RESIN COMPOSITION

Abstract

The present invention is a resin composition, including: a resin α1 having an aromatic dicarboxylic acid monomer unit A1 having a hydrophilic group, a dicarboxylic acid monomer unit B1 having no hydrophilic group, and an aromatic monomer unit C1; and a resin α2 having an aromatic dicarboxylic acid monomer unit A2 having a hydrophilic group, a dicarboxylic acid monomer unit B2 having no hydrophilic group, and an aliphatic monomer unit C2, wherein the resin α2 includes a monomer unit other than a monomer unit that constitutes the resin α1, and a mass ratio of a content of the resin α1 to a content of the resin α2 is 0.9 or more and 20 or less. According to the present invention, a resin composition that can be removed only with water while maintaining the heat resistance of polymer materials can be provided.

Claims

1: A resin composition, comprising: a resin α1 having an aromatic dicarboxylic acid monomer unit A1 having a hydrophilic group, a dicarboxylic acid monomer unit B1 having no hydrophilic group, and an aromatic monomer unit C1; and a resin α2 having an aromatic dicarboxylic acid monomer unit A2 having a hydrophilic group, a dicarboxylic acid monomer unit B2 having no hydrophilic group, and an aliphatic monomer unit C2, wherein the resin α2 includes a monomer unit other than a monomer unit that constitutes the resin α1, and a mass ratio of a content of the resin α1 to a content of the resin α2 is 0.9 or more and 20 or less.

2: The resin composition according to claim 1, wherein a content of the resin α1 in the resin composition is 40% by mass or more and 90% by mass or less.

3: The resin composition according to claim 1, wherein a percentage of the aromatic monomer unit C1 based on a total of all monomer units derived from a monomer having two functional groups that are reactive with a carboxy group in the resin α1 is 80 mol % or more and 100 mol % or less.

4: The resin composition according to claim 1, wherein a molar ratio of the aromatic dicarboxylic acid monomer unit A1 to the dicarboxylic acid monomer unit B1 in the resin α1 is 20/80 or more and 90/10 or less.

5: The resin composition according to claim 1, wherein a molar ratio of the aromatic dicarboxylic acid monomer unit A2 to the dicarboxylic acid monomer unit B2 in the resin α2 is 10/90 or more and 70/30 or less.

6: The resin composition according to claim 1, comprising an organic salt compound R represented by General Formula (7) below:
(R.sub.2—SO.sub.3.sup.−).sub.nX.sup.n+  (7) wherein R.sup.2 represents a hydrocarbon group optionally having a substituent and having 1 to 30 carbon atoms, n represents a number of 1 or 2, X.sup.n+ represents a sodium ion, a potassium ion, a lithium ion, an ammonium ion, or a phosphonium ion when n is 1, and X.sup.n+ represents a magnesium ion, a calcium ion, a barium ion, or a zinc ion when n is 2.

7: The resin composition according to claim 1, wherein a percentage of the aromatic dicarboxylic acid monomer unit A1 based on a total of all dicarboxylic acid monomer units in the resin α1 is 20 to 90 mol %.

8: The resin composition according to claim 1, comprising a resin having a percentage of the aromatic dicarboxylic acid monomer unit A2 based on a total of all dicarboxylic acid monomer units in the resin α2 of 10 to 70 mol %.

9: The resin composition according to claim 1, wherein a content of a hydrophilic group other than a hydrophilic group that constitutes polymerization related to production of the resin in the resin α1 is 0.5 to 3.0 mmol/g.

10: The resin composition according to claim 1, wherein a content of a hydrophilic group other than a hydrophilic group that constitutes polymerization related to production of the resin in the resin α2 is 0.5 to 3.0 mmol/g.

11: The resin composition according to claim 1, wherein a weight average molecular weight of the resin α1 is 1,000 to 80,000.

12: The resin composition according to claim 1, wherein a weight average molecular weight of the resin α2 is 5,000 to 60,000.

13: The resin composition according to claim 1, wherein the hydrophilic group is a sulfonate group.

14: The resin composition according to claim 1, wherein the aromatic monomer unit C1 is derived from an aromatic monomer having two functional groups that are reactive with a carboxy group.

