JP2013194171A - Polyacrylate resin composition and molded article made by molding the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyacrylate resin composition having excellent heat resistance, transparency and hydrolysis resistance.SOLUTION: A polyacrylate resin composition contains 100 pts.mass total of 10-100 mass% polyacrylate resin and 90-0 mass% polycarbonate resin, 0.1-5 pts.mass polycarbodiimide compound having a number average molecular weight of ≥5,000 and 0.01-1 pts.mass phosphorus compound. The polyacrylate resin composition has excellent heat resistance and transparency and therefore is used for electric and electronic components, automobile interior and exterior components, housing equipment or the like and further suitably used for components used in the outdoor such as components related to displays and illuminations or automobiles or the like because of the excellent hydrolysis resistance.

Description

  The present invention relates to a polyarylate resin composition having excellent heat resistance, transparency, and hydrolysis resistance.

  Conventionally, polyarylate resins and polycarbonate resins have been used in applications such as optical lenses, electronic parts such as OA parts, sheets, automobile parts, and construction materials, taking advantage of excellent heat resistance, molding fluidity, and transparency. ing. Of these, polyarylate resins are widely used in interior and exterior parts for automobiles because they have better heat resistance than polycarbonate resins. In such applications, improvement of hydrolysis resistance as well as heat resistance has been desired.

Patent Documents 1 and 2 disclose a resin composition in which hydrolysis resistance is improved by adding a carbodiimide compound to an aromatic polycarbonate resin. Such a carbodiimide compound was able to improve the hydrolysis resistance of the polyarylate resin, but the effect of improving the hydrolysis resistance was low and insufficient as compared with the case where it was added to the polycarbonate resin or the polyester resin. It was.
On the other hand, the polyarylate resin has higher heat resistance than the polycarbonate resin, but has a high resin melting temperature in melt kneading and molding, and the added carbodiimide compound is thermally decomposed, and the resin composition is colored and yellowed. There was a problem. Patent Document 3 discloses a mixture containing aluminum oxide and aluminum oxyhydroxide as a stabilizer for a carbodiimide compound. Such a mixture increases the durability of the carbodiimide compound and can be suitably used for polycarbonate resins and the like. However, the effect of polyarylate resin was insufficient.

JP 2009-108149 A JP 2010-106171 A Special table 2009-540050 gazette

  An object of this invention is to provide the polyarylate resin composition excellent in heat resistance, transparency, and hydrolysis resistance.

The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems.
That is, the gist of the present invention is as follows.

(1) 10 to 100% by mass of polyarylate resin, 100 parts by mass of polycarbonate resin 90 to 0% by mass, 0.1 to 5 parts by mass of polycarbodiimide compound having a number average molecular weight of 5000 or more, and 0.01 to 0.1% of phosphorus compound A polyarylate resin composition containing 1 part by mass.
(2) The polyarylate resin composition according to (1), wherein the phosphorus compound is a phosphite compound represented by the following general formula (I).
In general formula (I), R ¹ is an aliphatic alcohol residue, and R ³ represents a phenyl group. R ² represents an aliphatic alcohol residue or a phenyl group. Both R ¹ and R ² may be the same residue derived from the same polyhydric alcohol compound.
(3) The polyarylate resin composition according to (1) or (2), further comprising 0.01 to 1 part by mass of a silane compound represented by the following general formula (II).
In general formula (II), R ⁴ represents any one of a vinyl group having 1 to ⁴ carbon atoms, an acryl group, and a methacryl group. R ^{5 to} R ⁷ represent an alkoxy group having 1 to 4 carbon atoms or an alkyl group.
(4) A molded article obtained by molding the polyarylate resin composition of (1) to (3).

  ADVANTAGE OF THE INVENTION According to this invention, the polyarylate resin composition excellent in heat resistance, transparency, and hydrolysis resistance can be provided.

  The polyarylate resin composition of the present invention comprises a polyarylate resin, a polycarbonate resin, and a specific polycarbodiimide compound.

  The polyarylate resin in the present invention is an aromatic polyester composed of an aromatic dicarboxylic acid residue unit and a bisphenol residue unit.

