JP2014031401A - Aqueous polyarylate resin dispersion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aqueous polyarylate resin dispersion having excellent stability, which can form a resin film having high hardness.SOLUTION: The aqueous polyarylate resin dispersion comprises a polyarylate resin composed of an aromatic dicarboxylic acid component and a divalent phenolic component and satisfying the following (i) to (iii), a basic compound and water, and does not substantially contain an emulsifier: (i) the aromatic dicarboxylic acid component includes terephthalic acid (TPA) and isophthalic acid (IPA) as main components with TPA/IPA=60/40 to 40/60 (mole ratio); (ii) the divalent phenol component includes 20 to 50 mol% of 4,4'-(hexafluoroisopropylidene)diphenol and 20 to 50 mol% of resorcinol; and (iii) an acid value is 4 to 40 mgKOH/g.

Description

  The present invention relates to an aqueous dispersion of a polyarylate resin that can form a resin film having high hardness and is excellent in storage stability.

  In recent years, polyarylate resins have been used in various applications because of their excellent transparency and heat resistance. For example, amorphous polyarylate composed of 2,2-bis (4-hydroxyphenyl) propane and terephthalic acid and isophthalic acid is already well known as an engineering plastic and is used in the fields of electricity, electronics, automobiles, machinery, etc. Widely used.

  Polyarylate resin is often processed in a molten state like extrusion molding or injection molding, but its excellent film-forming properties, adhesion, and transparency can be dissolved in an organic solvent to dissolve metal, glass, resin, and wood. It is increasingly used as a resin film for coating a substrate such as the above.

  On the other hand, the tendency to curb the use of organic solvents has been increasing in recent years for reasons such as environmental protection, regulation of dangerous goods under the Fire Service Act, and improvement of the workplace environment. Aqueous dispersion in which existing resin is finely dispersed in an aqueous medium There is a need for a body, and its development is actively underway.

  For example, Patent Documents 1 and 2 disclose an aqueous dispersion in which a polyarylate resin using 20 mol% or more of terephthalic acid, isophthalic acid and 4,4 ′-(hexafluoroisopropylidene) diphenol is dispersed in an aqueous medium. Is disclosed.

JP 2010-18770 A JP 2010-65155 A

  However, the aqueous dispersions of Patent Documents 1 and 2 sometimes have poor storage stability depending on the composition of the polyarylate resin used. Further, when used as a coating agent, depending on the composition of the polyarylate resin to be used, the resin film has a low hardness and may be damaged.

  In view of the conventional technology, an object of the present invention is to provide an aqueous dispersion of a polyarylate resin that can form a resin film having high hardness and is excellent in storage stability.

  As a result of intensive studies to solve such problems, the present inventor can obtain a resin film having high hardness by using a polyarylate resin containing resorcinol in a specific ratio, storage The present inventors have found that an aqueous dispersion excellent in stability can be obtained, and reached the present invention.

That is, the gist of the present invention is as follows.
(1) A polyarylate resin aqueous solution comprising a polyarylate resin composed of an aromatic dicarboxylic acid component and a dihydric phenol component and satisfying the following (i) to (iii), a basic compound and water, and substantially free of an emulsifier: Dispersion.
(I) The aromatic dicarboxylic acid component contains terephthalic acid (TPA) and isophthalic acid (IPA) as main components, and TPA / IPA = 60/40 to 40/60 (molar ratio).
(Ii) As the dihydric phenol component, 20 to 50 mol% of 4,4 ′-(hexafluoroisopropylidene) diphenol and 20 to 50 mol% of resorcinol are contained.
(Iii) Acid value is 4-40 mgKOH / g.
(2) The polyarylate resin aqueous dispersion according to (1), wherein the glass transition temperature of the polyarylate resin is 150 ° C. or higher.
(3) The polyarylate resin aqueous dispersion according to (1) or (2), wherein the polyarylate resin has a weight average molecular weight of 10,000 or more.
(4) A resin film obtained by applying and drying the aqueous polyarylate resin dispersion according to any one of (1) to (3).

  The aqueous polyarylate resin dispersion according to the present invention is superior in storage stability compared to conventional ones and can be stored for a long period of time. In addition, the resin film obtained by applying and drying the aqueous dispersion of the present invention has high hardness and excellent film-forming properties, adhesion, alcohol resistance, transparency, and heat resistance. It can be used suitably. Moreover, since the aqueous dispersion of the present invention comprises a polyarylate resin and water as main components, the use of an organic solvent can be suppressed, and environmental protection, work environment improvement, and operability can be improved. .

  Hereinafter, the present invention will be described in detail.

  The aqueous polyarylate resin dispersion used in the present invention (hereinafter sometimes simply referred to as “aqueous dispersion”) is obtained by dispersing a polyarylate resin in an aqueous medium.

  The polyarylate resin used in the present invention is composed of an aromatic dicarboxylic acid component and a dihydric phenol component.

  The aromatic dicarboxylic acid component contains terephthalic acid (TPA) and isophthalic acid (IPA) as main components, and the content ratio thereof is TPA / IPA = 60/40 to 40/60 (molar ratio). It is necessary and it is preferable that TPA / IPA = 50/50 (molar ratio). When TPA / IPA (molar ratio) exceeds 60/40 or less than 40/60, the polyarylate resin becomes difficult to dissolve in an organic solvent in the dissolution step of the production method described later, and storage stability Becomes bad. Further, the film forming property is poor. The aromatic dicarboxylic acid component may contain an aromatic dicarboxylic acid other than TPA and IPA as long as the polyarylate resin can be dissolved in the dissolving step of the production method described later. Examples of such aromatic dicarboxylic acids include phthalic acid, 2,6-naphthalenedicarboxylic acid, 3-tert-butylisophthalic acid, and diphenic acid.

  As the dihydric phenol component, it is necessary to contain 4,4 ′-(hexafluoroisopropylidene) diphenol (BisAF), and the content thereof is 20 to 50 mol% of the total dihydric phenol component. It is necessary, and it is preferable to set it as 30-50 mol%, and it is more preferable to set it as 35-45 mol%. When the BisAF content is less than 20 mol%, the polyarylate resin is difficult to dissolve in the organic solvent, and the storage stability is poor. In addition, the film forming property is poor, which is not preferable. On the other hand, when the BisAF content exceeds 50 mol%, the resulting coating has poor alcohol resistance.

  The dihydric phenol component requires resorcinol to be 20 to 50 mol% of all dihydric phenol components, preferably 30 to 50 mol%, and preferably 35 to 45 mol%. It is more preferable. When the content of resorcinol is less than 20 mol%, the hardness of the polyarylate resin is low. On the other hand, when the content of resorcinol exceeds 50 mol%, the film forming property is poor.