15: The resin composition according to claim 14, wherein the aromatic monomer is an aromatic diol.

16: The resin composition according to claim 1, wherein the aliphatic monomer unit C2 is derived from an aliphatic monomer having two functional groups that are reactive with a carboxy group.

17: The resin composition according to claim 16, wherein the aliphatic monomer is an aliphatic diol.

18-20. (canceled)

21: The resin composition according to claim 4, wherein the mass ratio of a content of the resin α1 to a content of the resin α2 is 3 or less.

Description

EXAMPLES

[0176] The pressure is expressed in an absolute pressure. “Normal pressure” refers to 101.3 kPa.

<Method for Preparing Resin Composition>

[0177] The method for preparing resin compositions 1 to 17 will be described below. Each weight average molecular weight of the resins α1 and α2 contained in the resin compositions 1 to 6, 14, and 15 and each percentage of the monomer units A1, A2, B1, B2, C1, and C2 based on a total of all monomer units of the resins α1 and a2 are shown in Tables 1 and 2. Each glass transition temperature of the resin compositions and the contents of the resin α1, the resin α2, and the organic salt compound β in the resin compositions calculated from the amounts of raw materials added are shown in Tables 3, 5, 7, and 8. Each percentage of the monomer units B1, B2, C1, and C2 based on a total of all the monomer units of the resins α1 and a2 was calculated from the amounts of the raw materials added under the assumption that the excessive amount of ethylene glycol and 1,3-propanediol was distilled off to the outside of the reaction system and the diol unit and the dicarboxylic acid unit reacted in equal amounts.

[Preparation of Resin Composition 1]

[0178] Into a 2 L stainless steel separable flask (with a K tube, a stirrer, a nitrogen inlet tube), 23.7 g of dimethyl 2,6-naphthalenedicarboxylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 52.1 g of dimethyl sodium 5-sulfoisophthalate (manufactured by Tokyo Chemical Industry Co., Ltd.), 22.4 g of ethylene glycol (manufactured by FUJIFILM Wako Pure Chemical Corporation), 26 mg of titanium tetrabutoxide (manufactured by Tokyo Chemical Industry Co., Ltd.), 117.3 g of bisphenoxyethanolfluorene (manufactured by Osaka Gas Chemicals Co., Ltd.), and 866 mg of anhydrous sodium acetate (manufactured by FUJIFILM Wako Pure Chemical Corporation) were charged, the temperature of the surface of a mantle heater was raised from 160° C. to 260° C. over 1 hour with the mantle heater with stirring under normal pressure and a nitrogen atmosphere, and the mixture was stirred for 6 hours and 30 minutes at the temperature to perform a transesterification reaction. Then, 17.6 g of tetrabutylphosphonium dodecylbenzenesulfonate (manufactured by TAKEMOTO OIL & FAT Co., Ltd., ELECUT S-418) was added, the temperature of the surface of the heater was raised from 260° C. to 290° C. over 30 minutes, and the mixture was stirred for 1 hour and 20 minutes. Then, the pressure was reduced from normal pressure to 2 kPa, and the temperature of the surface of the heater was raised from 290° C. to 315° C. over 35 minutes to perform a reaction. The temperature was raised to 315° C., then the mixture was stirred for 2 hours, and then stirred for 3 hours while gradually increasing the degree of pressure reduction from 2 kPa to 28 Pa to perform a reaction, and the pressure was returned to normal pressure to obtain a resin composition 1 including the resin α1 and the organic salt compound B.

[Preparation of Resin Composition 2]

