WO2014050776A1 - Organosiloxane-copolymerized resin, and resin mixture, resin solution, coating film and film each produced using said resin - Google Patents

Abstract

A resin produced by copolymerizing an organosiloxane according to the present invention contains a specific bisphenol residue containing a fluorine atom, a specific aromatic dicarboxylic acid residue and a specific organosiloxane residue. The resin has an inherent viscosity of 0.90 dL/g or less as measured in 1,1,2,2-tetrachloroethane at a temperature of 25˚C at a concentration of 1 g/dL. When the resin is heated at 180˚C for 10 minutes, the amount of a siloxane-containing component that is volatilized from the resin is 700 ppm by mass or less.

Description

Organosiloxane copolymer resin and resin mixture, resin solution, coating film and film using the same

The present invention relates to an organosiloxane copolymer resin, and a resin mixture, a resin solution, a coating film, and a film using the same.

Conventionally, polyarylate resins containing bisphenol residues and aromatic dicarboxylic acid residues are well known as engineering plastics. In particular, a polyarylate resin comprising 2,2-bis (4-hydroxyphenyl) propane [bisphenol A], terephthalic acid and isophthalic acid has high transparency and heat resistance, and is a machine represented by impact strength. Excellent in mechanical strength and dimensional stability. For this reason, polyarylate resins are widely used in molded products used in the automobile and electrical / electronic fields. Polyarylate resins are used for films and the like by taking advantage of their excellent transparency and heat resistance.

By the way, in order to impart water repellency to the polyarylate resin, a bisphenol component, terephthalic acid and isophthalic acid are copolymerized with a siloxane component to obtain an organosiloxane copolymer resin containing the siloxane component in the polyarylate resin. Has been proposed (Patent Document 1).

JP 2009-46667 A

However, when a solution of an organosiloxane copolymer resin is applied to a substrate, bubbles are more likely to be generated than the applied resin solution, and the generated bubbles are difficult to disappear and handling properties are reduced.
In addition, a coating film obtained by applying the resin solution to a substrate has low surface smoothness, and minute voids are easily formed. As a result, the adhesion between the coating film and the substrate is lowered, and the coating film is easily peeled off from the substrate.

In the organosiloxane copolymer resin, a volatile component containing a low molecular weight siloxane (decomposition product generated in the resin production process, organosiloxane that did not contribute to the copolymerization, etc.) remains. When the amount of the volatile component is large, a bleed out occurs in the coating film formed by applying the resin solution to the substrate, thereby causing a problem that the peripheral members are contaminated. Therefore, in electronic material use and food use, it has been required to reduce the content of volatile components in the resin.
However, since the above volatile component acts as an antifoaming agent, if the volatile component is reduced in order to prevent the occurrence of bleeding out, the above-described foaming is likely to occur.
For this reason, it was difficult to simultaneously realize the suppression of the occurrence of the bleed-out and the suppression of the generation of the bubbles.

Furthermore, the resin used in the food packaging body is required to appropriately release moisture generated from the contents of the packaging body in order to extend the shelf life of the food, and is required to have high strength and high water vapor permeability. ing.

Therefore, in order to solve the above problems, the present invention suppresses the generation of bubbles when used as a resin solution, and is excellent in strength, heat resistance, adhesion, surface smoothness, and water vapor permeability, It aims at providing the organosiloxane copolymer resin which can form the coating film or film in which generation | occurrence | production is suppressed. Moreover, it aims at providing the resin mixture, resin solution, coating film, and film using the organosiloxane copolymer resin.

As a result of intensive studies to solve the above problems, the present inventors have found that the following organosiloxane copolymer resin has a specific bisphenol residue containing a fluorine atom, a specific aromatic carboxylic acid residue, When a specific organosiloxane residue is included, the inherent viscosity is in a specific range, and the amount of siloxane-containing volatile components contained in the resin is reduced to a specific range, the generation of bubbles when used as a resin solution The present inventors have found that it is possible to form a coating film or a film that is suppressed and excellent in strength, heat resistance, adhesion, surface smoothness, and water vapor permeability and in which the occurrence of bleed out is suppressed.

The gist of the present invention is as follows.
[1] A resin containing a bisphenol residue represented by the general formula (1), an aromatic dicarboxylic acid residue represented by the general formula (2), and an organosiloxane residue represented by the general formula (3) ,
Inherent viscosity measured at a temperature of 25 ° C. and a concentration of 1 g / dL in 1,1,2,2-tetrachloroethane of the resin is 0.90 dL / g or less,
An organosiloxane copolymer resin characterized in that when the resin is heated at 180 ° C. for 10 minutes, the amount of the siloxane-containing component volatilized from the resin is 700 ppm by mass or less.

 

In formula (1), R ¹ and R ² independently represent a hydrocarbon group having 1 to 6 carbon atoms, a halogenated alkyl group, or a halogen atom. p and q independently represent an integer of 0 to 4. X represents a divalent group containing a fluorine atom.

 

 

In formula (3), R ³ and R ⁴ independently represent an aliphatic group and / or an aromatic group, and may contain a nitrogen atom or an oxygen atom. R ⁵ , R ⁶ , R ⁷ , and R ⁸ independently represent an aliphatic group or an aromatic group. m represents a number of 5 or more.

[2] The organosiloxane copolymer resin according to [1], wherein the content of the organosiloxane residue represented by the general formula (3) in the resin is more than 7% by mass and less than 80% by mass. .
[3] The organo described in [1] or [2], wherein the bisphenol residue represented by the general formula (1) is a 2,2-bis (4-hydroxyphenyl) hexafluoropropane residue Siloxane copolymer resin.

[4] The aromatic dicarboxylic acid residue represented by the general formula (2) is a mixture of a terephthalic acid residue and an isophthalic acid residue,
The molar ratio of terephthalic acid residue to isophthalic acid residue in the mixture: terephthalic acid / isophthalic acid is 90/10 to 10/90, according to any one of [1] to [3] Organosiloxane copolymer resin.

[5] A resin mixture obtained by mixing the organosiloxane copolymer resin according to any one of [1] to [4] and a resin other than the organosiloxane copolymer resin.
[6] The resin mixture according to [5], wherein the resin other than the organosiloxane copolymer resin is a resin containing a bisphenol residue represented by the general formula (4) or (5).

 

In formula (4), R ⁹ and R ¹⁰ independently represent an aliphatic group having 1 to 12 carbon atoms. r and s independently represent an integer of 1 to 4.

 

In formula (5), R ¹¹ , R ¹² and R ¹³ independently represent an aliphatic group having 1 to 12 carbon atoms. t and u each independently represents an integer of 0 to 4. v represents an integer of 0 to 10.

[7] The resin mixture as described in [6], wherein the bisphenol residue represented by the general formula (4) is a 2,2-bis (3-methyl-4-hydroxyphenyl) propane residue.
[8] The resin mixture as described in [6], wherein the bisphenol residue represented by the general formula (5) is a 1,1-bis (4-hydroxyphenyl) cyclohexane residue.

