JP2010024346A - Organosiloxane copolymer resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition exhibiting transparency and flexibility while retaining heat resistance, suppressing color change due to UV radiation, further having excellent water repellency, a low friction coefficient, and low solution viscosity. <P>SOLUTION: The polyester has a block structure and contains 60 mol% or more alicyclic dicarboxylic acid represented by general formula (I) based on the total dicarboxylic acid, wherein the polyorganosiloxane represented by general formula (II) accounts for 0.05 mass% or more and less than 80 mass% in the resin. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a resin composition having transparency and flexibility, excellent water repellency, low coefficient of friction, excellent surface properties, and low solution viscosity and excellent handling properties while maintaining heat resistance. .

  Polyarylates obtained from 2,2-bis (4-hydroxyphenyl) propane (sometimes abbreviated as bisphenol A), terephthalic acid and isophthalic acid are already well known as engineering plastics. Such polyarylate has high heat resistance and is excellent in mechanical strength and dimensional stability represented by impact strength, and its molded products are widely applied in fields such as electric / electronics, automobiles and machines.

  In addition, it has excellent electrical characteristics (insulating properties, dielectric properties, etc.) and heat resistance, so it can be used as a film for electronic parts such as capacitors, an optical film for liquid crystal displays, a base film for microfabrication, etc. Applied.

  In general, a resin material that is hardly changed in color is suitable as a resin material used for optical applications. However, it is known that polyarylate undergoes a color change by ultraviolet irradiation. Therefore, there are cases where there is a limit when developing for optical applications, and a material design that does not cause a color change due to ultraviolet irradiation has been demanded (Patent Document 1).

  In recent years, flexibility has been required for these applications, and flexibility has been required for resin materials, but polyarylate has been insufficient (patents). References 2, 3).

  Furthermore, the requirements for antifouling and water repellency, friction and wear on the resin surface are becoming increasingly severe. For example, there is a problem that a sliding component material is scratched by frictional sliding with a metal or other plastic material, and a low friction material is required.

In addition, when it is intended to achieve antifouling properties, water repellency and low friction properties with the surface coating of molded products, it is desirable that the resin material used for the coating liquid has a low solution viscosity from the viewpoint of handling properties. It is.
Japanese Patent Laid-Open No. 2000-255016 Japanese Patent Laid-Open No. 2000-243988 JP 2000-243144 A

  The present invention has transparency and flexibility while maintaining heat resistance, suppresses color change due to ultraviolet rays, and further has excellent water repellency, a low coefficient of friction, excellent surface characteristics, and solution viscosity. It aims at providing a low resin composition.

  As a result of intensive studies in order to solve such problems, the present inventors have found that a siloxane copolymer resin composed of an acid component having a specific structure and having an organosiloxane structure can achieve the above object. The present invention has been reached.

  That is, the gist of the present invention is as follows.

  (1) An organosiloxane copolymer resin composed of (A) a dicarboxylic acid residue, (B) a dihydric phenol residue, and (C) an organosiloxane residue, and 60 mol% based on the total dicarboxylic acid The alicyclic dicarboxylic acid containing the above alicyclic dicarboxylic acid is an alicyclic dicarboxylic acid represented by the following general formula (I), and the organosiloxane is represented by the following general formula (II) An organosiloxane copolymer resin, wherein the proportion of the organosiloxane residue in the resin is 0.05% by mass or more and less than 80% by mass.

[In General Formula (II), R ₁ and R ₂ may be the same or different, and are an aliphatic group or an aromatic group having 1 to 12 carbon atoms. R ₃ , R ₄ , R ₅ and R ₆ are all aliphatic groups or aromatic groups which may be the same or different. m is an integer of 5 or more, and X ₁ and X ₂ are any group of the general formula (III). In the general formula (III), R ₁₀ is 1-5 aliphatic group or an aromatic group carbon atoms, s is an integer of 0-4. ]
(2) The organosiloxane copolymer resin according to (1), wherein the dicarboxylic acid is alicyclic dicarboxylic acid / aliphatic dicarboxylic acid = 60/40 to 100/0 (molar ratio).
(3) A molded article, film or coat film obtained by molding the organosiloxane copolymer resin of (1) or (2).