[0179] Into a 2 L stainless steel separable flask (with a K tube, a stirrer, a nitrogen inlet tube), 97.7 g of dimethyl 2,6-naphthalenedicarboxylate (manufactured by Tokyo Chemical Industry Co., Ltd., first class), 40.6 g of dimethyl sodium 5-sulfoisophthalate (manufactured by Wako Pure Chemical Industries, Ltd.), 76.7 g of ethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd., highest quality), 82 mg of titanium tetrabutoxide (manufactured by Tokyo Chemical Industry Co., Ltd., first class), and 506 mg of sodium acetate (manufactured by Wako Pure Chemical Industries, Ltd., highest quality) were charged, the temperature of the surface of a mantle heater was raised from 140° C. to 260° C. over 1 hour with the mantle heater with stirring under normal pressure and a nitrogen atmosphere, and the mixture was stirred for 6 hours and 30 minutes at the temperature to perform a transesterification reaction. Then, 6.89 g of tetrabutylphosphonium dodecylbenzenesulfonate (manufactured by TAKEMOTO OIL & FAT Co., Ltd., product name: ELECUT S-418) was added thereto, and the resulting mixture was stirred for 15 minutes. Then, the temperature of the surface of the heater was raised from 260 to 290° C. over 30 minutes, and at the same time, the pressure was reduced from normal pressure to 5.3 kPa to perform a reaction for 1 hour and a half under the conditions. Then, a reaction was performed with stirring at 800 Pa for 30 minutes, and then the pressure was returned to normal pressure. The temperature of the surface of the heater was raised from 290° C. to 295° C. at normal pressure over 15 minutes, then a reaction was performed with stirring at 420 Pa for 15 minutes, then a reaction was performed with stirring while gradually increasing the degree of pressure reduction from 470 Pa to 100 Pa over 15 minutes, and the pressure was returned to normal pressure to obtain a resin composition 2 including the resin α2.

[Preparation of Resin Composition 3]

[0180] Into a 2 L stainless steel separable flask (with a K tube, a stirrer, a nitrogen inlet tube), 23.7 g of dimethyl 2,6-naphthalenedicarboxylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 52.1 g of dimethyl sodium 5-sulfoisophthalate (manufactured by Tokyo Chemical Industry Co., Ltd.), 22.4 g of ethylene glycol (manufactured by FUJIFILM Wako Pure Chemical Corporation), 26 mg of titanium tetrabutoxide (manufactured by Tokyo Chemical Industry Co., Ltd.), 117.3 g of bisphenoxyethanolfluorene (manufactured by Osaka Gas Chemicals Co., Ltd.), and 866 mg of anhydrous sodium acetate (manufactured by FUJIFILM Wako Pure Chemical Corporation) were charged, the temperature of the surface of a mantle heater was raised from 160° C. to 260° C. over 1 hour with the mantle heater with stirring under normal pressure and a nitrogen atmosphere, and the mixture was stirred for 6 hours and 30 minutes at the temperature to perform a transesterification reaction. Then, the temperature of the surface of the heater was raised from 260° C. to 290° C., the pressure was reduced from normal pressure to 1.5 kPa, and the temperature of the surface of the heater was raised from 290° C. to 315° C. over 20 minutes to perform a reaction. The temperature was raised to 315° C., then the mixture was stirred for 20 minutes, and then stirred for 1.5 hours while gradually increasing the degree of pressure reduction from 1.5 kPa to 500 Pa to perform a reaction, and the pressure was returned to normal pressure to obtain a resin composition 3 including the resin α1.

[Preparation of Resin Composition 4]

[0181] Into a 2 L stainless steel separable flask (with a K tube, a stirrer, a nitrogen inlet tube), 97.7 g of dimethyl 2,6-naphthalenedicarboxylate (manufactured by Tokyo Chemical Industry Co., Ltd., first class), 40.6 g of dimethyl sodium 5-sulfoisophthalate (manufactured by Wako Pure Chemical Industries, Ltd.), 76.7 g of ethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd., highest quality), 82 mg of titanium tetrabutoxide (manufactured by Tokyo Chemical Industry Co., Ltd., first class), and 506 mg of sodium acetate (manufactured by Wako Pure Chemical Industries, Ltd., highest quality) were charged, the temperature of the surface of a mantle heater was raised from 140° C. to 260° C. over 1 hour with the mantle heater with stirring under normal pressure and a nitrogen atmosphere, and the mixture was stirred for 6 hours and 30 minutes at the temperature to perform a transesterification reaction. Then, the temperature of the surface of the heater was raised from 260 to 290° C. over 30 minutes, and at the same time, the pressure was reduced from normal pressure to 3 kPa to perform a reaction for 1 hour and a half under the conditions. Then, a reaction was performed with stirring at 800 Pa for 30 minutes, then the temperature of the surface of the heater was raised from 290° C. to 295° C., then a reaction was performed by stirring for 3 hours while increasing the degree of pressure reduction to 500 Pa, and the pressure was returned to normal pressure to obtain a resin composition 4 including the resin α2.