[9] The organosiloxane copolymer resin according to any one of [1] to [4] or the resin mixture according to any one of [5] to [8] is dissolved in an organic solvent. Resin solution.

[10] A coating film formed using the resin solution according to [9].
[11] The coating film according to [10], wherein the arithmetic average roughness Ra of the surface is 0.5 μm or less.
[12] A film formed using the resin solution according to [9].
[13] The film according to [12], wherein the arithmetic average roughness Ra of the surface is 0.5 μm or less.

According to the present invention, the generation of bubbles when used as a resin solution is suppressed, and the coating film or the coating is excellent in strength, heat resistance, adhesion, surface smoothness, and water vapor permeability, and generation of bleed out is suppressed. An organosiloxane copolymer resin capable of forming a film can be provided.

Even if the amount of the siloxane-containing volatile component contained in the organosiloxane copolymer resin is reduced to a specific range, the organosiloxane copolymer resin has a specific bisphenol residue containing a fluorine atom and a specific aromatic carboxylic acid residue. And a specific organosiloxane residue, and if the inherent viscosity is in a specific range, the coating film is excellent in strength, heat resistance, adhesion, surface smoothness, and water vapor permeability and suppresses the occurrence of bleed out. Or while being able to form a film, it is possible to suppress generation | occurrence | production of the bubble at the time of using as a resin solution.
Furthermore, the organosiloxane copolymer resin of the present invention can be improved in mechanical strength by being used in combination with other specific resins.

Since the organosiloxane copolymer resin of the present invention and the mixture of the resin and other specific resin are excellent in water vapor permeability, for example, a protective film or a substrate film used in each member of a liquid crystal display or a plasma display, It is suitably used as a food packaging material.
In addition, since the organosiloxane copolymer resin of the present invention and a mixture of the resin and another specific resin are excellent in electrical characteristics, for example, a film or film for electronic parts such as a transformer or a capacitor, electrophotographic photosensitive resin, etc. It is suitably used for body binder resin, conductive film substrate, and diaphragm film for acoustic equipment.

Mode for carrying out the present invention

Hereinafter, the present invention will be described in detail.
The present invention is a resin copolymerized with an organosiloxane, and a resin containing a bisphenol residue and an aromatic dicarboxylic acid residue constituting the polyarylate resin and an organosiloxane residue (hereinafter referred to as resin A). )

The bisphenol residue needs to have a structure represented by the general formula (1).

 

In general formula (1), X must be a divalent group containing a fluorine atom.
In general formula (1), when X is a divalent group containing a fluorine atom, generation of bubbles when used as a solution containing resin A is suppressed, and strength, heat resistance, adhesion, and surface are reduced. A coating film or film having excellent water vapor permeability can be obtained without impairing the effect of obtaining a coating film or film having excellent smoothness and suppressing bleeding out.
The divalent group containing a fluorine atom has, for example, a structure represented by the general formula (1a).

 

In general formula (1a), R ^1a and R ^2a independently represent a trifluoromethyl group (CF ₃ group), a difluoromethyl group (CF ₂ H group), a monofluoromethyl group (CH ₂ F group), or It is a fluorine atom. Among these, it is preferable that R ^1a and R ^2a are trifluoromethyl groups.

R ¹ and R ² represent a substituent bonded to the benzene ring in the general formula (1).
In the general formula (1), R ¹ and R ² are each independently a compound having a carbon number of 1 to ² because the bisphenol giving the structure represented by the general formula (1) is industrially easily available or easily synthesized. 6 hydrocarbon group, halogenated alkyl group or halogen atom. Among these, a chlorine atom, a bromine atom, a methyl group, an ethyl group, a phenyl group, and a cyclohexyl group are preferable, and a bromine atom and a methyl group are more preferable.

p and q represent the number of substituents R ¹ and R ² bonded to the benzene ring, respectively, and are each independently an integer of 0 to 4. For example, if p and q is 0, indicating that all of the hydrogen atoms bonded to the benzene ring in the general formula (1) is not substituted with R ¹ and R ^2. When p is 2 to 4, a plurality of R ¹ may be the same or different from each other. When q is 2 to 4, the plurality of R ² may be the same or different from each other. Since bisphenol giving the structure represented by the general formula (1) is easily industrially available or easily synthesized, p and q are preferably 0.

Examples of the bisphenol that gives the structure represented by the general formula (1) include 2,2-bis (4-hydroxyphenyl) hexafluoropropane [BisAF], 2,2-bis (3,5-dimethyl-4-hydroxy). Phenyl) hexafluoropropane and 2,2-bis (tetramethyl-4-hydroxyphenyl) hexafluoropropane. BisAF is more preferable from the viewpoint of industrial availability. In the case of using BisAF, in the general formula (1), p = 0, q = 0, and X = —C (CF ₃ ) ₂ —.

In the present invention, the bisphenol residue may contain a residue of bisphenol other than bisphenol which gives the structure of the general formula (1) as long as the effects of the present invention are not impaired. Examples of bisphenols that give such residues include 2,2-bis (4-hydroxyphenyl) propane [BisA], 2,2-bis (3-methyl-4-hydroxyphenyl) propane [BisC], 9 , 9-bis (4-hydroxy-3-methylphenyl) fluorene [BCF], 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl)- 1-phenylethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) ethane, 1,1-bis (3-methyl-4-hydroxyphenyl) ethane, bis (4-hydroxyphenyl) methane, bis (3,5-dimethyl) 4-hydroxyphenyl) methane, bis (3-methyl-4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) hexane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) Hexane is mentioned.

From the viewpoint of water vapor permeability, the ratio of the bisphenol residue represented by the general formula (1) to the entire bisphenol residue is preferably 80 mol% or more, and more preferably 100 mol%.

The aromatic dicarboxylic acid residue needs to have a structure represented by the general formula (2).

 

The heat resistance can be improved by having the structure represented by the general formula (2).

Examples of the aromatic dicarboxylic acid that gives the structure represented by the general formula (2) include terephthalic acid, isophthalic acid, and orthophthalic acid. From the viewpoint of high reactivity, it is preferable to use terephthalic acid and isophthalic acid in combination. From the viewpoint of the stability of the resin solution, the molar ratio of terephthalic acid residue to isophthalic acid residue: terephthalic acid / isophthalic acid is preferably 90/10 to 10/90, more preferably 30/70 to 70/30. It is.

In the present invention, the aromatic dicarboxylic acid residue may contain a residue of an aromatic dicarboxylic acid other than the aromatic dicarboxylic acid that gives the structure of the general formula (2) as long as the effects of the present invention are not impaired. Good. Examples of aromatic dicarboxylic acids that give such residues include 2,6-naphthalenedicarboxylic acid, bis (p-carboxyphenyl) alkane diphenate, diphenyl ether-2,2′-dicarboxylic acid, diphenyl ether-2,3 Aromatic dicarboxylic acids such as' -dicarboxylic acid, diphenyl ether-2,4'-dicarboxylic acid, diphenyl ether-3,3'-dicarboxylic acid, diphenyl ether-3,4'-dicarboxylic acid, diphenyl ether-4,4'-dicarboxylic acid Is mentioned.