  According to the present invention, an organosiloxane copolymer resin comprising (A) a dicarboxylic acid residue, (B) a dihydric phenol residue, and (C) an organosiloxane residue having a specific structure maintains heat resistance. It is possible to provide an organosiloxane copolymer resin having transparency and flexibility, suppressing discoloration due to ultraviolet rays, having excellent water repellency, a low coefficient of friction, and a low solution viscosity. Insulation coatings such as motors, generators, interphase insulation, wire coatings, dielectric coatings such as transformers and capacitors, substrate films for liquid crystal displays, coating layers and laminated films thereof, substrates such as information recording disks, and the like It can be applied to laminates, optical lenses, binders for electrophotographic photoreceptors, diaphragms for acoustic equipment, etc., and has an extremely high industrial utility value.

  The organosiloxane copolymer resin of the present invention is composed of (A) a dicarboxylic acid residue, (B) a dihydric phenol residue, and (C) an organosiloxane residue having a specific structure.

  The dicarboxylic acid that gives the dicarboxylic acid residue constituting the organosiloxane copolymer resin of the present invention must be a cyclohexanedicarboxylic acid represented by the following general formula (I). Specific examples thereof include 1,2-cyclohexane. Examples include cyclohexanedicarboxylic acid such as dicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid. Among these, 1,4-cyclohexanedicarboxylic acid is particularly preferably used because of its excellent heat resistance.

  The alicyclic dicarboxylic acid is a dicarboxylic acid having a cyclohexane structure and may have a side chain such as a methyl group or a methoxy group.

  The cyclohexanedicarboxylic acid used in the organosiloxane copolymer resin of the present invention must be blended in an amount of 60 mol% or more with respect to all dicarboxylic acid components constituting the organosiloxane copolymer resin, and has heat resistance and ultraviolet rays when used as a film. In order to suppress yellowing, it is more preferably 90 mol% or more.

  The dicarboxylic acid used in the organosiloxane copolymer resin of the present invention may include other aliphatic dicarboxylic acids in addition to cyclohexanedicarboxylic acid as the alicyclic dicarboxylic acid. Specific examples include aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, adipic acid, and sebacic acid.

  When other aliphatic dicarboxylic acids are blended, it is necessary to mix in the range of alicyclic dicarboxylic acid / aliphatic dicarboxylic acid = 60/40 to 100/0 (molar ratio). 90/10 to 100/0 is desirable. When the amount of the aliphatic dicarboxylic acid exceeds 40 mol%, the organosiloxane copolymer resin excellent in heat resistance of the present invention cannot be obtained, which is not preferable.

  Specific examples of the dihydric phenol that gives the dihydric phenol residue constituting the organosiloxane copolymer resin of the present invention include 1,1-bis (4-hydroxyphenyl) methane and 1,1-bis (4-hydroxyphenyl). ) Ethane [bisphenol AP], 1,1-bis (4-methyl-2-hydroxyphenyl) methane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) methane, 1,1-bis (4 -Hydroxyphenyl) cyclohexane [bisphenol Z], 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 2,2-bis (4-hydroxyphenyl) propane [bisphenol A], 2,2-bis ( 3-methyl-4-hydroxyphenyl) propane [bisphenol C], 2,2-bis (3,5-dimethyl-4-hydroxy) Phenyl) propane [TM bisphenol A], 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4-hydroxyphenyl) -2-ethylhexane, 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-hydroxyphenyl) propane, 2,2-bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (3-sec-butyl-4-hydroxyphenyl) 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′-methylene Bisphenol, bis (3-methyl-4-hydroxyphenyl) methane, bis (4-hydroxypheny Propane, 1,1-bis (2-hydroxy-5-methylphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -3-methylbutane, bis (2-hydroxy-3,5-dimethylphenyl) 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-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-ditert -Butyl-4-hydroxyphenyl) methane, 1,1-bis (3,5-disec-butyl-4-hydro Ciphenyl) methane, 1,1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (2-hydroxy-3,5-ditert-butylphenyl) ethane, bis (3-nonyl-4) -Hydroxyphenyl) methane, 2,2-bis (3,5-ditert-butyl-4-hydroxyphenyl) propane, bis (2-hydroxy-3,5-ditert-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 (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (3-fluoro- 4-hydroxyphenyl) propane, bis (3-fluoro-4-hydroxyphenyl) -phenylmethane, bis (3-fluoro-4-hydroxyphenyl)-(p-fluorophenyl) methane, bis (4-hydroxyphenyl)-( p-fluorophenyl) methane, 2,2-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'-bipheno 3,3 ′, 5,5′-tetramethyl-4,4′-biphenol [TMBP], 3,3 ′, 5,5′-tetratert-butyl-4,4′-biphenol, bis (4- Hydroxyphenyl) ketone, 3,3′-difluoro-4,4′-biphenol, 3,3 ′, 5,5′-tetrafluoro-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-hydroxy) Phenyl) dodecane, 1,1-bis (3-tert-butyl-4-hydroxyphenyl) -1-phenylethane, 1,1-bis (3,5-ditert-butyl-4-hydroxyphenyl) -1- Phenylethane, 1,1-bis (2-methyl-4-hydroxy-5-cyclohexylphenyl) -2-methylpropane, 1,1-bis (2-hydroxy-3,5-ditert-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-hydroxyphenyl) -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-ditert-butyl-4-hydroxyphenyl) ethane, bis (2-hydroxy) Loxy-3,5-ditert-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-5-ethyl-cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethyl-cyclopentane, 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, 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-hydroxy) Phenyl) 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 (3-ethyl-4-hydroxyphenyl) sulfide, 2,4-dihydroxydiphenylsulfone and the like.

