JP2019143093A - Thermoplastic resin composition - Google Patents

Abstract

To provide a thermoplastic resin composition which is excellent in both transparency and chemical resistance and has high surface hardness.SOLUTION: The thermoplastic resin composition contains an amorphous polyester resin (B) having a structural unit derived from an alicyclic diol and a polyarylate resin (C) in a total amount of 25-400 pts.mass based on 100 pts.mass of a polycarbonate resin component (A) comprising 100-80 mass% of a polycarbonate resin (A1) having a structural unit represented by general formula (1) and 0-20 mass% of a bisphenol A type polycarbonate resin (A2). The mass ratio (B/C) of the content of the amorphous polyester resin (B) to the content of the polyarylate resin (C) is 0.8-3.5.SELECTED DRAWING: None

Description

  The present invention relates to a thermoplastic resin composition, and more particularly, to a polycarbonate resin-based thermoplastic resin composition that is excellent in both transparency and chemical resistance and has high surface hardness.

  Polycarbonate resins are widely used as interior materials for automobiles, housing materials for electric and electronic devices, etc., because they are excellent in strength, heat resistance and transparency, and the molded products obtained are also excellent in dimensional stability.

  However, the polycarbonate resin has a drawback of poor chemical resistance. As automotive interior materials, for example, when used for parts such as car navigation systems and car audios for vehicles, such as touch panels, it is applied to a fragrance or fingers placed in the car because it is operated by a human hand in the car. Chemical resistance to hand creams, sunscreen lotions, insect repellents, etc. is strictly required, and transparency and high hardness are also required. Moreover, various interior materials are used in the vehicle interior, and various components that volatilize therefrom, particularly alkaline components, tend to adversely affect the polycarbonate resin. Polycarbonate resin does not have sufficient chemical resistance such as alkali resistance.

As a technique for improving the chemical resistance of a polycarbonate resin, for example, Patent Document 1 proposes a method of blending an acrylic elastomer and a polyester resin with an aromatic polycarbonate resin. However, this resin composition has low transparency, is not sufficiently satisfactory in chemical resistance, and has insufficient hardness. In addition, in Patent Document 2 by the present applicants, a polycarbonate resin derived from a 2,2-bis (3-methyl-4-hydroxyphenyl) propane structural unit, a polyethylene terephthalate resin or a polybutylene terephthalate resin, and a phosphorus-based stabilizer. It has been proposed that a resin composition containing an agent has excellent chemical resistance and high surface hardness.
However, at present, no polycarbonate resin-based resin composition has been found that has sufficiently improved both chemical resistance and transparency.

Japanese Examined Patent Publication No. 62-37671 Japanese Patent No. 5946334

  An object (problem) of the present invention is to solve the above-described problems, and to provide an alloy of a polycarbonate resin and a polyester resin that is excellent in both transparency and chemical resistance and has a high surface hardness. .

As a result of intensive investigations to achieve the above-mentioned problems, the present inventors have identified amorphous polyester resins and polyarylate resins having a structural unit derived from an alicyclic diol as a specific structural unit polycarbonate resin. It has been found that the alloyed by the amount can solve the above-mentioned problems, and has completed the present invention.
The present invention relates to the following thermoplastic resin composition and molded article.

[1] Polycarbonate resin component (A) 100 comprising 100 to 80% by mass of a polycarbonate resin (A1) having a structural unit represented by the following general formula (1) and 0 to 20% by mass of a bisphenol A type polycarbonate resin (A2) A total of 25 to 400 parts by mass of an amorphous polyester resin (B) having a structural unit derived from an alicyclic diol and a polyarylate resin (C) with respect to parts by mass, and the amorphous polyester resin (B) A thermoplastic resin composition, wherein the mass ratio (B / C) of the content of the polyarylate resin (C) is 0.8 to 3.5.
(In general formula (1), R ¹ represents a methyl group, R ² and R ³ each independently represents a hydrogen atom or a methyl group, and X represents an alkylene group or an alkylidene group.)