The resin A of the present invention needs to have an organosiloxane residue represented by the general formula (3).

 

By having an organosiloxane residue represented by the general formula (3), water vapor permeability and adhesion can be imparted.

In the general formula (3), R ³ and R ⁴ are independently an aliphatic group and an organosiloxane that gives a structure represented by the general formula (3) is industrially available or easily synthesized. / Or an aromatic group. R ³ and R ⁴ may contain a nitrogen atom or an oxygen atom. R ³ and R ⁴ preferably contain a divalent group represented by the general formula (6). These divalent groups may be directly bonded to the silicon atom, or may be bonded to the silicon atom via an aromatic group and / or an aliphatic group having 1 to 5 carbon atoms.

 

Since versatility is high, R ³ and R ⁴ are preferably a substituent represented by the general formula (7) or (8). In the general formula (3), the substituent of the general formula (7) or (8) is arranged so that —O— in the general formula (7) or —NH— in the general formula (8) is terminated. .

 

 

In the general formula (7), R ¹⁴ is a hydrocarbon group having 1 to 6 carbon atoms, R ¹⁵ is an aliphatic group having 1 to 5 carbon atoms, and w is an integer of 0 to 4 is there. When w is an integer of 2 to 4, the plurality of R ¹⁴ may be the same or different from each other.
In the general formula (8), R ¹⁶ is an aliphatic group having 1 to 5 carbon atoms.

In the general formula (3), R ⁵ , R ⁶ , R ⁷ , and R ⁸ are independently selected because the organosiloxane giving the structure represented by the general formula (3) is easily industrially available or easily synthesized. And an aliphatic group or an aromatic group. Examples of the aromatic group used in R ⁵ , R ⁶ , R ⁷ , and R ⁸ include a phenyl group. The aliphatic group used in R ⁵ , R ⁶ , R ⁷ , and R ⁸ has, for example, 1 to 6 carbon atoms.

In general formula (3), m represents the number of repeating organosiloxane residues. Organosiloxane is a mixture of components having different repeating numbers, and m represents an average value of the mixture. m must be a number of 5 or more, preferably 10 to 250, and more preferably 20 to 100. When m is 5 or more, heat resistance and water vapor permeability are sufficiently obtained. When m is 250 or less, the mechanical strength and solubility of the resin can be sufficiently obtained.
For example, m in the general formula (3) can be adjusted by changing the compounding ratio of the cyclic dimethylsiloxane and the terminal group.

From the viewpoint of moderate handling properties of the resin A, the content of the organosiloxane residue represented by the general formula (3) in the resin A is preferably more than 7% by mass and less than 80% by mass. When the content of the organosiloxane residue is more than 7% by mass, water vapor permeability can be further improved. On the other hand, when the content of the organosiloxane residue is less than 80% by mass, the mechanical strength and heat resistance of the resin can be further increased. The content of the organosiloxane residue represented by the general formula (3) in the resin A is more preferably 10 to 75% by mass, further preferably 10 to 60% by mass, and 10 to 25% by mass. It is particularly preferred that

The inherent viscosity of the resin A of the present invention measured in 1,1,2,2-tetrachloroethane at a temperature of 25 ° C. and a concentration of 1 g / dL must be 0.9 dL / g or less. 8 dL / g or less is preferable, and 0.7 dL / g or less is more preferable.
If the inherent viscosity exceeds 0.9 dL / g, the resin A solution tends to foam and the surface smoothness of the coating film or film decreases. The inherent viscosity of the resin A can be controlled, for example, by changing the amount of an end-capping agent to be described later.

When the resin A is heated at 180 ° C. for 10 minutes, the amount of the siloxane-containing component that volatilizes from the resin A (hereinafter referred to as siloxane-containing volatile component) needs to be 700 mass ppm or less, and 500 mass. It is preferably not more than ppm, and more preferably not more than 200 mass ppm. The siloxane-containing volatile component mentioned here is a decomposition product of resin A or a siloxane component having a structure represented by general formula (1) contained in resin A (a low-molecular siloxane component that does not contribute to copolymerization) and its decomposition product. including.
When the amount of the siloxane-containing volatile component exceeds 700 ppm by mass, the adhesiveness of the coating film obtained by applying the resin solution is lowered, or bleeding out of the volatile component occurs in the coating film or film. In addition, the elongation at break may decrease over time. The amount of the siloxane-containing volatile component can be adjusted by, for example, the degree of washing of the precipitate obtained by the interfacial polymerization method.

The sodium remaining in the resin A of the present invention is preferably 10 ppm by mass or less. If the amount of residual sodium exceeds 10 ppm by mass, the electrical properties of the resin A may deteriorate.

From the viewpoint of the solubility of the resin A, the stability of the resin solution, the electrical characteristics, and the suppression of coloring during melt molding, the concentration of the terminal phenolic hydroxyl group in the resin A is preferably 30 mol / ton or less, It is more preferably 10 mol / ton or less, and further preferably less than 4 mol / ton.

The concentration of the terminal carboxyl group in the resin A is preferably 30 mol / ton or less. When the concentration of the terminal carboxyl group in the resin A exceeds 30 mol / ton, it becomes easy to hydrolyze or to be colored after melt molding, and the electrical breakdown voltage, arc resistance, dielectric constant, etc. of the resin The characteristics may deteriorate. In addition, the stability of the resin solution decreases. When the stability of the resin solution is lowered, it becomes cloudy with time, precipitates or insolubles are formed, and the resin is thickened and gelled. As a result, the smoothness of the coating film decreases, and the mechanical properties and electrical characteristics of the coating film may decrease. When the concentration of the terminal carboxyl group in the resin A exceeds 30 mol / ton and the concentration of the terminal phenolic hydroxyl group in the resin A exceeds 10 mol / ton, it is completely dissolved when the resin is dissolved in the solvent. Insoluble matter may be generated in the resin solution.

The resin A of the present invention includes an aliphatic diol residue, an alicyclic diol residue, an aliphatic dicarboxylic acid residue, and an alicyclic dicarboxylic acid residue within a range not impairing the effects of the present invention. You may go out. Examples of the aliphatic diol include ethylene glycol and propylene glycol. Examples of the alicyclic diol include 1,4-cyclohexanediol, 1,3-cyclohexanediol, and 1,2-cyclohexanediol. Examples of the aliphatic dicarboxylic acid include oxalic acid, malonic acid, succinic acid, adipic acid, and sebacic acid. Examples of the alicyclic dicarboxylic acid include 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,2-cyclohexanedicarboxylic acid.