  The dihydric phenol component may contain other dihydric phenol components in addition to BisAF and resorcinol. Examples of other dihydric phenol components include 1,1-bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, and 1,1-bis (4-methyl-2-hydroxy). Phenyl) methane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxyphenyl) -4- Methylpentane, 2,2-bis (4-hydroxyphenyl) propane [BisA], 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4- Hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4-hydroxyphenyl) -2-ethylhe Sun, 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, 1,1-bis (3-methyl-4-hydroxyphenyl) methane, 4,4'-biphenol, 2,2-bis (4 -Hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) -2-methylpropane, 1,1-bis (4-hydroxyphenyl) -1-phenylmethane, 2,2-bis (4-hydroxyphenyl) ) Octane, 1,1-bis (3-methyl-4-hydroxyphenyl) cyclohexane, 2,2-bis (3-allyl-4-hydroxyphenyl) propane, 2,2-bis (3-isopropyl-4-hydroxy) Phenyl) propane, 2,2-bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (3-sec-butyl-4-hydroxy) Droxyphenyl) propane, bisphenolfluorene, 1,1-bis (2-methyl-4-hydroxy-5-tert-butylphenyl) -2-methylpropane, 4,4 ′-[1,4-phenylene-bis ( 2-propylidene) -bis (3-methyl-4-hydroxyphenyl)], 1,1-bis (3-phenyl-4-hydroxyphenyl) cyclohexane, 4,4′-dihydroxyphenyl ether, bis (2-hydroxyphenyl) ) Methane, 2,4'-methylenebisphenol, bis (3-methyl-4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) propane, 1,1-bis (2-hydroxy-5-methylphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -3-methylbutane, bis (2-hydroxy-3,5- Methylphenyl) methane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (3-methyl-4-hydroxyphenyl) cyclopentane, 3,3-bis (4-hydroxyphenyl) pentane, 3,3-bis (3-methyl-4-hydroxyphenyl) pentane, 3,3-bis (3,5-dimethyl-4-hydroxyphenyl) pentane, 2,2-bis (2-hydroxy-3,5- Dimethylphenyl) propane, 2,2-bis (4-hydroxyphenyl) nonane, 1,1-bis (3-methyl-4-hydroxyphenyl) -1-phenylethane, 1,1-bis (3,5-dimethyl) -4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxyphenyl) decane, 1,1-bis (4-hydroxyphenyl) decane Bis (2-hydroxy-3-tert-butyl-5-methylphenyl) methane, bis (4-hydroxyphenyl) diphenylmethane, terpene diphenol, 1,1-bis (3-tert-butyl-4-hydroxyphenyl) cyclohexane 1,1-bis (2-methyl-4-hydroxy-5-tert-butylphenyl) -2-methylpropane, 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, 1,1-bis (3,5-di-tert-butyl-4-hydroxyphenyl) methane, 1,1-bis (3,5-di-sec-butyl-4-hydroxyphenyl) methane, 1,1-bis (3-cyclohexyl) -4-hydroxyphenyl) cyclohexane, 1,1-bis (2-hydroxy-3,5-di-tert-butylphenol) Nyl) ethane, bis (3-nonyl-4-hydroxyphenyl) methane, 2,2-bis (3,5-di-tert-butyl-4-hydroxyphenyl) propane, bis (2-hydroxy-3,5- Di-tert-butyl-6-methylphenyl) methane, 1,1-bis (3-phenyl-4-hydroxyphenyl) -1-phenylethane, bis (3-fluoro-4-hydroxyphenyl) methane, bis (2 -Hydroxy-5-fluorophenyl) methane, 2,2-bis (3-fluoro-4-hydroxyphenyl) propane, bis (3-fluoro-4-hydroxyphenyl) -phenylmethane, bis (3-fluoro-4-hydroxy) Phenyl)-(p-fluorophenyl) methane, bis (4-hydroxyphenyl)-(p-fluorophenyl) methane, , 2-bis (3-chloro-4-hydroxy-5-methylphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (3-chloro-4) -Hydroxyphenyl) propane, 1,1-bis (3,5-dibromo-4-hydroxyphenyl) methane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 2,2-bis ( 3-nitro-4-hydroxyphenyl) propane, 3,3′-dimethyl-4,4′-biphenol, 3,3 ′, 5,5′-tetramethyl-4,4′-biphenol, 3,3 ′, 5,5′-tetra-tert-butyl-4,4′-biphenol, bis (4-hydroxyphenyl) ketone, 3,3′-difluoro-4,4′-biphenol, 3,3 ′, 5,5 ′ -Tetrafur B-4,4′-biphenol, bis (4-hydroxyphenyl) dimethylsilane, bis (3-methyl-4-hydroxyphenyl) ether, bis (3,5-dimethyl-4-hydroxyphenyl) ether, bis (2 , 3,5-trimethyl-4-hydroxyphenyl) -phenylmethane, 2,2-bis (4-hydroxyphenyl) dodecane, 2,2-bis (3-methyl-4-hydroxyphenyl) dodecane, 2,2- Bis (3,5-dimethyl-4-hydroxyphenyl) dodecane, 1,1-bis (3-tert-butyl-4-hydroxyphenyl) -1-phenylethane, 1,1-bis (3,5-di-) tert-butyl-4-hydroxyphenyl) -1-phenylethane, 1,1-bis (2-methyl-4-hydroxy-5-cyclohexylfe) ) -2-methylpropane, 1,1-bis (2-hydroxy-3,5-di-tert-butylphenyl) ethane, isatin bisphenol, isatin biscresol, 2,2 ′, 3,3 ′, 5,5'-hexamethyl-4,4'-biphenol, bis (2-hydroxyphenyl) methane, 2,4'-methylenebisphenol, 1,2-bis (4-hydroxyphenyl) ethane, 2- (4-hydroxy Phenyl) -2- (2-hydroxyphenyl) propane, bis (2-hydroxy-3-allylphenyl) methane, 1,1-bis (2-hydroxy-3,5-dimethylphenyl) -2-methylpropane, 1 , 1-bis (2-hydroxy-5-tert-butylphenyl) ethane, bis (2-hydroxy-5-phenylphenyl) methane, 1,1-bis 2-methyl-4-hydroxy-5-tert-butylphenyl) butane, bis (2-methyl-4-hydroxy-5-cyclohexylphenyl) methane, 2,2-bis (4-hydroxyphenyl) pentadecane, 2,2 -Bis (3-methyl-4-hydroxyphenyl) pentadecane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) pentadecane, 1,2-bis (3,5-di-tert-butyl-4 -Hydroxyphenyl) ethane, bis (2-hydroxy-3,5-di-tert-butylphenyl) methane, 2,2-bis (3-styryl-4-hydroxyphenyl) propane, 1,1-bis (4- Hydroxyphenyl) -1- (p-nitrophenyl) ethane, bis (3,5-difluoro-4-hydroxyphenyl) methane, bis 3,5-difluoro-4-hydroxyphenyl) phenylmethane, bis (3,5-difluoro-4-hydroxyphenyl) diphenylmethane, bis (3-fluoro-4-hydroxyphenyl) diphenylmethane, 2,2-bis (3- Chloro-4-hydroxyphenyl) propane, 3,3 ′, 5,5′-tetra-tert-butyl-2,2′-biphenol, 2,2′-diallyl-4,4′-biphenol, 1,1- Bis (4-hydroxyphenyl) -3,3,5-trimethyl-cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5,5-tetramethyl-cyclohexane, 1,1-bis (4 -Hydroxyphenyl) -3,3,4-trimethyl-cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3-dimethyl- -Ethyl-cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethyl-cyclopentane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) -3,3 5-trimethyl-cyclohexane, 1,1-bis (3,5-diphenyl-4-hydroxyphenyl) -3,3,5-trimethyl-cyclohexane, 1,1-bis (3-methyl-4-hydroxyphenyl)- 3,3,5-trimethyl-cyclohexane, 1,1-bis (3-phenyl-4-hydroxyphenyl) -3,3,5-trimethyl-cyclohexane, 1,1-bis (3,5-dichloro-4- Hydroxyphenyl) -3,3,5-trimethyl-cyclohexane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (3-methyl-4) -Hydroxyphenyl) fluorene, 1,1-bis (3,5-dibromo-4-hydroxyphenyl) -3,3,5-trimethyl-cyclohexane, bis (4-hydroxyphenyl) sulfone [BisS], bis (2- Hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, bis (3,5-diethyl-4-hydroxyphenyl) sulfone, bis (3-methyl-4-hydroxyphenyl) sulfone, bis ( 3-ethyl-4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfide, bis (3,5-dimethyl-4-hydroxyphenyl) sulfide, bis (3,5-diethyl-4-hydroxyphenyl) sulfide, Bis (3-methyl-4-hydroxyphenyl) sulfide, bis ( - ethyl-4-hydroxyphenyl) sulfide, 2,4-dihydroxydiphenyl sulfone, 2,2-bis (4-hydroxyphenyl) propanoic acid methyl ester.