  Examples of the polyarylate raw material for introducing the aromatic dicarboxylic acid residue unit include terephthalic acid and isophthalic acid. In the present invention, a polyarylate resin composition obtained by mixing both is particularly preferred in terms of melt processability and mechanical properties. The mixing ratio (terephthalic acid / isophthalic acid) is preferably in the range of 90/10 to 10/90 in molar ratio, more preferably 70/30 to 30/70, and most preferably 50/50. Even if the mixing mole fraction of terephthalic acid is less than 10 mol% or more than 90 mol%, a sufficient degree of polymerization may not be achieved when polymerization is performed by the interfacial polymerization method.

  Examples of the polyarylate raw material for introducing a bisphenol residue unit include 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2 , 2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 4,4′-dihydroxydiphenylsulfone, 4,4′- Examples include dihydroxydiphenyl ether, 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxydiphenyl ketone, 4,4′-dihydroxydiphenylmethane, 1,1-bis (4-hydroxyphenyl) cyclohexane and the like. These compounds may be used alone or in combination of two or more, and for economic reasons, 2,2-bis (4-hydroxyphenyl) among these compounds. Propane is preferably used, and optimally the compound is used alone.

  The inherent viscosity of the polyarylate resin in the present invention is preferably 0.4 to 0.8, more preferably 0.4 to 0.7, from the viewpoint of mechanical properties and fluidity. The inherent viscosity can be determined from the solution viscosity measured at a temperature of 25 ° C. using 1,1,2,2-tetrachloroethane as a solvent.

  The production method of the polyarylate resin is not particularly limited, and those obtained by a known method can be used. A polyarylate resin obtained by an interfacial polymerization method or a melt polymerization method can be preferably used.

  As such a polyarylate resin, for example, commercially available U-100, U powder manufactured by Unitika Ltd. can be preferably used.

  The polycarbonate resin in the present invention is a polycarbonate comprising a bisphenol residue unit and a carbonate residue unit. Since the polycarbonate resin has a bisphenol residue unit similar to the polyarylate resin in the previous period, the polycarbonate resin often shows good compatibility with the polyarylate resin.

  Examples of the polycarbonate raw material for introducing the bisphenol residue unit include 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 2, 2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclohexane, , 1-bis (4-hydroxyphenyl) decane, 1,3-Mataha 1,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclododecane, 4,4′-dihydroxy Diphenyl ether, 4,4'-dithiodiphenol, 4,4'-dihydroxy-3,3'-dichlorodipheny Ether, 4,4'-dihydroxy-2,5-dihydroxydiphenyl ether, and the like. These may be used alone or in combination of two or more. Among these compounds, it is preferable to use at least 2,2-bis (4-hydroxyphenyl) propane. For economic reasons, the compound is optimally used alone.

  As precursors for introducing carbonate residue units, carbonyl halides such as phosgene and carbonates such as diphenyl carbonate can be used.

  The inherent viscosity of the polycarbonate resin in the present invention is preferably 0.4 to 0.8, more preferably 0.4 to 0.6, from the viewpoint of mechanical properties and fluidity.

  The production method of the polycarbonate resin is not particularly limited, and those obtained by known methods can be used. A polycarbonate resin obtained by an interfacial polymerization method or a melt polymerization method can be suitably used.

  As such a polycarbonate resin, for example, commercially available Caliber K200-30, 200-13, 200-3 manufactured by Sumitomo Dow can be preferably used.

  The blending ratio of the polyarylate resin and the polycarbonate resin in the present invention needs to be 10/90 to 100/0 (mass ratio), preferably 20/80 to 90/10, and 30/70 to 80 / More preferably, it is 20. When the polyarylate resin is less than 10% by mass, the effect of improving heat resistance is poor.

The polycarbodiimide compound having a number average molecular weight of 5000 or more in the present invention is a carbodiimide compound having a number average molecular weight of 5000 or more and having two or more carbodiimide groups in the molecule.
A carbodiimide compound refers to a compound having a carbodiimide group represented by (—N═C═N—) in the molecule. A compound having one carbodiimide group in the molecule is referred to as a monocarbodiimide compound, and a compound having two or more carbodiimide groups in the molecule is referred to as a polycarbodiimide compound. In the present invention, the number average molecular weight of the polycarbodiimide compound needs to be 5000 or more, preferably 5500 or more, and more preferably 6000 or more. If the number average molecular weight is less than 5,000, the polycarbodiimide compound may be sufficiently dispersed in the polyarylate resin, the effect of improving hydrolysis resistance may not be sufficient, and the polyarylate resin composition may turn yellow. is there.