In the present invention, the resin A may be mixed with other resins other than the resin A and used as a resin mixture. Other resins are used, for example, to improve mechanical strength. Examples of other resins include polyarylate resins and polycarbonate resins that do not contain an organosiloxane residue. Examples of the mixing method of the organosiloxane copolymer resin and other resins include a melt kneading method and a method of dissolving and mixing in an organic solvent. Among them, a method of dissolving and mixing in an organic solvent is preferable because the color tone does not deteriorate due to thermal decomposition and can be mixed uniformly.

As the resin other than the resin A, a resin containing a bisphenol residue represented by the following general formula (4) or general formula (5) (hereinafter referred to as a resin B) is preferable. While the mechanical strength of the resin is further increased, a uniform and stable resin mixture solution is obtained, and a uniform coating film is formed by using this resin mixture solution. In addition, the generation of foam when used as a solution containing a resin mixture is suppressed, forming a coating film or film that has excellent heat resistance, adhesion, surface smoothness, and water vapor permeability, and suppresses the occurrence of bleed out. can do.

 

Since bisphenol giving the structure represented by the general formula (4) is easily industrially available or easy to synthesize, in the general formula (4), R ⁹ and R ^{10 each} independently has 1 to 12 aliphatic groups, and r and s are integers of 1 to 4.

 

In the general formula (5), R ¹¹ , R ¹² , and R ¹³ are each independently carbon because the bisphenol giving the structure represented by the general formula (5) is industrially easily available or easily synthesized. It is an aliphatic group having a number of 1 to 12, t and u are integers of 0 to 4, and v is an integer of 0 to 10. When t is 2 to 4, the plurality of R ¹¹ may be the same or different from each other. When u is 2 to 4, the plurality of R ¹² may be the same or different from each other. When v is 2 to 10, the plurality of R ¹³ may be the same or different from each other.

Examples of the bisphenol component that gives the structure represented by the general formula (4) include 2,2-bis (3-methyl-4-hydroxyphenyl) propane and 2,2-bis (3,5-dimethyl-4-hydroxyphenyl). Examples include propane. In particular, 2,2-bis (3-methyl-4-hydroxyphenyl) propane is preferable because of excellent mechanical strength.

As the bisphenol component giving the structure represented by the general formula (5), 1,1-bis (4-hydroxyphenyl) cyclohexane is preferable because of its excellent mechanical strength.

Since the characteristics of the resin A and the characteristics of the resin B can be obtained with a good balance, the mass ratio of the resin A and the resin B in the resin mixture is preferably resin A / resin B = 1/9 to 5/5. ~ 3/7 is more preferred.

For example, an interfacial polymerization method, a solution polymerization method, or a melt polycondensation method is used as a method for producing the resin A of the present invention. From the viewpoint of polymerizability, appearance of a molded product obtained using a resin, and solution stability, it is preferable to use an interfacial polymerization method. For example, when solution polymerization is performed using an amine such as pyridine, the carboxylic acid value may increase and the solution stability may decrease.

Hereinafter, an example of the manufacturing method of resin A using the interfacial polymerization method will be shown.
An organosiloxane solution (organic phase 1) obtained by dissolving organosiloxane in an organic solvent is mixed with an alkaline aqueous solution (aqueous phase) containing bisphenol and a polymerization catalyst. Furthermore, a divalent carboxylic acid halide solution (organic phase 2) obtained by dissolving a divalent carboxylic acid halide in an organic solvent is added to the mixed solution. The mixed solution is stirred at a temperature of 50 ° C. or lower for 1 to 8 hours. In this way, bisphenol, divalent carboxylic acid halide, and organosiloxane are polymerized.

Examples of the alkaline aqueous solution used for the aqueous phase include aqueous solutions of sodium hydroxide and potassium hydroxide.

Examples of the polymerization catalyst include quaternary ammonium salts and quaternary phosphonium salts. Examples of the quaternary ammonium salt include tri-n-butylbenzylammonium halide, tetra-n-butylammonium halide, trimethylbenzylammonium halide, and triethylbenzylammonium halide. Examples of the quaternary phosphonium salt include tri-n-butylbenzylphosphonium halide, tetra-n-butylphosphonium halide, trimethylbenzylphosphonium halide, and triethylbenzylphosphonium halide. Of these, tri-n-butylbenzylammonium halide, tetra-n-butylammonium halide, tri-n-butylbenzylphosphonium halide, and tetra-n-butylphosphonium halide are preferable from the viewpoint of polymerizability.

The organic solvent used in the organic phase is preferably an organic solvent that is incompatible with water and that can dissolve the resin A. Examples of such organic solvents include methylene chloride, 1,2-dichloroethane, chloroform, carbon tetrachloride, chlorobenzene, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, o-dichlorobenzene. And halogenated hydrocarbon solvents such as m-dichlorobenzene and p-dichlorobenzene; aromatic hydrocarbons such as toluene, benzene and xylene; and ketone solvents such as cyclohexanone and cycloheptanone. Of these, methylene chloride, chloroform, toluene, o-xylene, m-xylene, p-xylene and cyclohexanone are preferable from the viewpoint of polymerizability.

In order to seal the terminal of the resin A, a terminal sealing agent may be added to the alkaline aqueous solution (aqueous phase) or the organic phase. The end-capping agent is not particularly limited, but is preferably monohydric phenol, monohydric acid chloride, monohydric alcohol, or monohydric carboxylic acid. Examples of the monohydric phenol include phenol, o-cresol, m-cresol, p-cresol, p-tert-butylphenol [PTBP], 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 chloride 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. Among these, PTBP is preferable from the viewpoints of reactivity and thermal stability.

After polymerization, acetic acid is added to the resin solution, and then the resin solution is repeatedly washed with water. Residual sodium can be made 10 ppm or less by washing until the electric conductivity of the water used for washing becomes 20 μS / cm or less.

Resin A can be precipitated by adding the resin solution to water having a temperature equal to or higher than the boiling point of the organic solvent used in the polymerization and dispersing the organic solvent (hot water method). Moreover, a resin solution can be added to a poor solvent to precipitate the resin A (reprecipitation method). The poor solvent is preferably an alcohol such as methanol, ethanol or isopropyl alcohol, or a hydrocarbon such as hexane. The precipitate can be isolated by filtration or the like, and then dried to obtain a solid content. Examples of the drying include drying under reduced pressure and drying while feeding hot air. In the case of drying under reduced pressure, the drying temperature is preferably more than 70 ° C and not more than 170 ° C. On the other hand, in the case of drying while supplying hot air, the drying temperature is preferably 150 ° C. or lower.

A film using the resin A of the present invention or a resin mixture of the resin A and the resin B can be obtained by a casting method or a melt extrusion method.
In the casting method, a resin solution obtained by dissolving resin A or a resin mixture of resin A and resin B in an organic solvent is applied to a substrate and dried to form a coating film. By using the resin A or the resin mixture of the present invention, it is possible to form a coating film having an arithmetic average roughness Ra of 5 μm or less and excellent in surface smoothness.
Then, the obtained coating film is peeled from the substrate to produce a film. In the melt extrusion method, a molten resin is extruded from a T die or the like onto a cooling roll, and the extruded material is scraped off. The casting method is preferably used because it does not cause a decrease in color tone due to thermal decomposition.