  In the present invention, an aliphatic dicarboxylic acid or a glycol may be contained in addition to the aromatic dicarboxylic acid component and the dihydric phenol component as long as the effects of the present invention are not impaired. When the aliphatic dicarboxylic acid or glycol is contained, the content may be 5 mol% or less with respect to 100 mol% of the total dicarboxylic acid component and 100 mol% of the total of the dihydric phenol component and the glycol component, respectively. preferable. In general, when an aliphatic dicarboxylic acid is used, the heat resistance decreases.

  The polyarylate resin used in the present invention is required to have an acid value of 4 to 40 mgKOH / g, preferably 4 to 30 mgKOH / g, and more preferably 6 to 20 mgKOH / g. When the acid value is less than 4 gKOH / g, uniform dispersion in an aqueous medium becomes difficult, or even if it can be dispersed, the storage stability of the aqueous dispersion becomes poor. On the other hand, when the acid value exceeds 40 mgKOH / g, the polyarylate resin obtained has a low weight average molecular weight, and thus the adhesion and hardness of the resin film are low. Further, the film forming property is poor. The acid value can be adjusted by controlling the amount of monohydric phenol, monohydric acid halide, monohydric alcohol, and monohydric carboxylic acid described later.

  The polyarylate resin used in the present invention preferably has a weight average molecular weight of 10,000 or more, more preferably 30,000 or more, and further preferably 50,000 or more. When the weight average molecular weight is less than 10,000, the film forming property may be poor.

  From the viewpoint of heat resistance, the glass transition temperature of the polyarylate resin used in the present invention is preferably 150 ° C. or higher, more preferably 170 ° C. or higher, and further preferably 200 ° C. or higher.

  Next, the manufacturing method of the polyarylate resin used for this invention is demonstrated.

  As a method for producing a polyarylate resin, it can be produced by using a known polyarylate resin polymerization method using the aforementioned dihydric phenol and aromatic dicarboxylic acid and / or a derivative thereof as raw materials. . Examples of the polymerization method include interfacial polycondensation, solution polymerization, and melt polymerization. The polyarylate resin used in the present invention is preferably polymerized by an interfacial polycondensation method. When the interfacial polycondensation method is used, the polymerization rate is high, and a high molecular weight polyarylate resin can be obtained. Moreover, the obtained polyarylate resin is hardly colored. On the other hand, a polyarylate resin polymerized by a method other than the interfacial polycondensation method, for example, a melt polymerization method using acetic anhydride is often colored, and a trace amount of acetic acid or the like remains and an aqueous dispersion described later May also affect the production of

  In the interfacial polycondensation method, an aqueous phase obtained by dissolving a dihydric phenol in an alkaline aqueous solution and an organic phase obtained by dissolving a divalent carboxylic acid halide in an organic solvent not dissolved in water are mixed in the presence of a catalyst. Is done.

  Examples of the alkali used in the aqueous phase include sodium hydroxide and potassium hydroxide. When the total molar amount of the dihydric phenol is 1, the amount of alkali is preferably 2.0 to 5.0 times mole, and more preferably 2.0 to 3.0 times mole. Generally, when the amount of alkali used in the interfacial polymerization method exceeds 5.0 times the total molar amount of dihydric phenol, the polymerization does not proceed easily and the number average molecular weight is low.

  As the organic solvent used in the organic phase, an organic solvent that is not compatible with water and can suitably dissolve the polyarylate resin to be generated is used. Examples of such organic solvents include methylene chloride, 1,2-dichloroethane, chloroform, carbon tetrachloride, chlorobenzene, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, and o-dichlorobenzene. , Chlorinated solvents such as m-dichlorobenzene and p-dichlorobenzene, and aromatic hydrocarbons such as toluene, benzene and xylene.

  Examples of the catalyst include trimethylamine, triethylamine, tri-n-butylamine, trihexylamine, tridodecylamine, N, N-dimethylcyclohexylamine, tertiary amines such as pyridine, quinoline and dimethylaniline, trimethylbenzylammonium halide, Quaternary ammonium salts such as tributylbenzylammonium halide, triethylbenzylammonium halide, tributylbenzylphosphonium halide, tetrabutylammonium halide, trimethylbenzylphosphonium halide, tributylbenzylphosphonium halide, triethylbenzylphosphonium halide, tetrabutylphosphonium halide, triphenylbenzyl Such as phosphonium halide, tetraphenylphosphonium halide, etc. Quaternary phosphonium salts. Among these, from the viewpoint of reaction rate, tributylbenzylammonium halide, tetrabutylammonium halide, and tetrabutylphosphonium halide are preferable.

  The end of the polyarylate resin used in the present invention may be sealed with a monohydric phenol, monohydric acid halide, monohydric alcohol, monohydric carboxylic acid or the like as long as the effects of the present invention are not impaired. Examples of the monohydric phenol include phenol, o-cresol, m-cresol, p-cresol, p-tert-butylphenol, o-phenylphenol, m-phenylphenol, p-phenylphenol, o-methoxyphenol, m- Methoxyphenol, p-methoxyphenol, 2,3,6-trimethylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5 -Xylenol, 2-phenyl-2- (4-hydroxyphenyl) propane, 2-phenyl-2- (2-hydroxyphenyl) propane, 2-phenyl-2- (3-hydroxyphenyl) propane. Examples of the monovalent acid halide include benzoyl chloride, benzoic acid chloride, methanesulfonyl chloride, and phenyl chloroformate. Examples of the monohydric alcohol include methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, pentanol, hexanol, dodecyl alcohol, stearyl alcohol, benzyl alcohol, and phenethyl alcohol. Examples of the monovalent carboxylic acid include acetic acid, propionic acid, octanoic acid, cyclohexanecarboxylic acid, benzoic acid, toluic acid, phenylacetic acid, p-tert-butylbenzoic acid, and p-methoxyphenylacetic acid.