  Examples of the polycarbodiimide compound include poly (4,4′-diphenylmethanecarbodiimide), poly (3,3′-dimethyl-4,4′-diphenylmethanecarbodiimide), poly (naphthylenecarbodiimide), and poly (p-phenylenecarbodiimide). , Poly (m-phenylenecarbodiimide), poly (methyl-diisopropylphenylenecarbodiimide), poly (triethylphenylenecarbodiimide), poly (triisopropylphenylenecarbodiimide), poly (1,3,5-triisopropylbenzene) carbodiimide, poly (1 , 5-diisopropylbenzene) carbodiimide, poly (1,3,5-triisopropylbenzene) carbodiimide, and poly (1,5-diisopropylbenzene) carbodiimide. Among them, poly (4,4′-methylenebiscyclohexylcarbodiimide) and poly (1,3,5-triisopropylbenzene) are excellent in dispersibility and high in the effect of improving the hydrolysis resistance of the polyarylate resin composition. Carbodiimide and poly (1,5-diisopropylbenzene) carbodiimide are preferred.

  The carbodiimide compound can be produced by a known method. For example, the method of manufacturing by the carbon dioxide removal reaction of a diisocyanate compound is mentioned. In the carbodiimide compound, an isocyanate group may remain at the terminal.

  The content of the polycarbodiimide compound needs to be 0.1 to 5 parts by mass with respect to 100 parts by mass in total of the polyarylate resin and the polycarbonate resin, and preferably 0.3 to 4 parts by mass, More preferably, it is 0.5-3 mass parts. If the content of the polycarbodiimide compound is less than 0.1 parts by mass, the effect of improving hydrolysis resistance is insufficient, and if it exceeds 5 parts by mass, the effect of improving hydrolysis resistance reaches saturation, and heat resistance is improved. May decrease. Moreover, since a polycarbodiimide compound is generally expensive, it is not preferable economically.

  The phosphorus compound in the present invention is a phosphite compound and / or a phosphonite compound. Specific examples include, for example, trisnonyl phosphite, trisphenyl phosphite, tristridecyl phosphite, tris (monononylphenyl) phosphite, tris (mono-dinonylphenyl) phosphite, tris (2,4-di-). -T-butylphenyl) phosphite, tris (2-t-butylphenyl) phosphite, tris (2,4-di-t-butyl-5-methylphenyl) phosphite, tris (2,5-di-t -Butylphenyl) phosphite, tris (2-t-butylphenyl) phosphite, tris [2- (1,1-dimethylpropyl) phenyl] phosphite, tris [2,4-di- (1,1-dimethyl) Propyl) phenyl] phosphite, tris (2-cyclohexylphenyl) phosphite, trisphenylphos Ite, tris (octylthioethyl) phosphite, tris (octylthiopropyl) phosphite, tris (cresylthiopropyl) phosphite, tris (3,5-di-t-butyl-4-hydroxyphenyl) phosphite, bis (Nonylphenyl) pentaerythritol diphosphite, 4,4′-butylidene-bis (3-methyl-6-tert-butylphenyl-di-tridecyl) phosphite, 4,4′-butylidene-bis (3-methyl-) 6-t-butylphenyl-di-octyl) phosphite, 1,1,3-tris (2-methyl-4-ditridecyl phosphite-5-t-butylphenyl) butane, bis (2,4-di-) t-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-methylphenol) ) Pentaerythritol-diphosphite, bis (2,6-di-t-butyl-4-ethylphenyl) pentaerythritol-diphosphite, bis (2,4,6-tri-t-butylphenyl) spiropentaerythritol-diphosphite, Tetrakis (2,4-t-butylphenyl) [1,1-biphenyl] -4,4′-diylbisphosphonite, bis (2,4-bis (1,1-dimethylethyl) -6-methylphenyl) Examples thereof include ethyl ester phosphorous acid.

  Among the phosphorus compounds, by using a specific phosphite compound, a polyarylate resin composition having more excellent hydrolysis resistance and color tone can be obtained.