[2] The thermoplastic resin composition according to the above [1], wherein the content of the amorphous polyester resin (B) is 15 to 280 parts by mass with respect to 100 parts by mass of the polycarbonate resin component (A).
[3] The thermoplastic resin composition according to the above [1] or [2], wherein the content of the polyarylate resin (C) is 10 to 200 parts by mass with respect to 100 parts by mass of the polycarbonate resin component (A).
[4] The thermoplastic resin composition according to any one of [1] to [3], wherein the amorphous polyester resin (B) is an amorphous polyester resin having a structural unit derived from tetramethylcyclobutanediol.
[5] The thermoplastic resin composition according to [4], wherein the amorphous polyester resin (B) is an amorphous polyester resin further having a structural unit derived from cyclohexanedimethanol. [6] A molded product obtained by molding the thermoplastic resin composition according to any one of [1] to [5].

The thermoplastic resin composition of the present invention is excellent in both transparency and chemical resistance and has a high surface hardness.
Amorphous polyester resin (B) and polyarylate resin (C) having a structural unit derived from an alicyclic diol are not compatible with each other even when blended alone with the polycarbonate resin (A1). The thermoplastic resin composition obtained by compatibilizing with the polycarbonate resin (A1) for the first time by blending both the resin (B) and the polyarylate resin (C) is excellent in both transparency and chemical resistance. And it becomes possible to have high surface hardness.

  Hereinafter, the present invention will be described in detail with reference to embodiments and examples, but the present invention is not limited to the following embodiments and examples and the like, and is within the scope of the present invention. Any change can be made.

  The thermoplastic resin composition of the present invention comprises 100 to 80% by mass of a polycarbonate resin (A1) having a structural unit represented by the general formula (1) and 0 to 20% by mass of a bisphenol A type polycarbonate resin (A2). Amorphous polyester resin (B) and polyarylate resin (C) having a structural unit derived from an alicyclic diol is contained in a total of 25 to 400 parts by mass with respect to 100 parts by mass of the polycarbonate resin component (A). The mass ratio (B / C) of the content of the conductive polyester resin (B) and the polyarylate resin (C) is 0.8 to 3.5.

[Polycarbonate resin component (A)]
The polycarbonate resin component (A) used in the thermoplastic resin composition of the present invention is composed of 100 to 80% by mass of a polycarbonate resin (A1) having a structural unit represented by the following general formula (1) and a bisphenol A type polycarbonate resin ( A2) It consists of 0 to 20% by mass.

[Polycarbonate resin (A1)]
The polycarbonate resin (A1) is a polycarbonate resin having a structural unit represented by the following general formula (1).
(In general formula (1), R ¹ represents a methyl group, R ² and R ³ each independently represents a hydrogen atom or a methyl group, and X represents an alkylene group or an alkylidene group.)

In the general formula (1), R ¹ is a methyl group, and R ² and R ³ are each independently a hydrogen atom or a methyl group, but R ² and R ³ are particularly preferably a hydrogen atom.
X is an alkylene group or an alkylidene group, and the alkylene group is preferably an alkylene group having 1 to 6 carbon atoms, and may be linear or branched. Examples thereof include methylene, 1,2-ethylene, 1,3-propylene, 1,4-butylene, 1,6-hexylene and the like.
The alkylidene group is preferably an alkylidene group having 2 to 10 carbon atoms, and examples thereof include ethylidene, 2,2-propylidene, 2,2-butylidene, and 3,3-hexylidene.
X is preferably an alkylidene group, particularly preferably a 2,2-propylidene group (that is, an isopropylidene group).

Preferable specific examples of the polycarbonate resin (A1) include the following polycarbonate resins (a) and (b).
A) Those having a 2,2-bis (3-methyl-4-hydroxyphenyl) propane structural unit, that is, a structural unit in which R ¹ is a methyl group, R ² and R ³ are hydrogen atoms, and X is an isopropylidene group Having
B) 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane structural unit, that is, a structural unit in which R ¹ is a methyl group, R ² and R ³ are methyl groups, and X is an isopropylidene group thing,
Of the above, the polycarbonate resin (a) is particularly preferable.

  These polycarbonate resins are produced using 2,2-bis (3-methyl-4-hydroxyphenyl) propane and 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane as dihydroxy compounds. be able to.

  As the polycarbonate resin (A1), one type may be used, or two or more types may be used in any combination and in any ratio.