  Among the above-mentioned dihydric phenols, 2,2-bis (4-hydroxyphenyl) propane [bisphenol A] and 2,2-bis (3-methyl) are easy to obtain industrially and have excellent heat resistance. -4-hydroxyphenyl) propane [bisphenol C], 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane [TM bisphenol A], 2,2-bis (3,5-dimethyl-4- Hydroxyphenyl) methane [TM bisphenol F], 1,1-bis (4-hydroxyphenyl) -1-phenylethane [bisphenol AP], 1,1-bis (4-hydroxyphenyl) cyclohexane [bisphenol Z] are preferred. These may be used alone or in combination of two or more.

  Among them, 2,2-bis (3-methyl-4-hydroxyphenyl) propane [bisphenol C], 2,2-bis (3,5-dimethyl-4-hydroxy) are used as dihydric phenols having a methyl group in the side chain. When phenyl) propane [TM bisphenol A] is dissolved in a solvent and used as a coating solution, the solution viscosity can be lowered without lowering the solution concentration, so that the solution viscosity can be kept low. Handling is improved, which is particularly preferable.

  Further, as a dihydric phenol having no methyl group in the side chain, 2,2-bis (4-hydroxyphenyl) propane [bisphenol A], 1,1-bis (4-hydroxyphenyl) -1-phenylethane [bisphenol When AP] and 1,1-bis (4-hydroxyphenyl) cyclohexane [bisphenol Z] are used, the degree of yellowing is suppressed when irradiated with ultraviolet rays, which is particularly preferable.

  The organosiloxane constituting the organosiloxane copolymer resin of the present invention is represented by the following formula (II).

In the general formula (II), R ₁ and R ₂ may be the same or different and are an aliphatic group or an aromatic group having 1 to 12 carbon atoms. R ₃ , R ₄ , R ₅ and R ₆ are all aliphatic groups or aromatic groups which may be the same or different. m is an integer of 5 or more, and X ₁ and X ₂ represent any one of the general formula (III). In the general formula (III), R ₁₀ represents an aliphatic group or aromatic group having 1 to 5 carbon atoms, and s is an integer of 0 to 4.

  In the above general formula (II) indicating the siloxane length of the organosiloxane structure, m is an integer of 5 or more, preferably 10 or more and 250 or less, particularly preferably 20 or more and 100 or less. When m is 4 or less, the heat resistance is lowered, and when it exceeds 250, the handling property at the time of polymerization is lowered due to the increase in viscosity or solubility of the organosiloxane, or the transparency of the resulting organosiloxane copolymer resin. May decrease.

  In the organosiloxane copolymer resin, the content of the organosiloxane residue represented by the general formula (II) is from 0.05% by mass to 80% by mass, preferably from 0.05% by mass to 50% by mass. It is as follows. If the amount is less than 0.05% by mass, the elasticity of the resin may be lowered to give flexibility, or the effect of introducing siloxane such as water repellency may be insufficient. There may be a shortage.