The specific phosphorous ester compound used in the present invention is represented by the following general formula (I).
In general formula (I), R ¹ is an aliphatic alcohol residue, and R ³ represents a phenyl group. R ² represents an aliphatic alcohol residue or a phenyl group. Both R ¹ and R ² may be the same residue derived from the same polyhydric alcohol compound. For example, an example of such a polyhydric alcohol is pentaerythritol.

Such phosphite compounds include bis (2,6-di-t-butyl-4-ethylphenyl) pentaerythritol-diphosphite, bis (2,4,6-tri-t-butylphenyl) spiropenta. Erythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-methylphenyl) ) Pentaerythritol-diphosphite, bis (2,4-bis (1,1-dimethylethyl) -6-methylphenyl) ethyl ester phosphorous acid and the like, and the hydrolysis resistance and color tone of the polyarylate resin composition are improved. Bis (2,6-di-t-butyl-4-methylphenyl) pentaeryth is highly effective Toll - diphosphite, bis (2,4-bis (1,1-dimethylethyl) -6-methylphenyl) can be preferably used ethyl ester phosphorous acid.
Examples of such phosphite compounds include commercially available PEP-36 manufactured by ADEKA, IRGAFOS 38 manufactured by BASF, and the like.

  The content of the phosphorus compound needs to be 0.01 to 1 part by mass with respect to 100 parts by mass in total of the polyarylate resin and the polycarbonate resin, and preferably 0.02 to 0.5 parts by mass. 0.03-0.2 parts by mass is more preferable. When the content of the phosphorus compound is less than 0.01 parts by mass, the effect of preventing discoloration at the time of molding and processing during the melt kneading of the polyarylate resin composition becomes poor, and when the content exceeds 1 part by mass, The effect of suppressing discoloration may be saturated, and heat resistance may be reduced. Two or more types of phosphorus compounds may be used in combination, and in that case, the total amount thereof may be within the above range.

  The inherent viscosity of the polyarylate resin composition of the present invention is preferably 0.40 to 0.60, more preferably 0.42 to 0.58, and 0.44 to 0.56. Is more preferable. When the inherent viscosity exceeds 0.60, the melt viscosity becomes high and injection molding becomes difficult. When the inherent viscosity is less than 0.40, the impact strength of the obtained molded product tends to be insufficient.

  In this invention, it can be set as the polyarylate resin composition which was more excellent in hydrolysis resistance and color tone by mix | blending a specific silane compound further.

The silane compound blended in the polyarylate resin composition of the present invention is represented by the following general formula (II).
In general formula (II), at least two of R ^{4 to} R ⁷ represent a functional group selected from an alkoxy group having 1 to 4 carbon atoms, an acryl group, a methacryl group, and a vinyl group. The rest represents other than an alkoxy group having 1 to 4 carbon atoms, a vinyl group, and an acrylic group, and examples thereof include hydrogen having 1 to 4 carbon atoms, an alkyl group, and an epoxy group. Examples of the alkoxy group include a methoxy group and an ethoxy group. Examples of the vinyl group include a vinyl group and a p-styryl group. Examples of the acrylic group include a 3-methacryloxypropyl group and a 3-acryloxypropyl group. Examples of the alkyl group include a methyl group and an ethyl group. Examples of the epoxy group include 3-glycidoxypropyl group and 2- (3,4-epoxycyclohexyl) group.