The polycarbonate resin (A1) can also have other carbonate structural units other than the structural unit represented by the general formula (1). For example, the structural unit represented by the following general formula (2) or as described later It may have a structural unit derived from other dihydroxy compound. In this case, the copolymerization amount of structural units other than the structural unit represented by the general formula (1) is usually preferably 50 mol% or less, more preferably 40 mol% or less, and further preferably 30 mol% or less. preferable.
(Wherein X has the same meaning as X in formula (1)).

As a preferable specific example of the polycarbonate structural unit represented by the general formula (4), 2,2-bis (4-hydroxyphenyl) propane, that is, derived from bisphenol A represented by the structural unit of the following chemical formula (3) This is a carbonate structural unit.

Examples of other dihydroxy compounds include the following aromatic dihydroxy compounds.
Bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) -4-methyl Pentane, 1,1-bis (4-hydroxyphenyl) decane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxy) Phenyl) phenylmethane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclooctane, 9,9-bis (4-hydroxyphenyl) fluorene, 4,4 ′ -Dihydroxybenzophenone, 4,4'-dihydroxyphenyl ether and the like.

  The viscosity average molecular weight (Mv) of the polycarbonate resin (A1) is preferably 23,000 to 35,000. When the viscosity average molecular weight is in this range, it is easy to obtain a molded product having good moldability, high mechanical strength and good scratch resistance. When the viscosity average molecular weight is below 23,000, the pencil hardness of the resin composition is lowered. In addition, the wear resistance tends to decrease, and if it exceeds 35,000, the melt viscosity increases and injection molding tends to be difficult. The lower limit of the molecular weight of the polycarbonate resin (A1) is more preferably 24,000, still more preferably 25,000, particularly preferably 26,000, and the upper limit thereof is more preferably 33,000, particularly 32,000. Is preferred.

In the present invention, the viscosity average molecular weight (Mv) of the polycarbonate resin is determined by using methylene chloride as a solvent and obtaining an intrinsic viscosity [η] (unit dl / g) at a temperature of 25 ° C. using an Ubbelohde viscometer, It is a value calculated from the following Schnell viscosity equation.
[Η] = 1.23 × 10 ⁻⁴ Mv ^0.83

  The manufacturing method of polycarbonate resin (A1) is not specifically limited, A well-known arbitrary method is employable. Examples thereof include an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, and a solid phase transesterification method of a prepolymer.

[Bisphenol A type polycarbonate resin (A2)]
The polycarbonate resin contained in the polycarbonate resin composition of the present invention is a bisphenol A type polycarbonate resin (A2).
The bisphenol A type polycarbonate resin (A2) is produced from bisphenol A, that is, 2,2-bis (4-hydroxyphenyl) propane, and a carbonate precursor as a raw material dihydroxy compound.

  Among the monomers used as the raw material for the polycarbonate resin (A2), carbonyl halides, carbonic acid diesters and the like are used as examples of the carbonate precursor. In addition, 1 type may be used for a carbonate precursor and it may use 2 or more types together by arbitrary combinations and a ratio.

  Specific examples of carbonyl halides include phosgene; haloformates such as bischloroformate of dihydroxy compounds and monochloroformate of dihydroxy compounds.

  Specific examples of the carbonic acid diester include diaryl carbonates such as diphenyl carbonate and ditolyl carbonate; dialkyl carbonates such as dimethyl carbonate and diethyl carbonate; biscarbonate bodies of dihydroxy compounds, monocarbonate bodies of dihydroxy compounds, and cyclic carbonates. And carbonate bodies of dihydroxy compounds such as

The polycarbonate resin (A2) may be a copolymerized polycarbonate resin in which another dihydroxy compound other than bisphenol A is used in combination. However, the polycarbonate resin (A2) is a resin different from the polycarbonate resin (A1).
Examples of other dihydroxy compounds other than bisphenol A include the following aromatic dihydroxy compounds.
Bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) -4-methyl Pentane, 1,1-bis (4-hydroxyphenyl) decane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxy) Phenyl) phenylmethane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclooctane, 9,9-bis (4-hydroxyphenyl) fluorene, 4,4 ′ -Dihydroxybenzophenone, 4,4'-dihydroxyphenyl ether, 2,2-bis (3-methyl-4-hydride) Kishifeniru) propane.