[Preparation of Resin Composition 5]

[0182] Into a 2 L stainless steel separable flask (with a K tube, a stirrer, a nitrogen inlet tube), 84.4 g of dimethyl 2,6-naphthalenedicarboxylate (manufactured by Tokyo Chemical Industry Co., Ltd., first class), 176.0 g of bisphenoxyethanolfluorene (manufactured by Osaka Gas Chemicals Co., Ltd.), 98.5 g of dimethyl sodium 5-sulfoisophthalate (manufactured by Wako Pure Chemical Industries, Ltd.), 71.9 g of ethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd., highest quality), 79.8 mg of titanium tetrabutoxide (manufactured by Tokyo Chemical Industry Co., Ltd., first class), 1.50 g of anhydrous sodium acetate (manufactured by Wako Pure Chemical Industries, Ltd.), and 30.0 g of tetrabutylphosphonium dodecylbenzenesulfonate (manufactured by TAKEMOTO OIL & FAT Co., Ltd., product name: ELECUT S-418) were charged, the temperature of the surface of a mantle heater was raised from 160° C. to 260° C. over 50 minutes with the mantle heater with stirring under normal pressure and a nitrogen atmosphere, and the mixture was stirred for 6 hours and 30 minutes at the temperature to perform a transesterification reaction. Then, the temperature of the surface of the heater was raised from 260 to 290° C. over 30 minutes, and at the same time, the pressure was reduced from normal pressure to 5 kPa to perform a reaction for 40 minutes under the conditions. Then, the temperature of the surface of the heater was raised from 290 to 315° C., at the same time, the pressure was reduced from normal pressure to 5 kPa to 0.7 kPa, a reaction was performed with stirring for 2 hours, and the pressure was returned to normal pressure to obtain a resin composition 5 including the resin α1.

[Preparation of Resin Composition 6]

[0183] Into a 2 L stainless steel separable flask (with a K tube, a stirrer, a nitrogen inlet tube), 100.0 g of dimethyl terephthalate (manufactured by Tokyo Chemical Industry Co., Ltd.), 100.0 g of dimethyl isophthalate (manufactured by Tokyo Chemical Industry Co., Ltd.), 91.5 g of dimethyl sodium 5-sulfoisophthalate (manufactured by SANYO CHEMICAL INDUSTRIES, LTD.), 145.6 g of 1,4-cyclohexanedimethanol (manufactured by FUJIFILM Wako Pure Chemical Corporation, cis-trans mixture), 103.4 g of 1,3-propanediol (manufactured by Tokyo Chemical Industry Co., Ltd.), 210 mg of titanium tetrabutoxide (manufactured by Tokyo Chemical Industry Co., Ltd.), and 563 mg of sodium acetate (manufactured by FUJIFILM Wako Pure Chemical Corporation) were charged, the temperature of the surface of a mantle heater was raised from 160° C. to 220° C. over 25 minutes with the mantle heater with stirring under normal pressure and a nitrogen atmosphere, and the mixture was stirred for 6 hours at the temperature to perform a transesterification reaction. Then, the temperature of the surface of the heater was raised from 220 to 240° C. over 10 minutes, and at the same time, the pressure was reduced from normal pressure to 1.5 kPa to perform a reaction for 8 hours under the conditions. Then, the pressure was further reduced to 0.3 kPa while maintaining the temperature at 240° C. to perform a reaction for 5.5 hours, finally, nitrogen was introduced into the stainless steel separable flask, and the pressure was returned to normal pressure to obtain a resin composition 6 including the resin α2.

[Preparation of Resin Compositions 7 to 13]

[0184] Resin compositions having masses shown in Table 3 and Table 5 were melt-kneaded at 295° C. and 90 r/min for 10 minutes using a melt-kneading machine (manufactured by Toyo Seiki Seisaku-sho, Ltd.: Labo Plastmill 4C150) to obtain each resin composition as a yellow mixture. The glass transition temperatures of resin compositions are shown in Tables 4 and 6. Resin compositions used for melt-kneading were subjected to a treatment at 60° C. under reduced pressure to achieve a constant weight before weighing.