  A commercial item can be used as such a silane compound, for example, tetramethoxysilane (GE Toshiba Silicone TSL8114, Shin-Etsu Chemical KBM-04), tetraethoxysilane (GE Toshiba Silicone TSL8124, Shin-Etsu). Chemical industry KBE-04), methyltrimethoxysilane (GE Toshiba Silicone TSL8113, Shin-Etsu Chemical KBM-13), methyltriethoxysilane (GE Toshiba Silicone TSL813, Shin-Etsu Chemical KBE- 13), dimethyldimethoxysilane (GE Toshiba Silicone TSL8112), dimethyldiethoxysilane (GE Toshiba Silicone TSL8122, Shin-Etsu Chemical KBE-22), methyldimethoxysilane (GE Toshiba Silicone TSL8117), Tildiethoxysilane (GE Toshiba Silicone TSL8127), dimethylethoxysilane (GE Toshiba Silicone TSL8126), phenyltrimethoxysilane (GE Toshiba Silicone TSL8173), phenyltriethoxysilane (GE Toshiba Silicone TSL8178, Shin-Etsu Chemical KBE-103), diphenyldimethoxysilane (GE Toshiba Silicone TSL8172), diphenyldiethoxysilane (GE Toshiba Silicone TSL8177), hexyltrimethoxysilane (Shin-Etsu Chemical KBM-3063), Decyltrimethoxysilane (KBM-3103C manufactured by Shin-Etsu Chemical Co., Ltd.), 3-glycidoxypropyldimethoxymethylsilane (TSL-8355 manufactured by GE Toshiba Silicone), 3-glycidoxy Lopyltrimethoxysilane (GE Toshiba Silicone TSL-8350, Shin-Etsu Chemical KBM-403), dimethylvinylmethoxysilane (GE Toshiba Silicone TSL8317), methylvinyldimethoxysilane (GE Toshiba Silicone TSL8315) , Methylvinyldiethoxysilane (GE Toshiba Silicone, Inc. TSL8316), dimethylvinylethoxysilane (GE Toshiba Silicone, Inc. TSL8318), vinyltrimethoxysilane (Shin-Etsu Chemical KBM-1003), vinyltriethoxysilane (GE Toshiba) Silicone TSL8311, Shin-Etsu Chemical KBE-1003), 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (Shin-Etsu Chemical KBM-303), 3-glycidoxypropyl Tildiethoxysilane (KBE-402 manufactured by Shin-Etsu Chemical Co., Ltd.), p-styryltrimethoxysilane (KBM-1403 manufactured by Shin-Etsu Chemical Co., Ltd.), 3-methacryloxypropylmethyldimethoxysilane (TSL8375 manufactured by GE Toshiba Silicone Co., Ltd., Shin-Etsu Chemical) KBM-502 manufactured by Kogyo Co., Ltd., 3-methacryloxypropyltrimethoxysilane (TSL8370 manufactured by GE Toshiba Silicone, KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.), KBE manufactured by Shin-Etsu Chemical Co., Ltd. -502), 3-methacryloxypropyltriethoxysilane (KBE-503 manufactured by Shin-Etsu Chemical Co., Ltd.), 3-acryloxypropyltrimethoxysilane (KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd.), 3-acryloxypropylmethyldimethoxysilane (Shin-Etsu Chemical Company made KBM-5102), and the like.

  Among them, a silane compound having one functional group selected from an acrylic group having 1 to 4 carbon atoms, a methacryl group, and a vinyl group and having 3 alkoxy groups having 1 to 4 carbon atoms is advantageous in improving the crystallization speed. preferable. Specific examples and trade names of such silane compounds include vinyltrimethoxysilane (KBE-1003 manufactured by Shin-Etsu Chemical Co., Ltd.), vinyltriethoxysilane (GE Toshiba Silicone Co., Ltd. TSL8311, Shin-Etsu Chemical Co., Ltd. KBE- 1003), p-styryltrimethoxysilane (KBM-1403 manufactured by Shin-Etsu Chemical Co., Ltd.), 3-methacryloxypropyltrimethoxysilane (TSL8370 manufactured by GE Toshiba Silicone Co., Ltd., KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.), 3-methacryloxy Examples thereof include propyltriethoxysilane (KBE-503 manufactured by Shin-Etsu Chemical Co., Ltd.), 3-acryloxypropyltrimethoxysilane (KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd.), and the like.

  The content of the silane compound is preferably 0.01 to 1 part by mass and more preferably 0.02 to 0.5 part by mass with respect to 100 parts by mass of the total amount of the polyarylate resin and the polycarbonate resin. Preferably, it is 0.03-0.2 mass part. When the content of the silane compound is less than 0.01 parts by mass, the effect of preventing discoloration at the time of molding of the polyarylate resin composition and discoloration by heat at the time of long-term use of the molded body may not be sufficient. There exists a tendency for the effect which prevents the discoloration by the heat | fever at the time of long-term use of a molded object to be scarce. When the content of the silane compound exceeds 1 part by mass, not only the effect of suppressing discoloration is saturated, but also economically undesirable. Two or more types of silane compounds may be used in combination, and in that case, the total amount thereof may be within the above range.

  In the present invention, a molded product having a better color tone can be obtained by using a phenolic compound in combination.