When the copolymeric polycarbonate resin is used, the component derived from bisphenol A is preferably 50 mol% or more, more preferably 70 mass% or more, still more preferably 80 mass% or more, especially 90 mass% or more, particularly 95. It is preferable that it is mass% or more.
Further, the polycarbonate resin (A2) may be linear or branched.

  The manufacturing method of polycarbonate resin (A2) is not specifically limited, A well-known arbitrary method is employable. Examples thereof include an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, and a solid phase transesterification method of a prepolymer.

  The viscosity average molecular weight (Mv) of the polycarbonate resin (A2) is preferably 15,000 to 30,000. When the viscosity average molecular weight is within this range, a molded article having good moldability and high mechanical strength is easily obtained. When the viscosity average molecular weight is less than 15,000, the surface impact resistance is remarkably lowered and exceeds 30,000. The melt viscosity increases and injection molding tends to be difficult. The lower limit of the molecular weight of the polycarbonate resin (A) is more preferably 16,000, still more preferably 17,000, and the upper limit thereof is more preferably 28,000.

As described above, the polycarbonate resin component (A) used in the thermoplastic resin composition of the present invention is 100 to 80% by mass of the polycarbonate resin (A1) having a structural unit represented by the general formula (1) and bisphenol A. The polycarbonate resin (A2) is composed of 0 to 20% by mass, and is preferably a mixture of the polycarbonate resin (A1) and the polycarbonate resin (A2). By adding the polycarbonate resin (A2), the compatibility of the polycarbonate resin (A1), the amorphous polyester resin (B) and the polyarylate resin (C) is improved, and the transparency is further improved.
A preferred ratio of the polycarbonate resin (A1) to the bisphenol A type polycarbonate resin (A2) is based on a total of 100% by mass of (A1) and (A2), and (A1) is 60 to 100% by mass, more preferably 60 to 95%. It is 70 mass%, More preferably, it is 70-95 mass%, (A2) is 40-0 mass%, More preferably, it is 30-5 mass%, More preferably, it is 20-5 mass%.

The viscosity average molecular weight (Mv) as the polycarbonate resin component (A) is preferably 16,000 to 28,000. If the viscosity average molecular weight is within this range, good moldability, large mechanical strength, and good scratch resistance can be easily obtained. If the viscosity average molecular weight is less than 16,000, the surface impact resistance is likely to be significantly reduced. If it exceeds 28,000, the melt viscosity increases and injection molding tends to be difficult. The lower limit of the molecular weight of the polycarbonate resin component (A) is more preferably 17,000, still more preferably 18,000, particularly preferably 20,000, and the upper limit is more preferably 27,000.
Here, the viscosity average molecular weight (Mv) of the polycarbonate resin component (A) refers to the viscosity average molecular weight (Mv) of the polycarbonate resin as a mixture when the above-mentioned polycarbonate resin is mixed and used, and constitutes the mixture. It is not excluded that the individual polycarbonate resins themselves deviate from the above-mentioned viscosity average molecular weight (Mv).

[Amorphous polyester resin (B) having a structural unit derived from alicyclic diol]
The thermoplastic resin composition of the present invention contains an amorphous polyester resin (B) having a structural unit derived from an alicyclic diol.

The alicyclic diol which is the diol component of the amorphous polyester resin (B) may be 2,2,4,4-tetramethyl-1,3-cyclobutanediol (cis, trans, or a mixture thereof) (Hereinafter also referred to as “TMCD”), 1,4-cyclohexanedimethanol (or a mixture of 1,3 and 1,4 cyclohexanedimethanol, cis, trans, or a mixture thereof. And the like.) Are preferred.
In particular, TMCD is preferably included as the alicyclic diol. And especially as alicyclic diol, it is preferable to have TMCD and CHDM together.

  As a constituent ratio of the alicyclic diol component, when the total mol% of the diol component is 100 mol%, the structural unit derived from TMCD is preferably 10 to 100 mol%, more preferably 20 to 100 mol%, Preferably, the content is 30 to 100 mol%, and when the structural unit derived from CHDM is contained together with the structural unit derived from TMCD, the structural unit derived from CHDM is preferably 10 to 90 mol%, more preferably 15 It is -80 mol%, More preferably, it is 20-70 mol%.