  In the interfacial polycondensation method, the organic phase solution is mixed with the aqueous phase solution described above, polycondensation is performed with stirring for 1 to 8 hours, and acetic acid is added to the mixed solution to complete the polymerization. The reaction temperature is usually 50 ° C. or lower. Thereafter, the organic phase is washed with repeated stirring with water to remove salts such as sodium and potassium, acetic acid, and ionic components such as a polymerization catalyst contained in the organic phase. The water used for washing may be acidic or basic, but it is necessary to wash repeatedly until the washing waste water becomes neutral. By adding a poor solvent to the washed organic phase, the resin as a solid content can be precipitated. At this time, the volume of the poor solvent is preferably at least 3 times the volume of the organic phase. Examples of the poor solvent include methanol, ethanol, isopropyl alcohol, acetone, acetonitrile, and hexane.

  By adding a poor solvent to the organic phase, the free aromatic dicarboxylic acid contained in the resin can be reduced. In particular, the content of free aromatic dicarboxylic acid can be further reduced by setting the immersion time in the poor solvent after the precipitation treatment to the poor solvent to be 1 minute or longer. In this case, when trimethylbenzylammonium halide or triethylbenzylammonium halide having relatively low polymerization activity is used as the polymerization catalyst, the immersion time is preferably set to 3 minutes or more. In order to further sufficiently reduce the amount of free aromatic dicarboxylic acid, the above-described operation of dissolving the obtained resin again in a solvent and adding a poor solvent to perform precipitation may be repeated.

  Next, the aqueous polyarylate resin dispersion of the present invention will be described.

  The aqueous polyarylate resin dispersion of the present invention is an emulsion obtained by dispersing a polyarylate resin in an aqueous medium. Here, the aqueous medium is a medium made of a liquid containing water, and may contain an organic solvent or a basic compound.

  The aqueous polyarylate resin dispersion of the present invention should contain substantially no emulsifier. The emulsifier as used in the present invention includes a surfactant, a compound having a protective colloid effect, a modified wax, an acid-modified product having a high acid value, a water-soluble polymer, and the like. In the present invention, “substantially free” means that no emulsifier is actively added during the production of the aqueous polyarylate resin dispersion of the present invention, resulting in the absence of these. To do. The content of such an emulsifier is preferably zero, but may be less than 0.1 parts by mass with respect to 100 parts by mass of the polyarylate resin component as long as the effects of the present invention are not impaired. When the aqueous dispersion contains 0.1 part by mass or more of an emulsifier, the water resistance of the resin film is lowered. By using an emulsifier, the polyarylate resin can be easily dispersed in an aqueous medium, while such a formulation significantly impairs water resistance.

  Examples of the surfactant include a cationic surfactant, an anionic surfactant, a nonionic surfactant, and an amphoteric surfactant. For example, anionic surfactants include higher alcohol sulfates, higher alkyl sulfonates, higher carboxylates, alkyl benzene sulfonates, polyoxyethylene alkyl sulfate salts, polyoxyethylene alkyl phenyl ether sulfates. Salt, vinyl sulfosuccinate, nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyethylene glycol fatty acid ester, ethylene oxide propylene oxide block copolymer, polyoxyethylene fatty acid Compounds having a polyoxyethylene structure such as amides, ethylene oxide-propylene oxide copolymers, and sorbitan derivatives can be mentioned, and amphoteric surfactants include lauryl Tyne, lauryl dimethyl amine oxide.

  Examples of the compound having a protective colloid effect include polyvinyl alcohol, carboxyl group-modified polyvinyl alcohol, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, modified starch, and polyvinyl pyrrolidone.

  Examples of the modified waxes include acid-modified polyolefin waxes having a number average molecular weight of 5000 or less, such as carboxyl group-containing polyethylene wax, carboxyl group-containing polypropylene wax, and carboxyl group-containing polyethylene-propylene wax, and salts thereof.

  Examples of the high acid value acid-modified compound include acrylic acid-maleic anhydride copolymer and salts thereof, styrene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid copolymer, isobutylene-anhydride. Examples thereof include a carboxyl group-containing compound having an unsaturated carboxylic acid content of 10% by mass or more, such as a maleic acid alternating copolymer and a (meth) acrylic acid- (meth) acrylic ester copolymer, and salts thereof.

  Examples of the water-soluble polymer include polyacrylic acid and salts thereof, polyitaconic acid and salts thereof, water-soluble acrylic copolymers having amino groups, gelatin, gum arabic, and casein.

  In the polyarylate resin aqueous dispersion of the present invention, the content of the polyarylate resin is preferably 5 to 50% by mass, and more preferably 15 to 40% by mass. Further, since the dispersed polyarylate resin is less likely to aggregate, storage stability is improved.

  The aqueous polyarylate resin dispersion of the present invention preferably has a pH of 6 or more, more preferably 7 or more, and even more preferably 8 or more. By setting the pH to 6 or more, the dispersed polyarylate resin is less likely to aggregate, so that the storage stability of the aqueous dispersion is improved.

  In the aqueous polyarylate resin dispersion of the present invention, the volume average particle size of the polyarylate resin fine particles is preferably less than 500 nm, more preferably less than 300 nm, and even more preferably less than 200 nm. By setting the volume average particle size to less than 500 nm, the dispersed polyarylate resin is less likely to aggregate, so that the storage stability of the aqueous dispersion is improved. The volume average particle diameter can be controlled by the amount of organic amine and the reaction temperature during phase inversion emulsification, as will be described later.

  Next, the manufacturing method of a polyarylate resin aqueous dispersion is demonstrated.

  The aqueous polyarylate resin dispersion used in the present invention is produced by a method in which the carboxyl group of the polyarylate resin is dispersed in an aqueous medium by neutralizing at least partly or entirely with a basic compound. Is done. By neutralizing the carboxyl group, a carboxyl anion is generated, and due to the electric repulsion between the anions, the dispersed polyarylate resin is less likely to aggregate and can exist stably.

  Examples of the method for producing the aqueous polyarylate resin dispersion used in the present invention include a transfer emulsification method and a self-emulsification method. The transfer emulsification method is a method in which a polyarylate resin is dissolved in an organic solvent (dissolution step), and a basic compound and water are added to the obtained polyarylate resin solution (phase inversion emulsification step). This is a method for obtaining an aqueous resin dispersion. In addition, the self-emulsification method is a method of preparing a polyarylate resin aqueous dispersion containing an organic solvent by charging a polyarylate resin, a basic compound, an organic solvent and water all at once and heating the system while stirring. It is.

  As used herein, “phase inversion emulsification” refers to adding an amount of water exceeding the amount of organic solvent contained in the organic solvent solution of the polyarylate resin to change the system of the organic solvent solution from the organic solvent phase to O. / W to change to an emulsion dispersion system.

  In the present invention, it is more preferable to use a transfer emulsification method because an aqueous dispersion can be easily obtained.

  In the production of the aqueous dispersion of the present invention, after each of the above emulsification steps, a step of removing the organic solvent and / or the basic compound from the polyarylate resin dispersion to obtain an aqueous polyarylate resin dispersion (desorption). (Solvent process) may be provided. In general, when the organic solvent remains in the aqueous dispersion, the storage stability of the aqueous dispersion is poor. Therefore, when the transfer emulsification method is used, it is preferable to provide a solvent removal step. The organic solvent content after the solvent removal step is preferably less than 1% by mass of the aqueous dispersion.