[Preparation of Resin Composition 14]

[0185] Into a glass reactor having an internal capacity of 500 mL and equipped with a stirring blade, 100 g of N-methylpyrrolidone (manufactured by Tokyo Chemical Industry Co., Ltd.) was placed. Subsequently, 3.62 g of terephthalic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.19 g of monosodium 5-sulfoisophthalate (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.696 g of hexamethylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.), 4.58 g of p-xylylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.), and 6.06 g of 4-methylmorpholine (manufactured by Tokyo Chemical Industry Co., Ltd.) were charged into the reactor, and stirred at 70 rpm for 2 hours. Then, the temperature was lowered to 5° C., 20.7 g of 4-(4,6-dimethoxy-1,3,5-triazine-2-yl)-4-methylmorpholinium chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and stirring was continued in the air for 6 hours while maintaining the temperature at 5° C. After the reaction, the temperature was returned to room temperature, a DMF/methanol mixed solution (mass ratio: 2/1) was poured, and the mixture was allowed to stand to precipitate the resin. The resin was separated by filtration and dried at 150° C. under reduced pressure (1 kPa or less) for 12 hours or more to obtain a resin composition 14 including the resin α1.

[Preparation of Resin Composition 15]

[0186] Into a glass reactor having an internal capacity of 500 mL and equipped with a stirring blade, 100 g of N-methylpyrrolidone (manufactured by Tokyo Chemical Industry Co., Ltd.) was placed. Subsequently, 3.62 g of terephthalic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.19 g of monosodium 5-sulfoisophthalate (manufactured by Tokyo Chemical Industry Co., Ltd.), 3.48 g of hexamethylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.), and 6.06 g of 4-methylmorpholine (manufactured by Tokyo Chemical Industry Co., Ltd.) were charged into the reactor, and stirred at 70 rpm for 2 hours. Then, the temperature was lowered to 5° C., 20.7 g of 4-(4,6-dimethoxy-1,3,5-triazine-2-yl)-4-methylmorpholinium chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and stirring was continued in the air for 6 hours while maintaining the temperature at 5° C. After the reaction, the temperature was returned to room temperature, a DMF/methanol mixed solution (mass ratio: 2/1) was poured, and the mixture was allowed to stand to precipitate the resin. The resin was separated by filtration and dried at 150° C. under reduced pressure (1 kPa or less) for 12 hours or more to obtain a resin composition 15 including the resin α2.

[Preparation of Resin Composition 16]

[0187] 5% by mass solutions of the resin compositions 4 and 14 in 1,1,1,3,3,3-hexafluoro-2-propanol (manufactured by FUJIFILM Wako Pure Chemical Corporation) were prepared and compounded in parts by mass shown in Table 8 to obtain a 1,1,1,3,3,3-hexafluoro-2-propanol solution including the resin α1 and the resin α2. These solutions were poured into an aluminum cup and dried under reduced pressure at 150° C. and 1 kPa or less for 12 hours or more to obtain a resin composition 16.

[Preparation of Resin Composition 17]

[0188] A polyimide film was laid on a hot plate (digital hot plate NINOS ND-1 manufactured by AS ONE Corporation). The resin composition 3 (1.0 g) and the resin composition 15 (1.0 g) were dried at 60° C. under reduced pressure, and then placed on the polyimide film, the hot plate was heated to 300° C., and the resins were mixed for 20 minutes while being melted to obtain a resin composition 17.

[Analysis Method]

[Percentage of Amount of Substance of Monomer Unit

[0189] (hereinafter, referred to as monomer unit A) derived from dimethyl sodium 5-sulfoisophthalate based on total of amount of substance of all monomer units in resin]