The amorphous polyester resin (B) may contain a diol component other than TMCD and CHDM. The content of the other diol is preferably 15 mol% or less, more preferably 10 mol% or less, and more preferably 10 mol% or less, when the total number of moles of the diol component of the amorphous polyester resin (B) is 100 mol%. Preferably it is 5 mol% or less.
Other diols other than TMCD and CHDM include diols containing 2 to 16 carbon atoms, such as ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, neopentyl glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, p-xylene glycol or mixtures thereof.

Examples of the dicarboxylic acid component of the amorphous polyester resin (B) include alicyclic dicarboxylic acids and aromatic dicarboxylic acids, and aromatic dicarboxylic acids are preferred. The aromatic dicarboxylic acid is preferably terephthalic acid, and the amount thereof is preferably 80 mol% or more, more preferably 90 mol% or more. In addition to terephthalic acid, the dicarboxylic acid component can have up to less than 50 mole percent of other dicarboxylic acids.
As aromatic dicarboxylic acids other than terephthalic acid, isophthalic acid, 4,4′-biphenyldicarboxylic acid, 1,4-, 1,5-, 2,6-, 2,7-naphthalenedicarboxylic acid, 4, Examples include 4'-stilbene dicarboxylic acid.
Furthermore, although it is possible to include an aliphatic dicarboxylic acid such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azalene acid, etc., the amount is preferably 10 mol% or less.

The intrinsic viscosity of the amorphous polyester resin (B) is preferably 0.3 to 1.2 dl / g, more preferably 0.5 to 1.0 dl / g, still more preferably 0.7 to 0.9 dl / g. Range. When the intrinsic viscosity is less than 0.3, there is a problem that moldability and strength are lowered, and when it exceeds 1.2, it becomes difficult to mold.
In the present invention, the intrinsic viscosity [η] of the polyester resin is measured at 25 ° C. in a 1: 1 (mass ratio) mixed solvent of 1,1,2,2-tetrachloroethane and phenol.

[Polyarylate resin (C)]
The thermoplastic resin composition of the present invention contains a polyarylate resin (C) in addition to the amorphous polyester resin (B). As described above, by blending both the amorphous polyester resin (B) and the polyarylate resin (C) together, the first thermoplastic resin composition becomes compatible with the polycarbonate resin (A1), and the resulting thermoplastic resin composition is transparent. It is possible to have both high resistance and chemical resistance and high surface hardness.

  The polyarylate resin (C) is obtained from an aromatic dicarboxylic acid or a derivative thereof and a dihydric phenol or a derivative thereof.

  Preferred examples of the aromatic dicarboxylic acid component include terephthalic acid, isophthalic acid, phthalic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, and 1,5-naphthalenedicarboxylic acid. Acid, methyl terephthalic acid, 4,4'-biphenyl dicarboxylic acid, 2,2'-biphenyl dicarboxylic acid, 4,4'-biphenyl ether dicarboxylic acid, 4,4'-diphenylisopropylidenedicarboxylic acid, 1,2-bis (4-Carboxyphenoxy) ethane, 5-sodium sulfoisophthalic acid and the like.

Among these, terephthalic acid and isophthalic acid are preferable, and using both in combination is preferable because a polyarylate resin excellent in melt processability and mechanical properties can be obtained.
When terephthalic acid and isophthalic acid are used in combination, the mixing ratio can be arbitrarily selected. However, considering the balance of melt processability and performance, terephthalic acid / isophthalic acid is expressed in mole fraction. It is preferably in the range of 90/10 to 10/90, more preferably 70/30 to 30/70, and still more preferably 55/45 to 45/55. If the mixing ratio of terephthalic acid and isophthalic acid is outside the above range, the degree of polymerization of the polyarylate resin may be insufficient, and the corrosion resistance discoloration of the resulting polyarylate resin may be exhibited.