Examples of the organic solvent used in the casting method include organic solvents used in the organic phase in the production process of the resin A.

Examples of the substrate used in the casting method include a polyethylene terephthalate (PET) film, a polyimide film, a glass plate, and a stainless plate.
Examples of the method of applying the resin solution to the substrate include a method using a wire bar coater, a film applicator, brush or spray. Examples of the application method include a gravure roll coating method, a screen printing method, a reverse roll coating method, a lip coating method, an air knife coating method, a curtain flow coating method, and a dip coating method.

The resin A or the resin mixture of the resin A and the resin B of the present invention includes, for example, substrates and laminated films for liquid crystal displays and plasma displays, substrates for transparent conductive films, binder resins for electrophotographic photosensitive members, and diaphragms for acoustic devices. It can be used for coatings for electronic parts such as films and capacitors.

Next, examples of the present invention will be specifically described, but the present invention is not limited to these examples.
<< Production Example 1 >>
First, an aqueous phase, an organic phase 1 and an organic phase 2 were prepared by the following method.
In a reaction vessel equipped with a stirrer, 100 parts by mass of 2,2-bis (4-hydroxyphenyl) hexafluoropropane [BisAF] as bisphenol and p-tert-butylphenol [PTBP] as end-capping agent2. 22 parts by weight, 26.0 parts by weight of sodium hydroxide [NaOH] as an alkali, 1.33 parts by weight of a 50% by weight aqueous solution of tri-n-butylbenzylammonium chloride [TBBAC] as a polymerization catalyst, and an antioxidant 0.6 parts by mass of sodium hydrosulfite [SHS] was dissolved in 1650 parts by mass of water to obtain an aqueous phase.

Further, 15.9 parts by mass of organosiloxane [ORGS] (m = 40) represented by the following formula (9) was dissolved in 500 parts by mass of methylene chloride to obtain an organic phase 1.

 

Furthermore, 62.9 parts by mass of phthalic acid chloride (MPC) obtained by mixing terephthalic acid chloride and isophthalic acid chloride as an aromatic dicarboxylic acid chloride in a molar ratio of 50:50 was dissolved in 900 parts by mass of methylene chloride. Organic phase 2 was obtained.

Using the aqueous phase, organic phase 1 and organic phase 2 obtained above, a resin (P-1) was obtained by the following method.
After adding the organic phase 1 into the aqueous phase under strong stirring, the organic phase 2 is added into the mixed solution of the aqueous phase and organic phase 1 previously stirred under strong stirring at 15 ° C. for 2 hours. Then, an interfacial polymerization reaction was performed. The molar ratio was BisAF: MPC: ORGS: PTBP: TBBAC: NaOH: = 96.0: 100.0: 1.56: 4.88: 0.68: 210.
Then, stirring was stopped and the aqueous phase and the organic phase were decanted and separated. After removing the aqueous phase, 500 parts by mass of methylene chloride, 2000 parts by mass of pure water, and 2 parts by mass of acetic acid were added to the organic phase to stop the reaction, followed by stirring at 15 ° C. for 30 minutes. Thereafter, the organic phase is washed 10 times or more with pure water having a volume twice that of the organic phase, and when the electric conductivity of the washed water becomes 20 μS / cm or less, the organic phase is added to methanol. To precipitate the polymer. The precipitated polymer was filtered and dried in vacuum at 120 ° C. 10 parts by mass of the obtained precipitate (organosiloxane copolymer resin) was dissolved in 300 parts by mass of methylene chloride, and then 1000 parts by mass of methanol was added for reprecipitation. The operation of recovering the polymer obtained by reprecipitation and drying it under reduced pressure at 180 ° C. for 24 hours was repeated twice. In this way, an organosiloxane copolymer resin (P-1) was obtained. The content of the organosiloxane residue in the organosiloxane copolymer resin was 10% by mass.

<< Production Examples 2-8, 19, 21-30 >>
Resins (P-2) to (P-8) were prepared in the same manner as in Production Example 1, except that the aromatic dicarboxylic acid chloride, bisphenol, organosiloxane, and end-capping agent were changed to the types and molar ratios shown in Tables 1 and 2. ), (P-19), (P-21) to (P-30).

 

 

<< Production Example 9 >>
In a reaction vessel equipped with a stirrer, 100 parts by mass of BisAF as a bisphenol component, 1.32 parts by mass of PTBP as an end-capping agent, 25.35 parts by mass of NaOH as an alkali, and a 50% by weight aqueous solution of TBBAC as a polymerization catalyst 1. 28 parts by mass and 0.5 parts by mass of hydrosulfite sodium as an antioxidant were dissolved in 1450 parts by mass of water to obtain an aqueous phase.

Separately from the aqueous phase, 61.3 parts by mass of MPC were dissolved in 1300 parts by mass of methylene chloride to obtain an organic phase.
The aqueous phase was agitated in advance, and the organic phase was added to the aqueous phase with vigorous stirring, and an interfacial polymerization reaction was carried out at 15 ° C. for 2 hours. The molar ratio was BisAF: MPC: PTBP: TBBBAC: NaOH = 98.52: 100.0: 2.96: 0.67: 210. In the subsequent steps, a resin (P-9) was obtained in the same manner as in Production Example 1.

<< Production Example 10 >>
First, an aqueous phase, an organic phase 1 and an organic phase 2 were prepared by the following method.
In a reaction vessel equipped with a stirrer, 100.0 parts by mass (99.25 mol parts) of BisAF as a dihydric phenol component, 0.99 parts by mass (2.2 mol parts) of PTBP as an end-capping agent, and alkali As a polymerization catalyst, 25.44 parts by mass of NaOH, 1.28 parts by mass of 50% by weight aqueous solution of TBBAC as a polymerization catalyst, and 0.53 parts by mass of SHS were dissolved in 1000 parts by mass of water to obtain an aqueous phase.

The organic phase 1 was obtained by dissolving 7.40 parts by mass (0.75 part by mol) of the organosiloxane represented by the above formula (9) in 200 parts by mass of methylene chloride.

In 400 parts by mass of methylene chloride, 61.51 parts by mass (101.1 parts by mol) of phthalic acid chloride [MPC] obtained by mixing terephthalic acid chloride and isoterephthalic chloride at a molar ratio of 50:50 was dissolved in an organic phase 2 was obtained.