  The molar ratio of the organosiloxane residue represented by the general formula (II) in the organosiloxane copolymer resin is preferably 0.001 mol% or more and less than 10 mol%, particularly preferably 0.001 mol%. It is 01 mol% or more and less than 1 mol%. When the amount is less than 0.001 mol%, the effect of introducing siloxane such as water repellency may be insufficient. When the amount is 10 mol% or more, heat resistance may be insufficient.

  The carboxyl value and amine value of the organosiloxane copolymer resin of the present invention must be 100 mol / t or less, preferably 50 mol / t or less, and optimally 30 mol / t or less. When the carboxyl value and amine value each exceed 100 mol / t, hydrolysis easily occurs, coloring is observed after melt molding, and electrical characteristics such as dielectric breakdown voltage, arc resistance and dielectric constant of the resin deteriorate. There is a tendency to. In addition, when a resin is dissolved in a solvent to form a coating solution, the storage stability of the solution tends to decrease. If the storage stability of the coating solution decreases, it will become cloudy, precipitate, insoluble, or thicken and gel with time, resulting in the formation of a uniform film. Mechanical and electrical characteristics may be degraded.

  The molecular weight of the organosiloxane copolymer resin of the present invention can be expressed by using the weight average molecular weight Mw as an index, and the weight average molecular weight Mw is preferably 30,000 to 300,000, more preferably 50,000 to 200,00. is there. If the weight average molecular weight Mw is less than 30,000, the strength of the resin may be insufficient. On the other hand, when the weight average molecular weight Mw exceeds 300,000, it tends to be difficult to handle due to high viscosity. The molecular weight of the resin can be controlled by the addition amount of the end-capping agent described later during the production.

  Examples of the method for producing the organosiloxane copolymer resin of the present invention include a method obtained by reacting in an organic solvent such as an interfacial polymerization method or a solution polymerization method, or a method of reacting in a molten state such as melt polycondensation. From the viewpoint of polymerizability and the appearance of the obtained resin, it is most preferable to produce by an interfacial polymerization method capable of reacting in an organic solvent, particularly at a low temperature.

  The interfacial polymerization method is a polymerization method for obtaining a polyester by mixing a divalent carboxylic acid halide dissolved in an organic solvent incompatible with water and a dihydric phenol dissolved in an alkaline aqueous solution. As literature on the interfacial polymerization method, W.W. M.M. EARECKSON J. Poly. Sci. XL399 1959, Japanese Examined Patent Publication No. 40-1959, and the like. Since the interfacial polymerization method is faster than the solution polymerization method, hydrolysis of the acid halide can be suppressed, and as a result, a high molecular weight resin can be obtained.

  The interfacial polymerization method will be illustrated in more detail. First, an aqueous alkali solution of a dihydric phenol is prepared as an aqueous phase, and then a polymerization catalyst is added. Next, as an organic phase, an organosiloxane is dissolved in an organic solvent that is incompatible with water and dissolves a resin, and this solution is mixed with the previous alkaline solution. On the other hand, an organosiloxane copolymer resin is polymerized by dissolving a divalent carboxylic acid halide in an organic solvent separately from this mixed solution and further adding this solution to the previous alkali / organic solvent mixed solution.

  As the polymerization conditions, a desired resin solution can be obtained by conducting a polymerization reaction while stirring preferably at a temperature of 50 ° C. or lower for 1 to 8 hours.

  Examples of the alkali used when preparing the dihydric phenol aqueous solution in the interfacial polymerization include sodium hydroxide and potassium hydroxide.

