URETHANE RESIN COMPOSITION, SURFACE TREATMENT AGENT, AND ARTICLE

Abstract

The present invention provides a urethane resin composition including a urethane resin (A), an olefin resin (B), water (C), and a carbodiimide compound (D) having a carbodiimide equivalent of 340 or more. Also, the present invention provides a surface treatment agent including the urethane resin composition described above. Further, present invention provides an article including a layer formed of the surface treatment agent. The content of urethane bond in the urethane resin (A) is preferably within a range of 980 to 4,000 mmol/kg. The content of urea bond in the urethane resin (A) is preferably within a range of 315 to 850 mmol/kg.

Claims

1. A urethane resin composition comprising a urethane resin (A). an olefin resin (B), water (C), and a carbodiimide compound (D) having a carbodiimide equivalent of 340 or more.

2. The urethane resin composition according to claim 1, wherein the content of the carbodiimide compound (D) is within a range of 0.01% to 20% by mass.

3. A surface treatment agent comprising the urethane resin composition according to claim 1.

4. An article comprising a layer formed of the surface treatment agent according to claim 3.

Description

EXAMPLES

[0071] The present invention is described in further detail below by using examples.

[Synthesis Example 1] Preparation of Urethane Resin (A-1) Water Dispersion

[0072] In a four-neck flask provided with a stirrer, a thermometer, and a nitrogen reflux tube, 250 parts by mass of methyl ethyl ketone and 0.001 parts by mass of stannous octylate were placed, and then 200 parts by mass of polycarbonatepolyol-1 (using 1,4-butanediol and 1,6-hexanediol as raw materials, number-average molecular weight: 1,000), 15 parts by mass of 2,2-dimethylolpropionic acid, 49 parts by mass of isophorone diisocyanate, and 34 parts by mass of hexamethylene diisocyanate were placed and reacted at 70° C. for 1 hour, preparing a methyl ethyl ketones solution of urethane prepolymer.

[0073] Next, 6.8 parts by mass of hydrazine and 15 parts by mass of triethylamine were mixed with the resultant methyl ethyl ketone solution of urethane prepolymer, and then 820 parts by mass of ion exchange water was added to prepare an emulsion in which a urethane resin (A-1) was dispersed in water.

[0074] Next, methyl ethyl ketone was distilled off from the resultant emulsion, and ion exchange water was further added, preparing a water dispersion of the urethane resin (A-1) with a nonvolatile content of 30% by mass.

[0075] The content of urethane bond in the resultant urethane resin (A-1) was 2,052 mmol/kg, the content of urea bond was 698 mmol/kg, and the content of an alicyclic structure was 715 mmol/kg.

[Synthesis Example 2] Preparation of Urethane Resin (A-2) Water Dispersion

[0076] In a four-neck flask provided with a stirrer, a thermometer, and a nitrogen reflux tube, 250 parts by mass of methyl ethyl ketone and 0.001 parts by mass of stannous octylate were placed, and then 220 parts by mass of polycarbonatepolyol-3 (using 1,6-hexanediol as a raw material, number-average molecular weight: 2,000), 12 parts by mass of 2,2-dimethylolpropionic acid, and 70 parts by mass of dicyclohexylmethane diisocyanate were placed and reacted at 70° C. for 1 hour, preparing a methyl ethyl ketones solution of urethane prepolymer.

[0077] Next, 4.5 parts by mass of piperazine and 9 parts by mass of triethylamine were mixed with the resultant methyl ethyl ketone solution of urethane prepolymer, and then 880 parts by mass of ion exchange water was added to the resultant mixture, preparing an emulsion in which a urethane resin (A-2) was dispersed in water.

[0078] Next, methyl ethyl ketone was distilled off from the resultant emulsion, and ion exchange was further added, preparing a water dispersion of the urethane resin (A-2) with a nonvolatile content of 32% by mass.

[0079] The content of urethane bond in the resultant urethane resin (A-2) was 1,278 mmol/kg, the content of urea bond was 435 mmol/kg, and the content of an alicyclic structure was 1,713 mmol/kg.

[Synthesis Example 3] Preparation of Urethane Resin (A-3) Water Dispersion

[0080] In a four-neck flask provided with a stirrer, a thermometer, and a nitrogen reflux tube, 250 parts by mass of methyl ethyl ketone and 0.001 parts by mass of stannous octylate were placed, and then 138 parts by mass of polycarbonatepolyol-4 (using 1,6-hexanediol as a raw material, number-average molecular weight: 2,000), 55 parts by mass of polycarbonatepolyol-5 (using 1,6-hexanediol as a raw material, number-average molecular weight: 500), 13 parts by mass of 2,2-dimethylolpropionic acid, and 100 parts by mass of dicyclohexylmethane diisocyanate were placed and reacted at 70° C. for 1 hour, preparing a methyl ethyl ketones solution of urethane prepolymer.