Using the aqueous phase, organic phase 1, and organic phase 2 obtained above, a resin (P-10) was obtained by the following method.
After adding the organic phase 1 into the aqueous phase under strong stirring, the organic phase 2 is added into the mixed solution of the aqueous phase and organic phase 1 previously stirred under strong stirring at 15 ° C. for 2 hours. Then, an interfacial polymerization reaction was performed.
The molar ratio was BisAF: MPC: organosiloxane: PTBP: TBBAC: NaOH: = 99.25: 101.1: 0.75: 2.2: 0.68: 210.
Then, stirring was stopped and the aqueous phase and the organic phase were decanted and separated. After removing the aqueous phase, 200 parts by mass of methylene chloride, 1000 parts by weight of pure water, and 1 part by mass of acetic acid were added to the organic phase to stop the reaction, and the mixture was stirred at 15 ° C. for 30 minutes. This organic phase was washed 5 times with pure water having a volume twice that of the organic phase, and then the organic phase was added into hexane to precipitate the polymer. The precipitated polymer was separated and recovered, and then dried at 50 ° C. under reduced pressure for 24 hours. In this way, a resin (P-10) was obtained.

<< Production Examples 11-18 >>
Resins (P-11) to (P-18) were obtained in the same manner as in Production Example 9, except that the aromatic dicarboxylic acid chloride, bisphenol, and terminal blocking agent were changed to the types and molar ratios shown in Table 1.

<< Production Example 20 >>
10 parts by mass of the resin (P-10) obtained in Production Example 10 was dissolved in 300 parts by mass of methylene chloride, and then 1000 parts by mass of methanol was added to reprecipitate the polymer. The reprecipitated polymer was collected and dried under reduced pressure at 180 ° C. for 24 hours. This operation was repeated three times. In this way, a resin (P-20) was obtained.

<< Production Example 31 >>
A methylene chloride solution containing 37.56 parts by mass (186 molar equivalents) of isophthalic acid chloride was mixed with 61.58 parts by mass of BisAF (185 molar equivalents) and 24.975 parts by mass of aminopropyl-terminated polydimethylsiloxane organosiloxane (1.85 mols). Equivalent) and a methylene chloride solution containing 36.6 parts by mass (463 molar equivalents) of pyridine to obtain a mixed solution. The addition temperature was 10 ° C., and the addition time was 45 minutes. Thereafter, the mixed solution was stirred at room temperature for 2 hours, and a methylene chloride solution of isophthalic acid chloride (concentration 1% by weight) was added dropwise to the mixed solution until the viscosity no longer increased, and then stirred for 1 hour. This solution was diluted with methylene chloride, washed with 10% hydrochloric acid and distilled water, and methanol was added to precipitate the resin. The resin precipitate obtained by filtration was washed with methanol and dried at 100 ° C. under reduced pressure. In this way, resin (P-31) was obtained.
Although the terminal blocking agent was not added above, the weight average molecular weight in terms of polystyrene obtained by measurement by GPC (gel permeation chromatography) was 67,000, and the terminal carboxylic acid value was 50 mol / ton.

<< Production Example 32 >>
10 parts by mass of the resin (P-31) obtained in Production Example 31 was dissolved in 300 parts by mass of methylene chloride, and then 1000 parts by mass of methanol was added to reprecipitate the polymer. The reprecipitated polymer was collected and dried under reduced pressure at 180 ° C. for 24 hours. This operation was repeated three times. In this way, Resin (P-32) was obtained.

The evaluation method is shown below.
<Evaluation methods>
1. Resin Characteristics (1-1) Inherent Viscosity The obtained resin was dissolved in 1,1,2,2-tetrachloroethane to prepare a sample solution having a concentration of 1 g / dL. Using an Ubbelohde viscometer, the drop time of the sample solution and the solvent was measured at a temperature of 25 ° C., and the inherent viscosity was determined using the following equation.
Inherent viscosity (dL / g) =
[Ln (sample solution drop time / solvent only drop time)] / resin concentration (g / dL)

(1-2) Glass transition temperature 10 mg of the obtained resin was heated at a heating rate of 10 ° C./min using a DSC (Differential Scanning Calorimetry) device (DSC7, manufactured by Perkin Elmer). An intermediate value between two bending point temperatures derived from the glass transition was taken as the glass transition temperature. A resin having a glass transition temperature of 150 ° C. or higher was evaluated as having excellent heat resistance.

(1-3) Residual Sodium Amount The amount of residual sodium in the obtained resin was measured by quantitative analysis based on a calibration curve method using an ICP emission spectroscopic analyzer (manufactured by Thermo Fisher Scientific, iCAP6500Duo).

(1-4) Amount of siloxane-containing volatile component 10 mg (sample) of the obtained resin was heated at 180 ° C. for 10 minutes using a double shot pyrolyzer PY-2020iD manufactured by Shimadzu Corporation, and then the gas chromatograph analyzer (Agilent・ Analysis using a technology company, 6890N), the amount of volatile components was determined (column: UA5 (MS / HT) -30M-0.25F, carrier gas: helium). The amount of the volatile component was calculated using a calibration curve (quantitative conversion based on the area ratio of the siloxane-containing component and the standard substance hexadecane) prepared using hexadecane as a standard sample. Specifically, an n-hexadecane / hexane solution with a known concentration is prepared, 500 μL of this solution is put into a sample cup, and hexane is volatilized. Then, the GC / MS method (gas chromatography mass is used under the same heating conditions as the sample. (Analysis method). A calibration curve of the peak area of n-hexadecane and the amount of substance was prepared, and quantified based on the peak area of the siloxane-containing volatile component.
As the siloxane-containing volatile component, a plurality of compounds containing siloxane bonds were identified by using an MS (mass spectrometry) database, and 5975C manufactured by Agilent Technologies was used as the apparatus.

(1-5) Resin composition and concentration of terminal phenolic hydroxyl group in the resin The obtained resin was dissolved in deuterated chloroform to obtain a sample solution. A ¹ H-NMR spectrum was measured using the sample solution. For the measurement, a high-resolution nuclear magnetic resonance apparatus (manufactured by JEOL Ltd., ECA500 NMR) was used. Based on the measurement results, the resin composition and the concentration of the terminal phenolic hydroxyl group in the resin were determined from the peak intensity of each component to be copolymerized (resolution: 500 MHz, solvent: deuterated chloroform, temperature: 25 ° C.). Moreover, content of the organosiloxane residue in resin was calculated | required from the obtained resin composition.
From the measurement results, it was confirmed that the polymerization ratio obtained for each resin was the same as the charge ratio.

(1-6) Concentration of terminal carboxyl group in resin 150 mg of the obtained resin was dissolved in 5 ml of benzyl alcohol by heating and then cooled, and further 10 ml of chloroform was added and mixed to obtain a sample solution. . This sample solution was used and titrated with 0.1N potassium hydroxide benzyl alcohol solution using phenol red as an indicator. Using the titrated value, the number of moles of carboxyl groups contained in 1 ton of resin was calculated.