  The terminal of the resin of the present invention may be sealed with monohydric phenol, monohydric acid chloride, monohydric alcohol, monohydric carboxylic acid or the like. Examples of monohydric phenols used as such end capping agents include phenol, o-cresol, m-cresol, p-cresol, p-tert-butylphenol, o-phenylphenol, m-phenylphenol, and 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 (“p- (α-cumyl) phenol)”. ) 2-phenyl-2- (2-hydroxyphenyl) propane, 2-phenyl-2- (3-hydroxyphenyl) propane and the like, and monovalent acid chlorides include benzoyl chloride, benzoic acid chloride, and methanesulfonyl chloride. , Phenyl chloroformate, etc., and monohydric alcohols include methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, pentanol, hexanol, dodecyl alcohol, stearyl alcohol, benzyl alcohol, phenethyl alcohol. Monovalent carboxylic acids include acetic acid, propionic acid, octanoic acid, cyclohexanecarboxylic acid, benzoic acid, toluic acid, phenylacetic acid, p-tert-butylbenzoic acid, p-methoxyphene Etc. Le acetic acid. Among these, a preferable end-capping agent includes p-tert-butylphenol.

  Interfacial polymerization catalysts include quaternary ammonium salts such as tributylbenzylammonium halide, tetrabutylammonium halide, trimethylbenzylammonium halide, triethylbenzylammonium halide, tributylbenzylphosphonium halide, tetrabutylphosphonium halide, trimethylbenzylphosphonium halide. And quaternary phosphonium salts such as triethylbenzylphosphonium halide. Among them, tributylbenzylammonium halide, tetrabutyl are preferable in that the polymerization is easily promoted and the amount of divalent carboxylic acid contained in the resin is easily reduced to 300 ppm or less. Ammonium halide, tributylbenzylphosphonium halide, and tetrabutylphosphonium halide are preferred.

  As the organic phase solvent in the interfacial polymerization, dichloromethane, 1,2-dichloroethane, chloroform, carbon tetrachloride, chlorobenzene, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, o-dichlorobenzene, 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 can be used. From this viewpoint, dichloromethane, chloroform, toluene, cyclohexanone and the like are preferably used.

  Acetic acid is added to the resin solution obtained after the polymerization, and after the polymerization is completed, the resin solution is repeatedly washed with water to remove ionic components such as sodium and potassium and a polymerization catalyst contained in the resin solution. The water used for washing may be acidic or basic, but it is desirable to wash repeatedly until the washing waste water becomes neutral.

  The organosiloxane copolymer resin solution obtained here is added to a poor solvent to precipitate a polymer (reprecipitation). Although it does not specifically limit as a poor solvent used here, Hydrocarbons, such as alcohols, such as methanol, ethanol, and isopropyl alcohol, hexane, etc. are used suitably. The polymer solid content obtained by the precipitation can be isolated by filtration or the like, and then dried to obtain the solid content.

  The organosiloxane copolymer resin of the present invention may be used alone or in combination of two or more.

  Moreover, you may add suitably an ultraviolet absorber, a light stabilizer, antioxidant, etc. to the organosiloxane copolymer resin of this invention as needed. As the ultraviolet absorber, known ones can be used, and the solubility in the solvent, the compatibility with the resin and the durability, particularly for clearing the thin film, is higher than that of a normal ultraviolet absorber without bleeding out. It is preferable to use a benzotriazole-based ultraviolet absorber that can be added.

  The organosiloxane copolymer resin of the present invention has transparency and flexibility while maintaining heat resistance, color change due to ultraviolet rays is suppressed, water repellency is excellent, the friction coefficient is small, and electrical characteristics (insulating properties, Excellent dielectric properties, etc.) Films for electronic parts such as capacitors, liquid crystal display devices, plasma displays, retardation films for organic EL, polarizing films, antireflection films, wide viewing angle films, high brightness films, diffusion films, In addition to optical films such as light guide films, coating layers and laminates thereof, touch panels provided with ITO films, base films for microfabrication, diaphragms for acoustic devices such as speakers, electronic circuit boards, liquid crystal drivers, It can be used as an insulating protective film for a wire harness or the like.

  In addition, because it has excellent transparency in the short wavelength region, it is used for optical recording media such as CD-R and DVD-R, flat displays, electrophotographic photoreceptor binders, optical lenses, and other semiconductors. It can be used as a light source material such as a laser or a light-emitting diode, and is particularly excellent in the transmittance of ultraviolet rays having a short wavelength of around 350 nm, so that it can be used for next-generation high-density optical recording media.

  Next, the present invention will be specifically described with reference to examples and comparative examples.

  In the examples, organosiloxanes having the structures of the following general formulas (IV) to (VII) were used. Table 1 shows the relationship between the molecular weight and m of the organosiloxane used.