  The phenolic compound used in the present invention is a compound containing a hindered phenol moiety having a substituent at the ortho position of the hydroxyl group, preferably including a hindered phenol moiety having a substituent at the two ortho positions of the hydroxyl group. A compound. Examples of the substituent at the ortho position include alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and t-butyl group. . When the phenolic compound has a substituent at two ortho positions of the hydroxyl group in the hindered phenol part, the two substituents may be the same or different, and preferably are t-butyl groups at the same time.

  Preferred phenol compounds containing a hindered phenol moiety having a substituent at two ortho positions of the hydroxyl group include, for example, propionate-based hindered phenol compounds, isocyanurate-based hindered phenol compounds, benzene-based hindered phenol compounds, and triazine-based hindered compounds. Examples include phenolic compounds and phosphoric acid hindered phenolic compounds.

  Specific examples of propionate-based hindered phenol compounds include, for example, triethylene glycol-bis-3- (3′-t-butyl-4′-hydroxy-5′-methylphenyl) propionate, hexamethylene glycol-bis- [β. -(3,5-di-t-butyl-4-hydroxy-phenyl) propionate], tetrakis [methylene-3 (3 ', 5'-di-t-butyl-4'-hydroxy-phenyl) propionate] methane, 2,2′-thio [diethyl-bis-3 (3 ″, 5 ″ -di-t-butyl-4 ″ -hydroxyphenyl) propionate], octadecyl-3- (4′-hydroxy-3 ′, 5′- And di-t-butylphenyl) propionate.

  Specific examples of the isocyanurate-based hindered phenol compound include, for example, 1,3,5-tris (3 ′, 5′-di-t-butyl-4′-hydroxybenzoyl) isocyanurate, 1,3,5-tris. (3 ′, 5′-di-t-butyl-4′-hydroxybenzyl) isocyanurate and the like can be mentioned.

  Specific examples of the benzene hindered phenol compound include, for example, 1,3,5-trimethyl-2,4,6-tris (3 ′, 5′-di-t-butyl-4′-hydroxy-benzyl) benzene. Can be mentioned.

  Specific examples of triazine-based hindered phenol compounds include, for example, 6- (4′-hydroxy-3 ′, 5′-di-t-butylanilino) -2,4-bis-octyl-thio-1,3,5- A triazine etc. can be mentioned. Specific examples of phosphoric acid hindered phenol compounds include, for example, 3 ′, 5′-di-t-butyl-4′-hydroxy-benzylphosphoric acid dimethyl ester, bis (3,5-di-t-butyl- 4-hydroxybenzyl phosphoric acid) monomethyl ester nickel salt and the like.

  Among the above specific examples, it is preferable to use propionate-based hindered phenol compounds, particularly octadecyl-3- (4'-hydroxy-3 ', 5'-di-t-butylphenyl) propionate.

  The content of the phenolic compound is preferably 0.01 to 1 part by mass and more preferably 0.02 to 0.2 part by mass with respect to 100 parts by mass of the total amount of the polyarylate resin and the polycarbonate resin. preferable. When the content of the phenolic compound content is less than 0.01 parts by mass, the effect of preventing discoloration during molding of the polyarylate resin composition and discoloration due to heat during long-term use of the molded product is not sufficient In particular, the effect of preventing discoloration due to heat during long-term use of the molded product tends to be poor. If the content of the phenolic compound content exceeds 1 part by mass, the effect of suppressing discoloration is saturated, which is economically undesirable. Two or more types of phenolic compounds may be used in combination, and in that case, the total amount thereof may be within the above range.

  A single compound in which phosphorus and phenol are synthesized can also be used. Such compounds include 6- [3- (3-t-butyl-4-hydroxy-5-methyl) propoxy] -2,4,8,10-tetra-t-butyldibenzo [d, f] [ 1,3,2] -dioxaphosphine, and a specific trade name is Sumitizer GP manufactured by Sumitomo Chemical Co., Ltd. The compounding amount in the case of using this in this invention should just be in the range of the sum total of the addition range of the phosphorus compound in this invention, and the addition range of a phenolic compound. Specifically, it is preferable that it is 0.02-0.2 mass part with respect to 100 mass parts of total amounts of polyarylate resin and polycarbonate resin.

  In addition to this, as long as the properties are not impaired, the sliding of pigments, dyes, weathering agents, heat stabilizers, flame retardants, mold release agents, antistatic agents, impact resistance improvers, ultrahigh molecular weight polyethylene, fluororesins, etc. A moving agent or the like can be added.