  In the production of the aqueous dispersion of the present invention, a filtration step for removing undispersed matter and aggregates by filtration may be appropriately provided. For example, a 600-mesh stainless steel filter (filtration accuracy: 25 μm, twill) may be installed, and atmospheric pressure filtration or pressure (air pressure 0.2 MPa) filtration may be performed.

  In the dissolving step, the polyarylate resin is dissolved in an organic solvent to obtain an organic solvent solution of the polyarylate resin. If the polyarylate resin is difficult to dissolve, it may be dissolved by heating.

  The organic solvent for dissolving the polyarylate resin preferably has a boiling point of 180 ° C. or lower, more preferably 150 ° C. or lower. When the boiling point of the organic solvent exceeds 180 ° C., it becomes difficult to completely remove the organic solvent in the solvent removal step, the organic solvent tends to remain in the aqueous dispersion, the storage stability decreases, and the remaining organic Water resistance may be reduced by the solvent. Moreover, it may be difficult to evaporate the organic solvent from the resin film by drying.

  Moreover, it is more preferable that the organic solvent has an azeotropic point with water of 60 to 150 ° C. When the azeotropic point with water exceeds 150 ° C., it becomes difficult to completely remove the organic solvent in the solvent removal step, the organic solvent tends to remain in the aqueous dispersion, the storage stability decreases, and the residue remains. The water resistance may decrease due to the organic solvent. Moreover, it may be difficult to evaporate the organic solvent from the resin film by drying. When the azeotropic point with water is less than 60 ° C., a time difference occurs between volatilization of the azeotrope and volatilization of water, and the film forming property of the resulting resin film may be inferior.

  Furthermore, it is more preferable that the organic solvent has a solubility in water at 20 ° C. of 5 g / L or more. If the solubility of the organic solvent in water is less than 5 g / L, it may not be possible to obtain an aqueous polyarylate resin dispersion.

  Examples of such an organic solvent include ethyl acetate (solubility: about 12 g / L, boiling point: 77.1 ° C., azeotropic point: 70.4 ° C.), n-propanol (solubility: infinite, boiling point: 97 .2 ° C., azeotropic point: 87.7 ° C., isopropanol (solubility: infinite, boiling point: 82.4 ° C., azeotropic point: 80.2 ° C.), methyl ethyl ketone (solubility: minimum about 290 g / L, boiling point: 79.6 ° C., azeotropic point: 73.4 ° C., tetrahydrofuran (solubility: infinity, boiling point: 66.0 ° C., azeotropic point: 64.0 ° C.), 1,4-dioxane (solubility: infinity, Boiling point: 101 ° C., azeotropic point: 87.8 ° C., cyclohexanone (solubility: about 110 g / L, boiling point: 156 ° C., azeotropic point: 95.0 ° C.), ethylene glycol monoethyl ether (solubility: infinite, Boiling point: 136 ° C., azeotropic point with water: 99. ℃), and the like. These may be used alone or in combination.

  The concentration of the polyarylate resin is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, and still more preferably 20 to 50% by mass. By setting the concentration of the polyarylate resin in the solution to 5 to 70% by mass, an increase in viscosity at the time of mixing with water in the next phase inversion emulsification step is suppressed, so the volume average particle size of the aqueous dispersion is It is possible to suppress the increase.

  As an apparatus used in the dissolution step, for example, any apparatus may be used as long as it has a tank into which a liquid can be charged and can be appropriately stirred. Such devices include those known as solid / liquid agitation devices and emulsifiers (eg homomixers).

  In the phase inversion emulsification step, a polyarylate resin dispersion is obtained by dispersing an organic solvent solution of a polyarylate resin in an aqueous medium together with a basic compound. Phase inversion emulsification may be performed under any conditions of normal pressure, reduced pressure, and increased pressure.

  As a method of dispersing the organic solvent solution of the polyarylate resin in the aqueous medium together with the basic compound, for example, the basic compound is added to the organic solvent solution of the polyarylate resin, and the aqueous medium is gradually added thereto. And a method of adding a basic compound in an aqueous medium and gradually adding it to an organic solvent solution of a polyarylate resin. Among these, the latter method is preferable from the viewpoint of preventing non-uniform mixing of the organic solvent solution of the polyarylate resin and the basic compound.

  The basic compound used in the phase inversion emulsification step is preferably one that can neutralize the carboxyl group. Examples of such basic compounds include ammonia, ethylamine, diethylamine, triethylamine, propylamine, isopropylamine, iminobispropylamine, 3-ethoxypropylamine, 3-diethylaminopropylamine, diethanolamine, triethanolamine, N , N-diethylethanolamine, N, N-dimethylethanolamine, aminoethanolamine, morpholine, N-methylmorpholine, N-ethylmorpholine, and other organic amines. Examples of the basic compound include metal hydroxides such as lithium hydroxide, potassium hydroxide, and sodium hydroxide, but the water resistance of the resin film obtained from the aqueous dispersion may be insufficient.

  As the basic compound, a tertiary amine is more preferable because it can suppress the hydrolysis reaction of the polyarylate resin in the aqueous dispersion as much as possible in the production process.

  Furthermore, since it is easy to volatilize a basic compound from a polyarylate resin film, it is more preferable to use a basic compound having a boiling point of 150 ° C. or less. Examples of such basic compounds include ammonia, triethylamine, and N, N-dimethylethanolamine.

  The basic compound is preferably added in an amount of 0.5 to 30 times equivalent, more preferably 1 to 20 times the equivalent of the acid value of the polyarylate resin to be used. By adding 0.5 to 30 equivalents of the basic compound, an aqueous dispersion having good storage stability can be obtained. In addition, there exists a tendency for volume average particle diameter to become small, so that the quantity of a basic compound is large.

  The reaction temperature in the phase inversion emulsification step is preferably 10 to 40 ° C, more preferably 10 to 30 ° C, still more preferably 15 to 30 ° C, and most preferably 15 to 20 ° C. preferable. By setting the reaction temperature to 10 to 40 ° C., it is possible to suppress an increase in the viscosity of the contents during the phase inversion emulsification step, so that a uniform aqueous dispersion having a small volume average particle size and good storage stability. Can be manufactured. In addition, there exists a tendency for a volume average particle diameter to become small, so that the reaction temperature of a phase inversion emulsification process is low.

  The input speed of the aqueous medium in the phase inversion emulsification step is not particularly limited, but the polyarylate resin is adjusted to 25 to 100 parts by mass / min with respect to 1000 parts by mass in total of the polyarylate resin solution and the basic compound. It is possible to facilitate uniform dispersion while suppressing the formation of lumps.

  The solid content concentration of the polyarylate resin dispersion after phase inversion emulsification is preferably 5 to 60% by mass. By setting the solid content concentration within this range, aggregation of the polyarylate resin can be suppressed in the subsequent solvent removal step.

  In the solvent removal step, the polyarylate resin dispersion is heated to remove the organic solvent and / or the basic compound to obtain an aqueous polyarylate resin dispersion. Solvent removal may be performed under normal pressure or reduced pressure.