  Various evaluations were performed on the obtained organosiloxane copolymer resin according to the following methods.

1. Resin properties (molecular weight)
Waters GPC system (1515 HPLC pump and 2414 differential refractometer), 2410 RI as detector, Mixed-D (packed silica gel particle size 5 μm, tube length 300 × inner diameter 7.5 mm) as column, solvent chloroform flow rate 1 ml / As a minute, the weight average molecular weight was measured in terms of polystyrene.
(Tg)
Using 15 mg resin as a sample, using a DSC (Differential Scanning Calorimetry) device (DSC7 manufactured by PerkinElmer Co., Ltd.), measuring from −80 ° C. to 300 ° C. under the temperature rising rate of 10 ° C./min is obtained. An intermediate value of the temperatures of two bending points derived from the glass transition in the temperature rising curve was determined, and this was taken as the glass transition temperature.
(Solubility)
90 parts by mass of chloroform was added to 10 parts by mass of the resin, and the mixture was stirred at 25 ° C. for 24 hours to determine whether the resin was dissolved without generating insoluble matter such as gel. What melt | dissolved was made into (circle), and what was not melt | dissolved was made into x.
(Solution viscosity)
Using chloroform as a solvent, a polymer solution having a resin solid content of 10% was prepared, and the solution viscosity at 15 ° C. was measured.
(Carboxyl value)
In a test tube, 0.15 g of resin was precisely weighed and dissolved in 5 ml of benzyl alcohol by heating. After mixing 10 ml of chloroform and a benzyl alcohol solution of the above resin, phenol red was added as an indicator, and neutralization titration was performed with a 0.1 N KOH benzyl alcohol solution while stirring to obtain a carboxyl value.
(Amine number)
The resin 0.5 g was dissolved in 20 ml of m-cresol at 60 ° C., cooled to room temperature, and titrated with a 0.1 N p-toluenesulfonic acid aqueous solution.

2. Film characteristics Using the solution prepared by adding 85 parts by mass of chloroform to 15 parts by mass of the resin to the organosiloxane copolymer resin obtained above, solution casting was performed on a PET film to prepare a 100 μm coating film. . About the obtained coating film, it dried at 120 degreeC under reduced pressure for 24 hours, and produced the resin film. And the following evaluation was performed.
(Transmittance)
Using a U-4000 type self-recording spectrophotometer manufactured by Hitachi, Ltd., the light transmittance at wavelengths of 350 nm and 450 nm of the obtained 100 μm resin film was measured, and a transmittance of 50% or more was regarded as acceptable.
(Tensile modulus / tensile elongation)
With the obtained 100 μm resin film, the tensile elastic modulus and the tensile elongation at the breaking point were measured according to JIS K-2318 using an Intesco tensile / compression tester.
(Contact angle)
With the obtained 100 μm resin film, in accordance with JIS R 3257, using a contact angle meter CA-DT • A type manufactured by Kyowa Interface Science Co., Ltd., in an environment of 20 ° C. × 50% RH, to a 50 μm resin film On the other hand, the contact angle was measured by dropping pure water. A larger contact angle indicates higher water repellency.
(Coefficient of friction)
The obtained 100 μm resin film was measured at a load of 50 g and a speed of 100 m / sec using a TS501 made by Kyowa Interface Science and using a linear contact made of SUS.
(UV irradiation)
As a simple test to ascertain the degree of yellowing when left outdoors, a sun light ray UV exposure device 10W-FL10BL6 that emits a wavelength near 360 nm is attached to a Sanhayato ultraviolet exposure device, and the film obtained above is used. Irradiated with ultraviolet rays for 24 hours. Measure yellow index (YI) before and after UV irradiation and measure ΔYI, which is the change in YI before and after UV irradiation, by using Z-Σ90 manufactured by Nippon Denshoku Kogyo Co., Ltd. It was. Incidentally, it denoted the YI before ultraviolet irradiation and YI _0.