  The production method of the polyarylate resin composition of the present invention is not particularly limited as long as each component is uniformly dispersed in a matrix resin composed of a polyarylate resin and a polycarbonate resin. Specific examples include a method in which a polyarylate resin, a polycarbonate resin, a phosphorus compound, a silane compound, and other additives are uniformly blended using a tumbler or a Henschel mixer, and then melt-kneaded and pelletized.

  Since the polyarylate resin composition of the present invention is excellent in heat resistance and transparency, it can be used in electricity, electronic parts, automotive interior / exterior parts, housing equipment and the like. Furthermore, since it is also excellent in hydrolysis resistance, it can be suitably used for related parts such as displays and lighting, and parts used outdoors such as automobiles. Specific examples of such applications include resin parts for electrical appliances such as displays around flat screen TVs, personal computers, mobile phones, and mobile devices, housings, and automotive exterior resin parts such as headlights and lamp reflectors. In addition to various lighting around the instrument panel, indicator lights, warning lights, interior resin parts for automobiles such as ceilings, legs, and door side interior lights.

  Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples.

1. Evaluation Method (1) Inherent Viscosity Using 1,1,2,2-tetrachloroethane as a solvent, a pellet of polyarylate resin composition was dissolved at a concentration of 1 g / dl to obtain a solution. Under the condition of a temperature of 25 ° C., the viscosity η of the solution and the viscosity η ₀ of the solvent were measured, and the inherent viscosity was calculated by the following formula.
(Inherent viscosity) = η / η ₀
From the viewpoint of fluidity and mechanical properties, 0.4 to 0.6 is appropriate.
(2) Number average molecular weight Using tetrahydrofuran as a solvent, pellets of the polyarylate resin composition were dissolved to a concentration of 1000 ppm to obtain a solution. The number average molecular weight was determined by GPC analysis, and was evaluated in terms of polystyrene.
(3) DTUL (deflection temperature under load)
According to the ISO75 standard, the load was measured at 1.8 MPa. DTUL is an index of heat resistance and is preferably 125 ° C. or higher.
(4) Yellow index (yellowness)
A molded body having a thickness of 2 mm was obtained, and a yellow index (YI) was measured with a D65 / 2 ° light source transmitted light using a spectral color difference meter (SE6000 type manufactured by Nippon Denshoku Industries Co., Ltd.). YI is preferably less than 10.
(5) Hydrolysis resistance The pellets of the polyarylate resin composition were subjected to a wet heat treatment at 80 ° C. × 95% RH for 1000 hours. The inherent viscosity before and after the wet heat treatment was measured according to the method of (1). The inherent viscosity after the wet heat treatment is preferably 0.45 or more.

2. Raw material / polyarylate resin: U-powder manufactured by Unitika (inherent viscosity 0.55). Hereinafter, it is referred to as PAR.
Polycarbonate resin: Caliber 200-13 manufactured by Sumitomo Dow (inherent viscosity 0.49). Hereinafter, it is referred to as PC.
-Polycarbodiimide compound; Stabuzol P (number average molecular weight of about 700) manufactured by Rhein Chemie. Hereinafter, it is referred to as STABAXOL P.
-Polycarbodiimide compound: Rhein Chemie's Stavacsol P400 (number average molecular weight of about 6400). Hereinafter, it is referred to as STABAXOL P400.
Phosphorus compound: bis (2,4-bis (1,1-dimethylethyl) -6-methylphenyl) ethyl ester phosphorous acid, IRGAFOS38 manufactured by BASF Corporation. Hereinafter, it is referred to as IRGAFOS38.
Phosphorus compound; bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, PEP-36 manufactured by ADEKA. Hereinafter, it is referred to as PEP-36.
Phosphorus compound: Tris (2,4-di-t-butylphenyl) phosphite, IRGAFOS 168 manufactured by BASF. Hereinafter, it is referred to as IRGAFOS168.
Silane compound; vinyltrimethoxysilane, KBM-1003 (molecular weight 190.3) manufactured by Shin-Etsu Chemical Co., Ltd. Hereinafter, it is referred to as KBM-1003.
Silane compound: 3-acryloxypropyltrimethoxysilane, KBM-5102 (molecular weight 218.4) manufactured by Shin-Etsu Chemical Co., Ltd. Hereinafter, it is referred to as KBM-5102.