[0190] A sample was dissolved in a mixed solvent of deuterated chloroform and deuterated trifluoroacetic acid, and an amount of substance A obtained by dividing an integral value A of a peak derived from a benzene ring in a monomer unit A by the number of protons corresponding to the benzene ring in the monomer unit A and an amount of substance B obtained by dividing an integral value B of a peak derived from a naphthalene ring or a benzene ring in a monomer unit (hereinafter, referred to as monomer unit B) derived from one or two selected from dimethyl 2,6-naphthalenedicarboxylate, dimethyl terephthalate, and dimethyl isophthalate by the number of protons corresponding to the naphthalene ring or the benzene ring in the monomer unit B were calculated by proton NMR measurement using NMR MR400 manufactured by Agilent. The value obtained by dividing the amount of substance A by 2 times the sum of the amount of substance A and the amount of substance B, expressed in percentage (100×amount of substance A/(2×(amount of substance A+amount of substance B)), was defined as the percentage of the amount of substance of the monomer unit A based on a total of the amount of substance of all monomer units in the water-soluble polyester resin.

[Weight Average Molecular Weight (Mw)]

(Resin Compositions 1 to 6)

[0191] A calibration curve was prepared from standard polystyrene using a gel permeation chromatograph (GPC) method under the following conditions to determine the weight average molecular weight (Mw) of the resin α or β in the resin composition. [0192] Apparatus: HLC-8320 GPC (Detector integrated type, manufactured by TOSOH CORPORATION) [0193] Column: α-M×2 columns (7.8 mmI.D.×30 cm, manufactured by TOSOH CORPORATION) [0194] Eluent: 60 mmol/L phosphoric acid+50 mmol/L brominated lithium dimethylformamide solution [0195] Flow rate: 1.0 mL/min [0196] Column temperature: 40° C. [0197] Detector: RI detector [0198] Standard substance: polystyrene

[0199] (Resin Compositions 14 and 15)

[0200] A calibration curve was prepared from standard polymethyl methacrylate under the same conditions as in the case of resin compositions 1 to 6 except for the conditions described below to determine the weight average molecular weight (Mw) of the resin α or β in the resin composition. [0201] Column: TSK-Gel Super AWM-H (manufactured by TOSOH CORPORATION) [0202] Eluent: HFIP/0.5 mM sodium trifluoroacetate [0203] Flow rate: 0.2 mL/min [0204] Standard substance: polymethyl methacrylate (PMMVA)

[Glass Transition Temperature]

[0205] A sample sandwiched between polyimide films was placed on a hot plate heated to 260° C., and a spatula was pressed from above to prepare a sheet having a thickness of about 0.2 mm. A sample (5 to 10 mg) was cut out from the sheet with scissors, precisely weighed, and sealed in an aluminum pan, the temperature was raised from 30° C. to 300° C. at 10° C./min, then the cooling rate was set to 150° C./min, and the sample was cooled to 30° C. using a DSC apparatus (DSC 7020 manufactured by Seiko Instruments Inc.). The temperature was raised again to 300° C. at 10° C./min to obtain a DSC curve, from which a glass transition temperature (° C.) was determined.

<Evaluation Method>

[Dissolution Test of Resin Composition]

Examples 1 to 7, Comparative Examples 1 to 6

[0206] Each (20 g) of the resin compositions shown in Tables 3 and 5 was ground with a coffee mill (Mini Blender manufactured by OSAKA CHEMICAL Co., Ltd.) (grinding time: 10 seconds) to prepare an evaluation sample. Sample powder (1.0 g) was placed in 20 g of deionized water in a 50 mL screw tube, the dissolution state of the resin compositions was observed with stirring at 300 rpm using a magnetic stirrer, and the time taken for the resin compositions to be dissolved in water (dissolution time) was measured. The results are shown in Tables 4 and 6. In Tables, “insoluble” represents a state where an insoluble matter is observed even 60 minutes after the sample powder was placed into the screw tube, and “-” represents that evaluation was not performed.

Example 8 and Comparative Example 7

[0207] Resin compositions described in Table 7 were placed in an aluminum bag and pulverized with a hammer to prepare an evaluation sample. Evaluation was performed under the same conditions as in Examples 1 to 7 and Comparative Examples 1 to 6 except that 0.20 g of sample powder was placed in 4 g of deionized water in a 20 mL screw tube. The results are shown in Table 7.