Production Example 1
In a reaction vessel equipped with a stirrer, 2,2-bis (4-hydroxyphenyl) propane (24.4219.67 parts by mass (97.2 mols)) as a dihydric phenol component and p-tert. -Butylphenol (PTBP) 0.50 parts by mass (3.0 parts by mole), sodium hydroxide 13.4010.82 parts by weight (300 parts by mole) as an alkali, and benzyl-tri-n-butylammonium chloride (BTBAC) as a polymerization catalyst ) 0.47 parts by mass and 0.17 parts by mass of hydrosulfite sodium (SHS) were charged and dissolved in 1000 parts by mass of water (aqueous phase). Separately, 9.85 parts by mass (2.8 mol parts) of an organosiloxane represented by the following formula (IV) was dissolved in 200 parts by mass of methylene chloride (organic phase 1). This organic phase 1 was added to the previously prepared aqueous phase under strong stirring, and the mixture was stirred at 15 ° C. for 30 minutes.

  Further, separately from the organic phase 1, 23.36 parts by mass (101.5 mol parts) of 1,4-cyclohexanedicarboxylic acid chloride was dissolved in 400 parts by mass of methylene chloride (organic phase 2). This organic phase 2 was added to a mixed solution of an aqueous phase and an organic phase 1 that had already been stirred under strong stirring, and a polymerization reaction was performed at 15 ° C. for 2 hours. Thereafter, 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 acetic acid were newly added to stop the reaction, followed by stirring at 15 ° C. for 30 minutes. After this organic phase was washed 5 times with pure water, the organic phase was added into hexane to precipitate a polymer, and after separation and drying, an organosiloxane copolymer resin (P-1) was obtained. The results are shown in Table 2. When the resin composition of the obtained organosiloxane copolymer resin (P-1) was confirmed by NMR, it was a resin composition as prepared.

Production Example 2
25.48 parts by mass (97.0 mol parts) of 2,2-bis (3-methyl-4-hydroxyphenyl) propane (BisC) as a dihydric phenol component, and p-tert-butylphenol (PTBP) as an end-capping agent 0.46 parts by mass (3.0 parts by mol), 12.48 parts by mass (300 parts by mol) of sodium hydroxide as an alkali, 9.83 parts by mass (3.0 parts by mol) of organosiloxane, 1,4-cyclohexanedicarboxylic acid An organosiloxane copolymer resin (P-2) was obtained in the same manner as in Production Example 1 except that the acid chloride was 21.75 parts by mass (101.5 mol parts). The results are shown in Table 2. When the resin composition of the obtained organosiloxane copolymer resin (P-2) was confirmed by NMR, it was a resin composition as prepared.

Production Example 3 to Production Example 8
In the same manner as in Production Example 1, organosiloxane copolymer resins (P-3) to (P-8) were produced. The results are shown in Table 2. The resin compositions of the obtained organosiloxane copolymer resins (P-3) to (P-8) were confirmed by NMR, and all were resin compositions as prepared.

Production Example 9 to Production Example 12
In the same manner as in Production Example 1, organosiloxane copolymer resins (P-9) to (P-12) were produced. The results are shown in Table 3. When the resin composition of the obtained organosiloxane copolymer resins (P-9) to (P-12) was confirmed by NMR, they were all resin compositions as prepared.

Production Example 13 to Production Example 15
In the same manner as in Production Example 1, polyarylate resins (P-13) to (P-15) were produced. The results are shown in Table 3. When the resin composition of the obtained polyarylate resins (P-13) to (P-15) was confirmed by NMR, all of them were resin compositions as prepared.

Example 1
Using a solution prepared by adding 85 parts by mass of chloroform to 15 parts by mass of the organosiloxane copolymer resin (P-1) prepared in Production Example 1, solution casting was performed on a PET film to prepare a 100 μm coating film. did. About the obtained coating film, it dried at 120 degreeC under reduced pressure for 24 hours, produced the resin film (F-1), and performed various evaluation. The results are shown in Table 4.

Example 2
A resin film (F-2) was produced in the same manner as in Example 1 except that the organosiloxane copolymer resin (P-2) was used instead of the organosiloxane copolymer resin (P-1), and various evaluations were made. I did it. The evaluation results are shown in Table 4.

Example 3
A resin film (F-3) was prepared in the same manner as in Example 1 except that the organosiloxane copolymer resin (P-3) was used instead of the organosiloxane copolymer resin (P-1), and various evaluations were made. I did it. The evaluation results are shown in Table 4.

