5 0 0 166,700 Favorable Example 5 A-3 100 B-1 0.5 0 0 57,300 Favorable Example 6 A-4 100 B-2 0.5 0 0 62,100 Favorable Example 7 A-5 100 B-1 0.5 0 0 60,000 Favorable Example 8 A-6 100 B-2 0.5 0 0 64,100 Favorable Example 9 A-7 100 B-1 0.5 0 0 56,300 Favorable Example 10 A-7 100 B-1 0.1 0 1 56,600 Favorable Example 11 A-7 100 B-1 2.0 0 0 56,400 Favorable Example 12 A-7 100 B-2 0.5 0 0 58,000 Favorable Example 13 A-7 100 B-2 2.0 0 0 61,300 Favorable Example 14 A-7 100 B-3 0.5 0 1 56,600 Favorable Example 15 A-8 100 B-1 0.5 0 0 95,000 Favorable Comparative A-1 100 5 5 58,800 Favorable example 1 Comparative A-1 100 B-1 0.1 5 5 58,800 Favorable example 2 Comparative A-1 100 B-4 2.0 5 5 58,800 Favorable example 3 Comparative A-1 100 B-5 0.5 0 0 44,600 Defective example 4 Comparative A-1 100 3 5 56,400 Favorable example 5

[0228] The abbreviations B-1 to B-5 in Table 2 denote the following. [0229] B-1: 3-Glycidyloxypropyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) [0230] B-2: 3-(Triethoxysilyl)propyl isocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) [0231] B-3: Vinyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) [0232] B-4: 3-(Trimethoxysilyl)propyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) [0233] B-5: 3-Aminopropyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0234] As described above, the resin composition of the present invention can improve the adhesiveness between a coating film and a base material and is also useful as a blend resin composition of the polycarbonate resin and other resin.

INDUSTRIAL APPLICABILITY

[0235] The resin composition of the present invention can be used as a coating resin solution for protecting articles. It is particularly suitable for coatings in fields where durability in daily life is required, such as IC cards and security cards.