2. Resin Solution Characteristics (2-1) Solubility Resin and chloroform were mixed so that the solid content was 15% by mass, and the state of the resin solution after stirring at 25 ° C. for 24 hours was judged visually.
`` Good '' is a transparent solution obtained without insoluble matter such as gels in the resin solution, while `` a little '' insoluble matter is floating and slightly cloudy. “Positive”, and those in which the resin was not dissolved and did not become a resin solution state were set to “impossible”

(2-2) Solution Stability For the resin solution judged “good” or “good” in the above (2-1), the state of the resin solution after standing at 25 ° C. for 3 days was judged visually.
“Good” when the solution is in a uniform state and the visual permeability does not change, “No” when no visual separation or gelation is observed, but “Perfect” when the visual permeability is slightly lowered. What was done or gelatinized was made "impossible".

(2-3) Foamability Resin and chloroform were mixed so that the solid content was 10% by mass, and the resin was completely dissolved to prepare a resin solution. The obtained resin solution was shaken for 60 minutes using a paint shaker (manufactured by Toyo Seiki Co., Ltd.) to generate bubbles. After the stirring was stopped, the height of the generated foam after standing for 1 minute was observed. When the height of the foam was equal to or higher than the height of the foam in Comparative Example 4, it was judged as “impossible”, and when the height of the foam was lower than the height of the foam in Comparative Example 4, it was judged as “Good”.

3. Coating film characteristics (3-1) Preparation of coating film Resin and chloroform were mixed so that the solid content would be 12.5% by mass, stirred for 1 hour with a paint shaker, and then allowed to stand for 24 hours to obtain a resin solution. It was. The obtained resin solution was used as a No. manufactured by Yasuda Seiki Seisakusho. Surface of the substrate (non-corona) of polyethylene terephthalate film (Embret made by Unitika Co., Ltd., thickness of about 120 μm) so that the thickness of the coated film after drying with a bar coater using a 542-AB automatic film applicator is 100 μm. Surface) and dried at room temperature to obtain a coating film.

(3-2) Adhesiveness of the coating film In (3-1), if the coating film partially peels off from the substrate during drying, the adhesion is “Yes”, and the coating film does not peel off from the substrate during drying. The adhesive was evaluated as having no adhesion.

4). Film Characteristics (4-1) Production of Film A resin and chloroform were mixed so that the solid content was 12.5% by mass, stirred for 1 hour with a paint shaker, and then allowed to stand for 24 hours to obtain a resin solution. The obtained resin solution was used as a No. manufactured by Yasuda Seiki Seisakusho. After coating the surface of the substrate made of PET film so that the thickness of the coating film after drying with a bar coater using a 542-AB automatic film applicator is 100 μm, the coating film is dried at 80 ° C. Obtained. Then, after cooling a coating film to room temperature, the coating film was peeled from the base material and the film was obtained. The obtained film was dried under reduced pressure at 120 ° C. for 24 hours. In this way, a film having a thickness of 100 μm was produced.

(4-2) Tensile modulus and tensile breaking strength The film obtained in (4-1) was measured for tensile modulus and tensile breaking strength using Model 2020 (manufactured by Intesco) according to JIS K 7127. did.

(4-3) Water Vapor Permeability Using the film obtained in (4-1), a non-voided portion was selected and a PERMATRAN-W 3/31 moisture permeability measuring device (manufactured by mocon) was used according to JIS K 7129. The water vapor permeability was measured under the conditions of 100% RH at 40 ° C.

(4-4) Bleed out The film obtained in (4-1) was allowed to stand in an environment of 100 ° C. for 24 hours. At this time, the case where the liquid substance was adhered to the film surface was evaluated as “bleeded out”, and the case where the liquid substance was not adhered to the film surface was evaluated as “no”. The presence or absence of adhesion of the liquid was determined by visually observing the film surface and touching it with a finger.

(4-5) Surface roughness A film was produced in the same manner as in (4-1) except that the standing time after stirring for 1 hour was changed to 30 minutes.
The surface of the peeled film opposite to the surface in contact with the substrate was measured for arithmetic average roughness Ra using a surface roughness meter SJ-400 manufactured by Mitutoyo Co., Ltd. according to JIS B 0601. A film having an arithmetic average roughness Ra of 0.5 μm or less was evaluated as having excellent surface smoothness.

(4-6) Void With respect to the sheet-like film (17 cm × 25 cm) obtained in (4-5), the central portion of the film (5 cm × 8 cm) excluding 35% of the edge from the periphery in each of the four directions was visually observed. did. When a void was observed, it was evaluated as “existing”, and when no void was observed, it was evaluated as “no”.

<< Examples 1 to 15 >>
Various properties were evaluated using the resins (P-1) to (P-6), (P-21) to (P-28), and (P-32). The evaluation results are shown in Tables 3 and 4.

 

 

<< Comparative Examples 1-8, 10-12 >>
Various properties were evaluated using the resins (P-7) to (P-12), (P-19) to (P-20), and (P-29) to (P-31). The evaluation results are shown in Tables 3 and 4.

<< Comparative Example 9 >>
The resin (P-10) resin of Comparative Example 4 obtained in Production Example 10 and chloroform were mixed so that the solid content was 12.5% by mass, stirred for 1 hour with a paint shaker, and then allowed to stand for 24 hours. Thus, a resin solution was obtained. In order to evaluate the case where there are many volatile components, for convenience, 1% by mass of organosiloxane (m = 40) represented by the chemical formula (9) was added to the resin solution with respect to the solid content of the resin (P-10). .
In Comparative Example 9, the characteristics of the resin as a resin (P-10) containing the organosiloxane added above (hereinafter referred to as resin (P-10) ′) were evaluated. Considering that the organosiloxane added above and not contributing to copolymerization also corresponds to the siloxane volatile component, the amount of the siloxane-containing volatile component in the resin (P-10) ′ was 3500 ppm.
Using the obtained resin solution, the properties of the resin solution, the coating film, and the film were evaluated. The evaluation results are shown in Table 3.

Example 16
A resin containing an organosiloxane residue (P-6) (4.5 parts by mass), another resin (P-12) containing no organosiloxane residue (10.5 parts by mass), and chloroform (85 parts by mass) The mixture was stirred for 24 hours to prepare a resin solution.
Using the obtained resin solution, the properties of the resin solution, the coating film, and the film were evaluated. The evaluation results are shown in Table 5.

<< Examples 17 to 27 and Comparative Example 13 >>
A resin solution was prepared in the same manner as in Example 16 except that the mixed resin composition of a resin containing an organosiloxane residue and another resin not containing an organosiloxane residue was changed as shown in Table 5.
Using the obtained resin solution, the properties of the resin solution, the coating film, and the film were evaluated. The evaluation results are shown in Table 5.