Example 4 to Example 10
The same operations as in Example 1 were performed to evaluate the resin films (F-4) to (F-10). The evaluation results are shown in Table 4.

Comparative Examples 1 to 5
The same operations as in Example 1 were performed to evaluate the resin films (F-11) to (F-15). The evaluation results are shown in Table 5.

Example 11
A solution prepared by adding 85 parts by mass of chloroform to 15 parts by mass of the organosiloxane copolymer resin (P-1) prepared in Production Example 1 and 0.15 parts by mass of Tinuvin P manufactured by Ciba Specialty Chemicals as an ultraviolet absorber. The solution was cast on a PET film to prepare a 100 μm coating film. About the obtained coating film, it dried at 120 degreeC under pressure reduction for 24 hours, produced the resin film (F-16), and performed various evaluation. The results are shown in Table 5.

Example 12
A resin film (F-17) was produced in the same manner as in Example 11 except that the organosiloxane copolymer resin (P-2) prepared in Production Example 2 was used, and various evaluations were performed. The evaluation results are shown in Table 5.

Examples 13-15
The same operations as in Example 11 were performed to evaluate the resin films (F-18) to (F-20). The evaluation results are shown in Table 5.

  The films obtained in the examples had a low tensile elastic modulus and excellent flexibility. Moreover, the contact angle was large and the friction coefficient was low. Therefore, the surface of the resin composition is hard to get dirty and is strong against friction and wear, and has excellent surface characteristics. Moreover, since the solution viscosity at the time of dissolution was low, the handling property was also excellent.

  Since the film obtained in Comparative Example 1 used MPC as the dicarboxylic acid component of the organosiloxane copolymer resin (P-11) used, yellowing during UV irradiation was significant.

  Since the film obtained in Comparative Example 2 used bisphenol C having a side chain as the dihydric phenol component of the organosiloxane copolymer resin (P-12) used, yellowing during ultraviolet irradiation was significant. Moreover, although the tensile elasticity modulus was low and it was excellent in the softness | flexibility, heat resistance was insufficient.

  The film obtained in Comparative Example 3 had high tensile elastic modulus and poor flexibility because the polyarylate resin (P-13) used was not copolymerized with organosiloxane.

  The film obtained in Comparative Example 4 uses SBC as a dicarboxylic acid component of the used polyarylate resin (P-14) in a predetermined amount or more, and is not flexible because organosiloxane is not copolymerized. It also lacked heat resistance.

The film obtained in Comparative Example 5 used MPC as the dicarboxylic acid component of the polyarylate resin (P-15) used, and because the organosiloxane was not copolymerized, yellowing during UV irradiation was significant. . Moreover, the elastic modulus was high and the flexibility was poor. Furthermore, the contact angle was small and the coefficient of friction was high. Therefore, the surface of the resin composition is easily soiled and weak against friction and wear, and the surface characteristics are insufficient.

Claims (3)

(A) An organosiloxane copolymer resin composed of a dicarboxylic acid residue, (B) a dihydric phenol residue, and (C) an organosiloxane residue, wherein 60 mol% or more of fat is contained with respect to the total dicarboxylic acid A cyclic dicarboxylic acid, the alicyclic dicarboxylic acid is an alicyclic dicarboxylic acid represented by the following general formula (I), and an organosiloxane is an organosiloxane represented by the following general formula (II): An organosiloxane copolymer resin, wherein a ratio of an organosiloxane residue in the resin is 0.05% by mass or more and less than 80% by mass.
[In General Formula (II), R ₁ and R ₂ may be the same or different, and are an aliphatic group or an aromatic group having 1 to 12 carbon atoms. R ₃ , R ₄ , R ₅ and R ₆ are all aliphatic groups or aromatic groups which may be the same or different. m is an integer of 5 or more, and X ₁ and X ₂ are any group of the general formula (III). In the general formula (III), R ₁₀ is 1-5 aliphatic group or an aromatic group carbon atoms, s is an integer of 0-4. ]  2. The organosiloxane copolymer resin according to claim 1, wherein the dicarboxylic acid is alicyclic dicarboxylic acid / aliphatic dicarboxylic acid = 60/40 to 100/0 (molar ratio). A molded article, film, or coat film obtained by molding the organosiloxane copolymer resin according to claim 1 or 2.