Example 1
1 part by mass of STABAXOL P400 and 0.05 part by mass of IRGAFOS38 are mixed together with 100 parts by mass of polyarylate resin, and then charged from the main hopper of the same direction twin screw extruder (TEM-37BS type manufactured by Toshiba Machine Co., Ltd.). The mixture was melt kneaded at a barrel temperature of 350 ° C. The polyarylate resin composition taken up in a strand form from the nozzle was immersed in a water bath, cooled and solidified, cut with a pelletizer, and then dried with hot air at 120 ° C. for 12 hours to obtain pellets of the polyarylate resin composition. Next, various test pieces were produced from the obtained polyarylate resin composition pellets using an injection molding machine (EC-100 type manufactured by Toshiba Machine Co., Ltd.) at a cylinder temperature of 300 to 340 ° C. and a mold temperature of 100 ° C. . Each test piece was allowed to stand at room temperature for one day or longer, and then DTUL and YI were measured for these specimens. Further, the polyarylate resin composition pellets were subjected to wet heat treatment at 80 ° C. × 95% RH and 1000 h, and the inherent viscosity before and after the treatment was measured.
Table 1 shows the blending ratio of the raw materials and the evaluation results of each characteristic value.

Examples 2 to 23, Comparative Examples 1 to 9
According to the blending ratios in Tables 1 to 3, the resin and additives were mixed together and the same operation as in Example 1 was performed to obtain a pellet of the polyarylate resin composition, and then evaluation was performed. Tables 1 to 3 show the mixing ratio of the raw materials and the evaluation results of the characteristic values.

  The polyarylate resin compositions obtained in Examples 1 to 23 were excellent in heat resistance, YI, and hydrolysis resistance. In particular, the polyarylate resin compositions obtained in Examples 17 to 23 were further improved in YI and hydrolysis resistance due to the addition of the silane compound.

  Comparative Examples 1 and 3 were inferior in hydrolysis resistance because the blending amount of the polycarbodiimide compound was too small.

  In Comparative Example 2, since the polycarbodiimide compound was not blended, the hydrolysis resistance was inferior.

  In Comparative Example 4, the heat resistance was inferior because the compounding amount of the polycarbodiimide compound was excessive.

  Since Comparative Example 5 did not use a polycarbodiimide compound having a predetermined molecular weight, YI and hydrolysis resistance were inferior.

  In Comparative Example 6, since the phosphorus compound was not blended, YI and hydrolysis resistance were inferior.

  Comparative Example 7 was inferior in YI and hydrolysis resistance due to an insufficient amount of phosphorus compound.

  Since the comparative example 8 had an excessive phosphorus compound compounding amount, heat resistance was inferior.

In Comparative Example 9, since the polyarylate resin was not blended, the heat resistance was inferior. In addition, the hydrolysis resistance is poor because the polycarbodiimide having a low melt viscosity and a high molecular weight is difficult to disperse.

Claims (4)

  100 to 100 parts by mass of polyarylate resin 10 to 100% by mass, 90 to 0% by mass of polycarbonate resin, 0.1 to 5 parts by mass of polycarbodiimide compound having a number average molecular weight of 5000 or more, and 0.01 to 1 part by mass of phosphorus compound Containing a polyarylate resin composition. The polyarylate resin composition according to claim 1, wherein the phosphorus compound is a phosphite compound represented by the following general formula (I).
In general formula (I), R ¹ is an aliphatic alcohol residue, and R ³ represents a phenyl group. R ² represents an aliphatic alcohol residue or a phenyl group. Both R ¹ and R ² may be the same residue derived from the same polyhydric alcohol compound. Furthermore, 0.01-1 mass part of silane compounds shown by the following general formula (II) are contained, The polyarylate resin composition of Claim 1 or 2 characterized by the above-mentioned.
In general formula (II), R ⁴ represents any one of a vinyl group having 1 to ⁴ carbon atoms, an acryl group, and a methacryl group. R ^{5 to} R ⁷ represent an alkoxy group having 1 to 4 carbon atoms or an alkyl group. The molded object formed by shape | molding the polyarylate resin composition of Claims 1-3.