Example 9 and Comparative Example 8

Preparation of Film

Example 9

[0208] Resin compositions 4 and 14 were dissolved in 1,1,1,3,3,3-hexafluoro-2-propanol (manufactured by FUJIFILM Wako Pure Chemical Corporation) to prepare solutions each having a concentration of 5% by mass. The solution of the resin composition 4 (1.0 g) and the solution of the resin composition 14 (1.0 g) were put in a glass bottle to obtain a mixed solution. Two drops of this mixed solution were dropped onto a slide glass using a dropper, and dried at 150° C. under reduced pressure (1 kPa or less) for 2 hours to prepare a film having a thickness of 30 μm. The thickness of the slide glass before the solution was dropped and the total of thicknesses of the film and the slide glass were measured using a micrometer, and the thickness of the film was calculated from the difference.

Comparative Example 8

[0209] A film having a thickness of 30 μm was prepared by performing the same operations as in Example 9 except that two drops of the solution of the resin composition 14 was dropped onto a slide glass using a dropper.

[Evaluation of Appearance of Film]

[0210] The appearance of each film was visually evaluated. The results are shown in Table 8.

[Evaluation of Water Dispersibility]

[0211] Deionized water (500 mL) was placed in a 500 mL beaker, the temperature was raised to the temperature described in Table 8 on a hot plate, and the temperature was maintained until the end of this evaluation. The slide glass after the film formation was put in the beaker, and the sample formed on the slide glass was immersed in the deionized water after the temperature was raised and held. The time until the film on the slide glass was removed from the slide glass was visually observed. The results are shown in Table 8. In Table 8, “insoluble” represents a state where the presence of a film is observed even 60 minutes after the slide glass was immersed in deionized water.

TABLE-US-00001 TABLE 1 Content of Weight Percentage of each monomer unit based on hydrophilic average Resin composition total of all monomer units in resin α1 [mol %] group molecular including resin α1 A1 B1 C1 C2 [mmol/g] weight Resin composition 1 32.2 17.8 49.0 1.00 1.00 29000 Resin composition 3 32.2 17.8 49.0 1.00 1.00 11800 Resin composition 5 24.5 25.5 29.6 20.4 1.00 25000 Resin composition 14 13.5 36.5 40.0 10.0 0.93 5200

TABLE-US-00002 TABLE 2 Percentage of each monomer unit based on Content of Weight total of all monomer hydrophilic average Resin composition units in resin α2 [mol%] group molecular including resin α2 A2 B2 C2 [mmol/g] weight Resin composition 2 12.5 37.5 50.0 1.00 17800 Resin composition 4 12.5 37.5 50.0 1.0 19500 Resin composition 6 12.0 38.0 50.0 0.82 11400 Resin composition 15 13.5 36.5 50.0 1.00 14200

TABLE-US-00003 TABLE 3 Mass (g) of resin composition Component of resin Content of used for melt-kneading composition (% by mass) resin α1 ÷ Resin Resin Resin Resin Organic salt Content of composition 1 composition 2 α1 α2 compound β.sup.1) resin α2 Example 1 Resin 47.5 2.5 86.4 4.80 8.80 18 composition 7 Example 2 Resin 45.0 5.0 81.8 9.50 8.70 8.6 composition 8 Example 3 Resin 37.5 12.5 68.2 23.8 8.00 2.9 composition 9 Example 4 Resin 25.0 25.0 45.5 47.6 6.90 0.96 composition 10 Comparative Resin — — 90.9 0 9.10 — Example 1 composition 1 Comparative Resin — — 0 95.2 4.80 0.00 Example 2 composition 2 .sup.1)Tetrabutylphosphonium dodecylbenzenesulfonate

TABLE-US-00004 TABLE 4 Amount of substance of alkyl sulfonic acid ion of organic salt compound β + Total of amount of substance of hydrophilic group of resin α1 and amount of substance of hydrophilic group of Tg Dissolution time resin α2 (° C.) 90° C. 80° C. Example 1 Resin 0.14  200, 30 min — composition 188 7 Example 2 Resin 0.14 186 20 min — composition 8 Example 3 Resin 0.13 175 10 min 60 min  composition 9 Example 4 Resin 0.11 155  3 min 8 min composition 10 Comparative Resin 0.15 201 Insoluble Insoluble Example 1 composition 1 Comparative Resin 0.079 109 — 3 min Example 2 composition 2