 

Examples 1 to 15 had sufficient heat resistance and water vapor permeability.
In Examples 1 to 4 in which the content of the organosiloxane residue represented by the general formula (3) in the organosiloxane copolymer resin is 10 to 25% by mass, the glass transition temperature is higher than that in Example 5, and the tensile fracture The strength was higher than in Example 6.
In Examples 1 to 15, since the inherent viscosity was 0.9 dL / g or less, the arithmetic average roughness Ra of the film surface was smaller than that of Comparative Example 2.
In Examples 1 to 15, the generation of bubbles was suppressed in the solution containing the resin A, the adhesiveness of the coating film was excellent, and voids and bleedout did not occur in the film.
In Example 15, since the concentration of the terminal phenolic hydroxyl group was 15 mol / ton and the concentration of the terminal carboxyl group was 40 mol / ton, most of the resin was dissolved in the organic solvent when the resin was dissolved in the organic solvent. Although it became a solution state, a trace amount of insoluble matter floated in the resin solution, and the resin solution became slightly cloudy.

Since Examples 16 to 19, 22, and 23 were a mixture of Resin A and Resin B, the resin solution did not undergo phase separation for 3 days, and the solution stability was good. The obtained film was higher in both tensile modulus and tensile breaking strength than Examples 1 to 6, and was excellent in mechanical strength.
Since Examples 20, 21, and 24-27 were a mixture of Resin A and another resin that was not Resin B, the resulting films were higher in both tensile modulus and tensile breaking strength than Examples 1-6. Although excellent in mechanical strength, the resin solution after standing for 3 days was phase-separated, and the solution stability was poor.
In Examples 16 to 27, when used as a resin solution, the generation of bubbles was suppressed, the adhesion of the coating film was excellent, and voids and bleedout did not occur in the film. In Examples 16 to 27, films excellent in surface smoothness and water vapor permeability were obtained.

In Comparative Example 1, since the fluorine atom was not contained in the bisphenol component, the water vapor permeability of the film was lowered.
Since Comparative Example 3 did not contain the organosiloxane residue represented by the general formula (3) in the resin, the water vapor permeability of the film was lowered.
In Comparative Examples 5 and 6, since the fluorine atom was not contained in the bisphenol component and the organosiloxane residue was not contained, the water vapor permeability of the film was lowered.

In Comparative Examples 2, 4, and 8, since the inherent viscosity was more than 0.9 dL / g, bubbles were generated in the solution containing the resin, and the surface smoothness of the film was lowered. In addition, voids were generated in the film, and the adhesion of the coating film to the substrate was reduced.
In Comparative Examples 4 and 12, since the amount of the siloxane-containing volatile component was more than 700 ppm by mass, bleeding out occurred.
In Comparative Example 9, although the inherent viscosity is more than 0.9 dL / g, the amount of the siloxane volatile component acting as an antifoaming agent is as large as 3500 mass ppm, so that foaming of the resin solution was suppressed. However, in Comparative Example 9, since the amount of the siloxane-containing volatile component was more than 700 ppm by mass, bleeding out occurred.

Since the comparative example 7 did not contain a fluorine atom, the water vapor permeability of the film was lowered. Although the inherent viscosity was 0.9 dL / g, since X in the general formula (1) is a fluorene group containing no fluorine atom, bubbles are generated when used as a resin solution. The adhesion was also low. Moreover, in the film of Comparative Example 7, voids were generated and the surface smoothness was lowered.
In Comparative Example 10, since m = 2 in the organosiloxane represented by the general formula (9), heat resistance and water vapor permeability were lowered.
In Comparative Example 11, when DSDC was used as the aromatic dicarboxylic acid chloride, the polymerization reaction did not proceed, a solid precipitated during the polymerization, and no resin was obtained.
In Comparative Example 13, since the resin containing the organosiloxane residue does not contain the bisphenol residue represented by the general formula (1), the water vapor permeability was lower than that of the films of Examples 16 to 27.

Claims (13)

1. A resin containing a bisphenol residue represented by the general formula (1), an aromatic dicarboxylic acid residue represented by the general formula (2), and an organosiloxane residue represented by the general formula (3),
   Inherent viscosity measured at a temperature of 25 ° C. and a concentration of 1 g / dL in 1,1,2,2-tetrachloroethane of the resin is 0.90 dL / g or less,
   An organosiloxane copolymer resin characterized in that when the resin is heated at 180 ° C. for 10 minutes, the amount of the siloxane-containing component volatilized from the resin is 700 ppm by mass or less.
   

   

   
   (In formula (1), R ¹ and R ² independently represent a hydrocarbon group having 1 to 6 carbon atoms, a halogenated alkyl group, or a halogen atom. P and q are independently 0 Represents an integer of ˜4, X represents a divalent group containing a fluorine atom.
   

   

   
   

   

   
   (In Formula (3), R ³ and R ⁴ independently represent an aliphatic group and / or an aromatic group, and may contain a nitrogen atom or an oxygen atom. R ⁵ , R ⁶ , R ⁷ And R ⁸ independently represents an aliphatic group or an aromatic group, and m represents a number of 5 or more.)
2. The organosiloxane copolymer resin according to claim 1, wherein the content of the organosiloxane residue represented by the general formula (3) in the resin is more than 7% by mass and less than 80% by mass.
3. 3. The organosiloxane copolymer resin according to claim 1, wherein the bisphenol residue represented by the general formula (1) is a 2,2-bis (4-hydroxyphenyl) hexafluoropropane residue.
4. The aromatic dicarboxylic acid residue represented by the general formula (2) is a mixture of a terephthalic acid residue and an isophthalic acid residue,
   The organosiloxane according to any one of claims 1 to 3, wherein a molar ratio of terephthalic acid residue to isophthalic acid residue: terephthalic acid / isophthalic acid in the mixture is 90/10 to 10/90. Copolymer resin.
5. 5. A resin mixture comprising the organosiloxane copolymer resin according to claim 1 and a resin other than the organosiloxane copolymer resin.
6. 6. The resin mixture according to claim 5, wherein the resin other than the organosiloxane copolymer resin is a resin containing a bisphenol residue represented by the general formula (4) or (5).
   

   

   
   (In Formula (4), R ⁹ and R ¹⁰ independently represent an aliphatic group having 1 to 12 carbon atoms. R and s independently represent an integer of 1 to 4)
   

   

   
   (In Formula (5), R ¹¹ , R ¹² , and R ¹³ independently represent an aliphatic group having 1 to 12 carbon atoms. T and u each independently represents an integer of 0 to 4) (V represents an integer of 0 to 10)
7. The resin mixture according to claim 6, wherein the bisphenol residue represented by the general formula (4) is a 2,2-bis (3-methyl-4-hydroxyphenyl) propane residue.
8. The resin mixture according to claim 6, wherein the bisphenol residue represented by the general formula (5) is a 1,1-bis (4-hydroxyphenyl) cyclohexane residue.
9. A resin solution obtained by dissolving the organosiloxane copolymer resin according to any one of claims 1 to 4 or the resin mixture according to any one of claims 5 to 8 in an organic solvent.
10. A coating film formed using the resin solution according to claim 9.
11. The coating film according to claim 10, wherein the arithmetic average roughness Ra of the surface is 0.5 μm or less.
12. A film formed using the resin solution according to claim 9.
13. The film according to claim 12, wherein the arithmetic average roughness Ra of the surface is 0.5 μm or less.