  The apparatus used for the phase inversion emulsification step and the solvent removal step may be any device that includes a tank into which a liquid can be charged, can be controlled to a temperature within the above-described range, and can be appropriately stirred.

  In the production method of the present invention, a filtration step can be provided after the dispersion step for the purpose of removing foreign substances and the like. In such a case, for example, a 600-mesh stainless steel filter (filtration accuracy: 25 μm, twill weave) may be installed, and atmospheric pressure filtration or pressure (air pressure 0.2 MPa) filtration may be performed. A filtration process may be provided immediately after a dispersion | distribution process, and when providing the above-mentioned solvent removal process, you may provide after a solvent removal process.

  In the production method of the present invention, the basic compound used in the phase inversion emulsification step can be added to the aqueous polyarylate resin dispersion after the solvent removal step. By adding the basic compound again after the solvent removal step, the pH of the aqueous dispersion can be easily adjusted to 6 or more. The basic compound is preferably added gradually while the aqueous dispersion is stirred. If the aqueous dispersion is added without stirring or a basic compound is added all at once, the polyarylate resin in the aqueous dispersion may aggregate and precipitate due to the impact of the addition.

  Next, a method for using the aqueous dispersion of the present invention will be described.

  Examples of the method for forming the resin film of the present invention include a gravure coating method, a Mayer bar coating method, a dipping method, a brush coating method, a spray coating method, and a curtain flow coating method. By uniformly coating the surface of various substrates by these methods, setting it at around room temperature as necessary, and then subjecting it to heat treatment for drying and baking, the uniform resin film is adhered to the surface of various substrates. Can be formed. As a heating device at this time, a normal hot air circulation oven, an infrared heater, or the like may be used. In addition, the heating temperature and the heating time are appropriately selected depending on the type of substrate to be coated, etc. In consideration of economy, the heating temperature is usually 60 to 250 ° C., 70 It is preferable to set it to -230 degreeC, and it is more preferable to set it as 80-200 degreeC. The heating time is usually 1 second to 30 minutes, preferably 5 seconds to 20 minutes, and more preferably 10 seconds to 10 minutes.

  In the polyarylate resin aqueous dispersion used in the present invention, water, an organic solvent, various curing agents, various additives, other water-based polyester resins, water-based urethane resins, water-based olefin resins, as long as the effects of the present invention are not impaired. An aqueous resin such as an aqueous acrylic resin may be blended.

  As water, any of distilled water, ion exchange water, city water, and industrial water can be used.

  Examples of the organic solvent include alcohols such as methanol, ethanol, n-propanol, and isopropanol.

  The curing agent is not particularly limited as long as it is a curing agent reactive with a functional group possessed by the polyarylate resin, such as a carboxyl group, its anhydride, and a hydroxyl group. Examples of such curing agents include amino resins such as urea resins, melamine resins, and benzoguanamine resins, polyfunctional epoxy compounds, polyfunctional isocyanate compounds, and various block isocyanate compounds, polyfunctional aziridine compounds, carbodiimide group-containing compounds. , An oxazoline group-containing polymer, and a phenol resin. These may be used alone or in combination.

  Examples of additives include repellency inhibitors, leveling agents, antifoaming agents, anti-waxing agents, rheology control agents, pigment dispersants, ultraviolet absorbers, and lubricants.

  The aqueous dispersion of the present invention is superior in storage stability compared to conventional ones, can be stored for a long period of time, and the resin film obtained therefrom has high hardness, film-forming property, adhesion, Since it is excellent in alcohol resistance, transparency and heat resistance, it can be suitably used as a surface coating agent for touch panels.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. The evaluation and measurement methods are as follows.

(1) Configuration of polyarylate resin By using ¹ H-NMR analysis using a high resolution nuclear magnetic resonance apparatus (manufactured by JEOL Ltd., ECA500 NMR), the resin composition was obtained from the peak intensity of each copolymer component. (Resolution: 500 MHz, solvent: deuterated trifluoroacetic acid, temperature: 25 ° C.). In addition, with respect to a resin containing a constituent monomer in which no assignable / quantifiable peak is observed on the ¹ H-NMR spectrum, it is subjected to methanol decomposition at 230 ° C. for 3 hours in a sealed tube, followed by gas chromatogram analysis for quantitative analysis. I did it.

(2) Acid value of polyarylate resin 0.5 g of polyarylate resin was precisely weighed and dissolved in 50 mL of water / 1,4-dioxane = 1/9 (volume ratio) at room temperature, and 0.1N using cresol red as an indicator. The number of mg of potassium hydroxide per 1 g of polyarylate resin consumed for neutralization (mg KOH / g) was defined as the acid value.

(3) Number average molecular weight and weight average molecular weight of polyarylate resin The number average molecular weight and weight average molecular weight in terms of polystyrene were measured under the following conditions using gel permeation chromatography (GPC).
Liquid feeding unit: LC-10ADvp manufactured by Shimadzu Corporation
Ultraviolet-visible spectrophotometer: SPD-6AV manufactured by Shimadzu Corporation, detection wavelength: 254 nm
Column: one Shodex KF-803 and two Shodex KF-804s connected in series Solvent: tetrahydrofuran Measurement temperature: 40 ° C

(4) Glass transition temperature of polyarylate resin 10 mg of polyarylate resin was used as a sample, and the temperature was raised using an input-compensated differential scanning calorimeter (Perkin Elmer, Diamond DSC, detection range: −50 to 200 ° C.). Measure at a rate of 10 ° C / min. In the obtained temperature rise curve, the straight line extending the low temperature side base line to the high temperature side and the slope of the step change part of the glass transition will be maximized. The temperature at the point of intersection with the tangent line drawn at a certain point was determined and used as the glass transition temperature.

(5) Solvent solubility of polyarylate resin 10 g of polyarylate resin and 90 g of methyl ethyl ketone (MEK) were mixed and stirred at 40 ° C. for 2 hours. After stirring, the solution state was visually observed and evaluated according to the following criteria.
A: The polyarylate resin was completely dissolved.
X: The polyarylate resin was not completely dissolved.
Further, MEK was changed to tetrahydrofuran (THF), and evaluation was performed in the same manner.

(6) Solid Concentration of Polyarylate Resin Aqueous Dispersion About 1 g of polyarylate resin aqueous dispersion was weighed (X ₁ g), and this was dried at 150 ° C. for 2 hours to weigh the residual mass. (Y ₁ g), and the solid content concentration was determined by the following equation.
Solid content concentration (% by mass) = (Y ₁ / X ₁ ) × 100

(7) pH of polyarylate resin aqueous dispersion
Using a pH meter (F-21, manufactured by Horiba, Ltd.), the pH of the polyarylate resin aqueous dispersion was measured at a measurement temperature of 25 ° C. after calibrating with standard buffer solutions of pH 7 and pH 9 (manufactured by Nacalai Tesque).

(8) Volume average particle size and number average particle size of polyarylate resin Dilute with water so that the concentration of polyarylate resin in the aqueous dispersion of polyarylate resin is 0.1% by mass, and measure laser diffraction particle size The volume average particle diameter and the number average particle diameter were measured using an apparatus (manufactured by Nikkiso Co., Ltd., MICROTRAC UPA (model 9340-UPA)). The refractive index of the polyarylate resin was set to 1.61, and the density of the polyarylate resin was set to 1.21 g / cm ³ .