TABLE-US-00005 TABLE 5 Mass (g) of resin composition Component of resin Content of used for melt-kneading composition (% by mass) resin α1 ÷ Resin Resin Resin Resin Resin Resin Organic salt Content of composition 3 composition 4 composition 5 composition 6 α1 α2 compound β.sup.1) resin α2 Example 5 Resin 37.1 12.9 — — 74.1 25.9 — 2.9 composition 11 Example 6 Resin — 12.9 37.1 — 68.1 25.9 6.00 2.6 composition 12 Example 7 Resin 37.1 — — 12.9 74.1 25.9 — 2.9 composition 13 Comparative Resin — — — — 100 0 — — Example 3 composition 3 Comparative Resin — — — — 0 100 — 0.00 Example 4 composition 4 Comparative Resin — — — — 91.9 0 8.10 — Example 5 composition 5 Comparative Resin — — — — 0 100 — 0.00 Example 6 composition 6 .sup.1)Tetrabutylphosphonium dodecylbenzenesulfonate

TABLE-US-00006 TABLE 6 Amount of substance of alkyl sulfonic acid ion of organic salt compound β + Total of amount of substance of hydrophilic group of resin α1 and amount of substance of hydrophilic group of Tg Dissolution time resin α2 (° C.) 90° C. 80° C. Example 5 Resin — 189 25 min — composition 11 Example 6 Resin 0.11 157  4 min 15 min composition 12 Example 7 Resin — 168 10 min 50 min composition 13 Comparative Resin — 215 Insoluble Insoluble Example 3 composition 3 Comparative Resin — 109 —  4 min Example 4 composition 4 Comparative Resin 0.13 175 Insoluble Insoluble Example 5 composition 5 Comparative Resin — 72 —  3 min Example 6 composition 6

TABLE-US-00007 TABLE 7 Parts by mass of resin composition Component of resin Content of used for preparation composition (% by mass) resin α1 ÷ Dissolution Resin Resin Resin Resin Content of time composition 3 composition 15 α1 α2 resin α2 Tg (° C.) 90° C. 80° C. Example 8 Resin 50 50 50 50 1.00 199 50 min — composition 17 Comparative Resin — — 0 100 0.00 168  7 min 30 min Example 7 composition 15

TABLE-US-00008 TABLE 8 Parts by mass of resin composition Component of resin Content of used for preparation composition (% by mass) resin α1 ÷ Resin Resin Resin Resin Content of composition 4 composition 14 α1 α2 resin α2 Example 9 Resin 50 50 50 50 1.00 composition 16 Comparative Resin — — 100 0 — Example 8 composition 14 Water dispersibility (Fine dispersion time/Visual Appearance of observation) Tg (° C.) film 80° C. 70° C. Example 9 Resin 204 Colorless and Less than 5 min composition 16 transparent 1 minute Comparative Resin 248 Colorless and Insoluble Insoluble Example 8 composition 14 transparent

[0212] Table 4 shows that the resin compositions 7 to 10 in which the resin composition 2 having a high solubility is compounded to the resin composition 1 having a low solubility in water have significantly improved solubilities in water at the same temperature while high glass transition temperatures are maintained.

[0213] Table 6 shows that the resin composition 11 in which the resin composition 4 having a high solubility is compounded to the resin composition 3 having a low solubility in water and the resin composition 13 in which the resin composition 6 having a high solubility is compounded to the resin composition 3 having a low solubility in water have significantly improved solubilities in water at the same temperature while high glass transition temperatures are maintained. Table 6 also shows that the resin composition 12 in which the resin composition 5 having a low solubility is compounded to the resin composition 4 having a high solubility in water has a significantly improved solubility in water at the same temperature while a high glass transition temperature is maintained.

[0214] Table 7 shows that the resin composition 17 in which the resin composition 15 having a high solubility is compounded to the resin composition 3 having a low solubility in water has a significantly improved solubility in water at the same temperature while a high glass transition temperature is maintained.

[0215] Table 8 shows that the resin composition 16 in which the resin composition 4 having a high dispersibility is compounded to the resin composition 14 having a low dispersibility in water has a significantly improved dispersibility at the same temperature while a high glass transition temperature is maintained.