[0081] Next, 5.6 parts by mass of piperazine and 10 parts by mass of triethylamine were mixed with the resultant methyl ethyl ketone solution of urethane prepolymer, and then 880 parts by mass of ion exchange water was added to prepare an emulsion in which a urethane resin (A-3) was dispersed in water.

[0082] Next, methyl ethyl ketone was distilled off from the resultant emulsion, and ion exchange was further added, preparing a water dispersion of the urethane resin (A-3) with a nonvolatile content of 30% by mass.

[0083] The content of urethane bond in the resultant urethane resin (A-3) was 1,747 mmol/kg, the content of urea bond was 576 mmol/kg, and the content of an alicyclic structure was 2,341 mmol/kg.

Example 1

[0084] A urethane resin composition was produced by mixing 40 parts by mass of the water dispersion of the urethane resin (A-1) prepared in Synthesis Example 1, 7 parts by mass of acid-modified unchlorinated polyolefin (“Arrowbase SD-1010” manufactured by Unitika Ltd., nonvolatile content: 20.5% by mass, abbreviated as “POf” hereinafter), 53 parts by mass of water, and 2.5 parts by mass of a carbodiimide compound (“Carbodilite V-02” manufactured by Nisshinbo Chemical Inc., carbodiimide equivalent: 590, nonvolatile content: 40% by mass, abbreviated as “NCN(1)” hereinafter).

Example 2

[0085] A urethane resin composition was produced by mixing 42 parts by mass of the water dispersion of the urethane resin (A-1) prepared in Synthesis Example 1, 6 parts by mass of POf, 3 parts by mass of a filler (“ACEMATT TS 100” manufactured by Evonik Degussa Corporation, silica particles produced by a dry method, average particle diameter: 10 μm, abbreviated as “silica” hereinafter), 49 parts by mass of water, and 3.5 parts by mass of NCN(1).

Example 3

[0086] A urethane resin composition was produced by the same method as in Example 1 except that the type of the carbodiimide compound was changed to “Carbodilite V-02-L2” manufactured by Nisshinbo Chemical Inc., carbodiimide equivalent: 385, nonvolatile content: 40% by mass, abbreviated as “NCN(2)” hereinafter).

Example 4

[0087] A urethane resin composition was produced by the same method as in Example 2 except that the type of the carbodiimide compound was changed to NCN(2).

Example 5

[0088] A urethane resin composition was produced by the same method as in Example 1 except that the type of the carbodiimide compound was changed to “Carbodilite SV-02” manufactured by Nisshinbo Chemical Inc., carbodiimide equivalent: 430, nonvolatile content: 40% by mass, abbreviated as “NCN(3)” hereinafter).

Example 6

[0089] A urethane resin composition was produced by the same method as in Example 2 except that the type of the carbodiimide compound was changed to NCN(3).

Example 7

[0090] A urethane resin composition was produced by the same method as in Example 1 except that the type of the carbodiimide compound was changed to “Carbodilite V-10” manufactured by Nisshinbo Chemical Inc., carbodiimide equivalent: 410, nonvolatile content: 40% by mass, abbreviated as “NCN(4)” hereinafter).

Example 8

[0091] A urethane resin composition was produced by the same method as in Example 2 except that the type of the carbodiimide compound was changed to NCN(4).

Example 9

[0092] A urethane resin composition was produced by the same method as in Example 1 except that the type of the carbodiimide compound was changed to “Carbodilite SW-12G” manufactured by Nisshinbo Chemical Inc., carbodiimide equivalent: 465, nonvolatile content: 40% by mass, abbreviated as “NCN(5)” hereinafter).

Example 10

[0093] A urethane resin composition was produced by the same method as in Example 2 except that the type of the carbodiimide compound was changed to NCN(5).

Example 11

[0094] A urethane resin composition was produced by the same method as in Example 1 except that the urethane resin (A-1) water dispersion was changed to the urethane resin (A-2) water dispersion prepared in Synthesis Example 2.

Example 12

[0095] A urethane resin composition was produced by the same method as in Example 1 except that the urethane resin (A-1) water dispersion was changed to the urethane resin (A-3) water dispersion prepared in Synthesis Example 3.

Comparative Example 1

[0096] A urethane resin composition was produced by the same method as in Example 1 except that the type of the carbodiimide compound was changed to “V-04” manufactured by Nisshinbo Chemical Inc. (carbodiimide equivalent: 335, abbreviated as “NCN-R(1)” hereinafter).

Comparative Example 2

[0097] A urethane resin composition was produced by the same method as in Example 2 except that the type of the carbodiimide compound was changed to NCN-R(1).

[Method for Measuring Number-Average Molecular Weight]

[0098] The number-average molecular weight of the polyol and the weight-average molecular weight of the olefin resin used in the synthesis examples represent values obtained by measurement by a gel permeation column chromatography (GPC) method under the following conditions.