(9) Storage stability of aqueous polyarylate resin dispersion 30 g of an aqueous polyarylate resin dispersion was sealed in a 50 mL glass sample bottle and stored at 25 ° C. for 180 days. After storage, the supernatant was collected from the sample bottle, the solid content concentration was measured, the ratio of the precipitated polyarylate resin was calculated by the following formula, and evaluated according to the following criteria.
Ratio of precipitated polyarylate resin (mass%) = {solid content concentration before storage (mass%) − solid content concentration after storage (mass%)} / {solid content concentration before storage (mass%)}
◎: Less than 0.1% by mass ○: 0.1% by mass or more and less than 0.5% by mass Δ: 0.5% by mass or more and less than 1.0% by mass ×: 1.0% by mass or more

(10) Film-forming property of resin coating A polyarylate resin aqueous dispersion is coated on a corona-treated surface of a biaxially stretched PET film (manufactured by Unitika Ltd., thickness 38 μm) on a desktop coating apparatus (manufactured by Yasuda Seiki Co., Ltd., film applicator). No. 542-AB type, equipped with a bar coater), and then dried for 1 minute in a hot air dryer set at 130 ° C. to form a resin film having a thickness of 3 μm.
The resin film was visually observed, and whether or not there were appearance defects such as cracks, fine irregularities, and whitening was evaluated according to the following criteria.
A: Appearance defect is not seen.
X: Appearance defect is seen.

(11) Adhesiveness of resin film Adhesive tape (width 18mm) specified in JIS Z1522 is applied to the resin film except for the end to the resin film obtained in (10), and then rubbed with an eraser. After sufficient adhesion, the end of the adhesive tape was made perpendicular to the film and then peeled off instantaneously. By analyzing the peeled surface of the adhesive tape using a surface infrared spectrometer (using a Perkin-Elmer SYSTEM2000, Ge60 ° 50 × 20 × 2 mm prism), a peak derived from the resin film is formed on the surface of the adhesive tape. The following criteria evaluated whether it was seen.
(Double-circle): A peak is not recognized.
X: A peak is recognized.

(12) Alcohol resistance of resin coating The PET film having the resin coating obtained in (10) was immersed in distilled water at 25 ° C., gently pulled up after 30 minutes, and allowed to air dry.
The resin film was visually observed and evaluated according to the following criteria.
A: No change in appearance.
○: Although the surface state was changed (the surface was clouded white, etc.), the resin film did not dissolve or swell.
X: The resin film was dissolved or swollen.

(13) Transparency of resin coating For the PET film having the resin coating obtained in (10), the total light transmittance in the visible light region is measured using Z-Σ90, Color Measuring System manufactured by Nippon Denshoku Industries Co., Ltd. did. In addition, as a blank, the PET film which has not given the resin film was used.
The total light transmittance is preferably 95% or more, and more preferably 99% or more.

(14) Heat-resistant retention of resin coating Polyarylate resin aqueous dispersion is applied to SUS304 (0.5 mm thickness) surface with a desktop coating device (Yasuda Seiki Co., Ltd., film applicator No. 542-AB type, bar coater mounted) After coating using, a resin film having a film thickness of 3 μm was formed by drying for 1 minute in a hot air dryer set at 150 ° C.
Next, two test plates having a width of 30 mm and a length of 100 mm were cut out and heated in an oven set at 320 ° C. until the surface of the test plate reached 250 ° C. Was pressure-bonded using a roll laminator so that the adhesion area was 30 mm × 30 mm. According to JIS Z1541, after standing in standard condition for 72 hours, leave it in an 80 ° C hot air circulating thermostat for 10 minutes, put a weight of 1 kg at the same temperature, and drop after 7 days The heat-resistant holding force was evaluated based on the presence or absence of.
(Double-circle): It did not fall.
X: It fell.

(15) Hardness of resin film Using the high-grade pencil specified in JIS S-6006, the pencil hardness of the resin film is measured in accordance with JIS K5600-5-4 with respect to the resin film obtained in (10). did.
The pencil hardness is preferably H or higher, and more preferably 2H or higher.

Example 1
In a reaction vessel equipped with a stirrer, 7.94 g of BisAF as a dihydric phenol component, 2.60 g of resorcinol (RC), 2.69 g of BisA, and 7.08 g of sodium hydroxide as an alkali (of dihydric phenol) When the total molar amount is 1, it corresponds to 3 times the molar amount), and 2.45 g (6.7 mol%) of tri-n-butylbenzylammonium chloride was charged as a polymerization catalyst and dissolved in 406 mL of water (aqueous phase) ). Separately, 5.99 g of terephthalic acid chloride (TPC) and 5.99 g of isophthalic acid chloride (IPC) were dissolved in 255 mL of dichloromethane (organic phase) (aqueous phase). Separately, in 255 mL of dichloromethane, terephthalic acid chloride (TPC / IPC / BisAF / RC / BisA = 50/50/40/40/20 (molar ratio)) The aqueous phase was previously stirred at 400 rpm, While maintaining the number of stirring, the organic phase was added to the aqueous phase at 20 mL / second, and polymerization was carried out by interfacial polymerization at 15 ° C. for 4 hours. After removing the aqueous phase, the reaction was stopped by adding 100 mL of dichloromethane, 800 mL of pure water and 2 mL of acetic acid, and stirred for 30 minutes at 15 ° C. Then, until the organic phase became neutral, After washing with pure water added and stirring, the organic phase was added to 1500 mL of methanol to precipitate the polymer, followed by stirring for another 30 seconds after dropping the whole amount. The resin was separated, 80 ° C., 12 hours drying under reduced pressure at 13 Pa, to obtain a polyarylate resin.

  By putting the obtained polyarylate resin 150 g and 350 g of MEK into a glass container with a jacket, and stirring with a stirrer (Mazela 1000, manufactured by Tokyo Rika Kikai Co., Ltd.) while heating the jacket through 60 ° C hot water, A polyarylate resin was dissolved in MEK to obtain 500 g of a resin solution having a solid concentration of 30% by mass. Next, 2.6 g of triethylamine (15 times equivalent to the acid value of the polyarylate resin) was added as a basic compound while keeping the system temperature at 13 ° C. through a jacket and stirring at a rotation speed of 600 rpm. Subsequently, 471 g of distilled water at 13 ° C. was added at a rate of 100 g / min to carry out phase inversion emulsification. Next, 800 g of the obtained aqueous dispersion was put into a 1 L flask, and the organic solvent was distilled off by distillation under normal pressure. Distillation ended when the amount of distillate reached 403 g, and after cooling to room temperature, 0.5 g of 28% by weight ammonia water was added while stirring the resulting aqueous dispersion, and then distilled water was added while stirring. The solid content concentration was adjusted to 30% by mass and filtered through a 1000 mesh stainless steel filter to obtain a polyarylate aqueous dispersion having a solid content concentration of 30% by mass.

Examples 2 and 3
A polyarylate resin was produced in the same manner as in Example 1 except that the monomers shown in Table 1 were used, and the resulting polyarylate resin was made water-like in the same manner as in Example 1 to produce poly An aqueous arylate dispersion was obtained.

Example 4
Except for using the monomers shown in Table 1 and changing the amount of triethylamine to 5.3 g (15 times equivalent to the acid value of the polyarylate resin), the same procedure as in Example 1 was followed. Production and aqueousization were carried out to obtain an aqueous polyarylate dispersion.

Example 5
Same as Example 1 except that the monomers shown in Table 1 are used, the organic solvent is THF, and the amount of triethylamine is changed to 2.8 g (15 times equivalent to the acid value of the polyarylate resin). By the above operations, the polyarylate resin was produced and made water-based to obtain an aqueous polyarylate dispersion.

Examples 6-9
Other than using the monomers shown in Table 1 and changing the amount of triethylamine to 2.4 g, 2.4 g, 2.7 g, 2.8 g (15 times equivalent to the acid value of polyarylate resin), respectively. In the same manner as in Example 1, a polyarylate resin was produced and made aqueous to obtain a polyarylate aqueous dispersion.

Comparative Example 1
Example except that the monomers shown in Table 1 were used, the amount of triethylamine was changed to 17.0 g (15 times equivalent to the acid value of the polyarylate resin), and the amount of distilled water was changed to 457 g. In the same manner as in No. 1, polyarylate resin was produced and made water-based to obtain an aqueous polyarylate dispersion.

Comparative Examples 2, 3, 9
Except that the monomers shown in Table 1 were used and the organic solvent was changed to THF, the polyarylate resin was produced and made aqueous by the same operations as in Example 1 to obtain an aqueous polyarylate dispersion. Since polyarylate resin could not be completely dissolved in THF, triethylamine was added in a dispersed state.

Comparative Example 4
Except for using the monomers shown in Table 1, a polyarylate aqueous dispersion was obtained by the same procedure as in Example 1 to produce a polyarylate resin and make it water-based. Since polyarylate resin could not be completely dissolved in MEK, triethylamine was added in a dispersed state.

Comparative Example 5
Except that the monomers shown in Table 1 were used and the organic solvent was changed to THF, the polyarylate resin was produced and made aqueous by the same operations as in Example 1 to obtain an aqueous polyarylate dispersion. However, many aggregates were observed in the obtained aqueous polyarylate resin dispersion.

Comparative Example 6
Except for using the monomers shown in Table 1 and changing the amount of triethylamine to 2.4 g (15 times equivalent to the acid value of the polyarylate resin), the same procedure as in Example 1 was followed. Production and aqueousization were carried out to obtain an aqueous polyarylate dispersion.

Comparative Example 7
Except for using the monomers shown in Table 1 and changing the amount of triethylamine to 2.5 g (15 times equivalent to the acid value of the polyarylate resin), the same procedure as in Example 1 was followed. Production and aqueousization were carried out to obtain an aqueous polyarylate dispersion.

Comparative Example 8
Except for using the monomers shown in Table 1, a polyarylate aqueous dispersion was obtained by the same procedure as in Example 1 to produce a polyarylate resin and make it water-based.

  Various evaluation was performed about the polyarylate resin aqueous dispersion obtained from Examples 1-9 and Comparative Examples 1-9, and the resin film obtained from it. The results are shown in Table 3.

In Table 1, abbreviations indicate the following.
TPC: terephthalic acid chloride IPC: isophthalic acid chloride BisAF: 4,4 ′-(hexafluoroisopropylidene) diphenol RC: resorcinol BisA: 2,2-bis (4-hydroxyphenyl) propane BisS: bis (4-hydroxyphenyl) ) Sulfone MEK: methyl ethyl ketone THF: tetrahydrofuran

  Each of the aqueous dispersions of Examples 1 to 8 has a storage stability of 3 months or more, and the resin coating obtained from the aqueous dispersion has film-forming properties, adhesion, transparency, and alcohol resistance. , Excellent in hardness and heat resistance. In addition, since the resin coating is obtained from an aqueous dispersion, the burden on the environment is small.

  In the aqueous dispersion of Comparative Example 1, the acid value of the polyarylate resin used exceeded 40 mgKOH / g. Therefore, the obtained resin film had poor adhesion and low hardness. Further, the film forming property was poor.

  In the aqueous dispersions of Comparative Examples 2 and 9, the TPA / IPA content ratio (molar ratio) of the aromatic dicarboxylic acid component of the polyarylate resin used was outside the range of 60/40 to 40/60. Therefore, the solvent solubility of the polyarylate resin was poor, and the storage stability of the obtained aqueous dispersion was poor. Further, the film forming property was poor.

  In the aqueous dispersion of Comparative Example 3, the content of BisAF in the dihydric phenol component of the polyarylate resin used was less than 20 mol% of the total dihydric phenol component. Therefore, the solvent solubility of the polyarylate resin was poor, and the storage stability of the obtained aqueous dispersion was poor. Further, the film forming property was poor.

  In the aqueous dispersion of Comparative Example 4, the content of resorcinol in the dihydric phenol component of the polyarylate resin used was less than 20 mol% of the total dihydric phenol component. Therefore, the hardness of the obtained resin film was low.

  In the aqueous dispersion of Comparative Example 5, the acid value of the polyarylate resin was less than 4 mgKOH / g. Therefore, the solvent solubility of the polyarylate resin was poor, and the storage stability of the obtained aqueous dispersion was poor.

  In the aqueous dispersion of Comparative Example 6, the content of BisAF in the dihydric phenol component of the polyarylate resin used exceeded 50 mol% of the total dihydric phenol component. Therefore, the obtained resin film had poor alcohol resistance.

  In the aqueous dispersion of Comparative Example 7, the content of resorcinol in the dihydric phenol component of the polyarylate resin used exceeded 50 mol% of the total dihydric phenol component. Therefore, the obtained resin film had low hardness and poor film forming property.

  Comparative Example 8 is a trial of Example 3 of Cited Document 2. The aqueous dispersion of Comparative Example 8 did not contain resorcinol in the dihydric phenol component of the polyarylate resin used. Therefore, the solvent solubility of the polyarylate resin was poor, and the storage stability of the obtained aqueous dispersion was poor. Further, the film forming property was poor.

Claims (4)

An aqueous polyarylate resin dispersion comprising a polyarylate resin composed of an aromatic dicarboxylic acid component and a dihydric phenol component and satisfying the following (i) to (iii), a basic compound and water, and containing substantially no emulsifier.
(I) The aromatic dicarboxylic acid component contains terephthalic acid (TPA) and isophthalic acid (IPA) as main components, and TPA / IPA = 60/40 to 40/60 (molar ratio).
(Ii) As the dihydric phenol component, 20 to 50 mol% of 4,4 ′-(hexafluoroisopropylidene) diphenol and 20 to 50 mol% of resorcinol are contained.
(Iii) Acid value is 4-40 mgKOH / g. The polyarylate resin aqueous dispersion according to claim 1, wherein the polyarylate resin has a glass transition temperature of 150 ° C or higher. The polyarylate resin aqueous dispersion according to claim 1 or 2, wherein the polyarylate resin has a weight average molecular weight of 10,000 or more. The resin film obtained by apply | coating and drying the polyarylate resin aqueous dispersion in any one of Claims 1-3.