[0099] Measurement apparatus: high-performance GPC apparatus (“HLC-8220GPC” manufactured by Tosoh Corporation)

[0100] Column: the following columns manufactured by Tosoh Corporation were connected in series and used.

[0101] “TSKgel G5000” (7.8 mm I. D.×30 cm)×1

[0102] “TSKgel G4000” (7.8 mm I. D.×30 cm)×1

[0103] “TSKgel G3000” (7.8 mm I. D.×30 cm)×1

[0104] “TSKgel G2000” (7.8 mm I. D.×30 cm)×1

[0105] Detector: RI (differential refractometer)

[0106] Column temperature: 40° C.

[0107] Eluent: tetrahydrofuran (THF)

[0108] Flow rate: 1.0 mL/min

[0109] Injection amount: 100 μL (tetrahydrofuran solution with a sample concentration of 0.4% by mass)

[0110] Standard sample: The following standard polystyrene was used for forming a calibration curve.

(Standard Polystyrene)

[0111] “TSKgel standard polystyrene A-500” manufactured by Tosoh Corporation

[0112] “TSKgel standard polystyrene A-1000” manufactured by Tosoh Corporation

[0113] “TSKgel standard polystyrene A-2500” manufactured by Tosoh Corporation

[0114] “TSKgel standard polystyrene A-5000” manufactured by Tosoh Corporation

[0115] “TSKgel standard polystyrene F-1” manufactured by Tosoh Corporation

[0116] “TSKgel standard polystyrene F-2” manufactured by Tosoh Corporation

[0117] “TSKgel standard polystyrene F-4” manufactured by Tosoh Corporation

[0118] “TSKgel standard polystyrene F-10” manufactured by Tosoh Corporation

[0119] “TSKgel standard polystyrene F-20” manufactured by Tosoh Corporation

[0120] “TSKgel standard polystyrene F-40” manufactured by Tosoh Corporation

[0121] “TSKgel standard polystyrene F-80” manufactured by Tosoh Corporation

[0122] “TSKgel standard polystyrene F-128” manufactured by Tosoh Corporation

[0123] “TSKgel standard polystyrene F-288” manufactured by Tosoh Corporation

[0124] “TSKgel standard polystyrene F-550” manufactured by Tosoh Corporation

[Method for Evaluating Ethanol Resistance]

[0125] The urethane resin composition produced in each of the examples and the comparative examples was prepared, coated by using a bar coater on a TPO sheet (thickness: 0.4 mm), which was surface-treated with corona by using bar coater No. 14, and then dried for 1 minute at 120° C., producing a sample for evaluation.

[0126] The coated film surface on the surface of the resultant sample for evaluation was rubbed with a cotton cloth dipped in a 30 mass % aqueous ethanol solution under a load of 500 g by using a Gakushin rubbing tester (“RT-200” manufactured by Daiei Kagaku Seiki Mfg. Co., Ltd.). The state of the coated film was observed and evaluated as follows.

[0127] “T”: No peeling of the coated film was observed even after 100 times of rubbing.

[0128] “F”: Peeling of the coated film was observed after less than 100 times of rubbing.

TABLE-US-00001 TABLE 1 Example Example Example Example Table 1 1 2 3 4 Urethane resin (A) (A-1) (A-1) (A-1) (A-1) Olefin resin (B) POf POf POf POf Carbodiimide Type NCN(1) NCN(1) NCN(2) NCN(2) compound (D) Carbodiimide 590 590 385 385 equivalent Evaluation of ethanol resistance T T T T

TABLE-US-00002 TABLE 2 Example Example Example Example Table 2 5 6 7 8 Urethane resin (A) (A-1) (A-1) (A-1) (A-1) Olefin resin (B) POf POf POf POf Carbodiimide Type NCN(3) NCN(3) NCN(4) NCN(4) compound (D) Carbodiimide 430 430 410 410 equivalent Evaluation of ethanol resistance T T T T

TABLE-US-00003 TABLE 3 Example Example Example Table 3 9 10 11 Urethane resin (A) (A-1) (A-1) (A-2) Olefin resin (B) POf POf POf Trisiloxane Type NCN(5) NCN(5) NCN(1) compound (D) Carbodiimide 465 465 590 equivalent Evaluation of ethanol resistance T T T

TABLE-US-00004 TABLE 4 Example Comparative Comparative Table 4 12 Example 1 Example 2 Urethane resin (A) (A-3) (A-1) (A-1) Olefin resin (B) POf POf POf Trisiloxane Type NCN(1) NCN-R(1) NCN-R(1) compound (D) Carbodiimide 590 335 335 equivalent Evaluation of ethanol resistance T F F

[0129] It was found that the urethane resin composition of the present invention has excellent ethanol resistance.

[0130] On the other hand, Comparative Examples 1 and 2 have a condition using the carbodiimide compound having a carbodiimide equivalent lower than the range specified in the present invention, and any one of the comparative examples has poor ethanol resistance.