  Examples of the raw material dihydric phenol component of the polyarylate resin include 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, and 2,2-bis. (4-hydroxy-3,5-dichlorophenyl) propane, 4,4′-dihydroxydiphenyl sulfone, 4,4′-dihydrodiphenyl ether, 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxydiphenyl ketone, 4, 4'-dihydroxydiphenylmethane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) cyclohexane 4,4'-dihydroxydiphenyl, hydroquinone, etc. Is, 2,2-bis (4-hydroxyphenyl) propane, i.e., bisphenol A is preferred. These may be used singly or in combination of two or more. Furthermore, a small amount of an aliphatic diol such as ethylene glycol or propylene glycol may be used in combination with these bisphenols, but the amount is preferably 20 mol% or less, more preferably 10 mol% or less, and particularly preferably 5 mol% or less. is there.

  The intrinsic viscosity of the polyarylate resin (C) is not particularly limited, but is preferably 0.4 to 0.8, and more preferably 0.4 to 0.7. If the intrinsic viscosity of the polyarylate resin exceeds 0.8, the melt viscosity becomes high and the fluidity is lowered, so that kneading extrusion and injection molding may be difficult. In addition, discoloration may occur during melt processing. On the other hand, when the molecular weight is less than 0.4, the molecular weight of the resulting resin composition becomes low, and thus mechanical properties such as impact strength and heat resistance tend to be lowered when formed into a molded product.

As described above, the content of the amorphous polyester resin (B) and the polyarylate resin (C) is a total of 100 parts by mass of the polycarbonate resin component (A) of the polycarbonate resin (A1) and the polycarbonate resin (A2). It is 25-400 mass parts, and mass ratio (B / C) of content of resin (B) and resin (C) is 0.8-3.5.
When the content of the resin (B) and the resin (C) is less than 25 parts by mass, the chemical resistance becomes insufficient, and when the content exceeds 400 parts by mass, the surface hardness becomes insufficient. Further, when B / C is less than 0.8, the transparency is low, and when it exceeds 3.5, the transparency is low.
It is preferable that content of an amorphous polyester resin (B) is 15-280 mass parts with respect to 100 mass parts of polycarbonate resin components (A), More preferably, it is 15-250 mass parts, More preferably, 20- 200 parts by mass, particularly preferably 25 to 150 parts by mass.
Moreover, it is preferable that content of polyarylate resin (C) is 10-200 mass parts with respect to 100 mass parts of polycarbonate resin component (A), More preferably, it is 10-170 mass parts, More preferably, it is 10-10 mass parts. 140 parts by mass, particularly preferably 15 to 100 parts by mass.

[Other ingredients]
The thermoplastic resin composition may contain other components other than those described above as necessary, as long as the desired physical properties are not significantly impaired. Examples of other components include resins other than those described above and various resin additives.
Examples of the resin additive include a release agent, an antioxidant, a heat stabilizer, an ultraviolet absorber, an antistatic agent, a flame retardant, a flame retardant aid, a dye / pigment, an antifogging agent, a lubricant, an antiblocking agent, and a fluid. Examples include property improvers, plasticizers, dispersants, and antibacterial agents. In addition, 1 type may contain resin additive and 2 or more types may contain it by arbitrary combinations and a ratio.
When other resins other than those described above are contained, the content thereof is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and more preferably 5 parts by mass with respect to 100 parts by mass of the polycarbonate resin component (A). It is preferable that the amount be 3 parts by mass or less, particularly 3 parts by mass or less.

<Release agent>
Examples of the release agent include aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15,000, polysiloxane silicone oils, and the like.

  Examples of the aliphatic carboxylic acid include saturated or unsaturated aliphatic monovalent, divalent or trivalent carboxylic acid. Here, the aliphatic carboxylic acid includes alicyclic carboxylic acid. Among these, preferable aliphatic carboxylic acids are monovalent or divalent carboxylic acids having 6 to 36 carbon atoms, and aliphatic saturated monovalent carboxylic acids having 6 to 36 carbon atoms are more preferable. Specific examples of such aliphatic carboxylic acids include palmitic acid, stearic acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, mellicic acid, tetrariacontanoic acid, montanic acid, adipine Examples include acids and azelaic acid.

  As aliphatic carboxylic acid in ester of aliphatic carboxylic acid and alcohol, the same thing as the said aliphatic carboxylic acid can be used, for example. On the other hand, examples of the alcohol include saturated or unsaturated monohydric or polyhydric alcohols. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these, monovalent or polyvalent saturated alcohols having 30 or less carbon atoms are preferable, and aliphatic saturated monohydric alcohols or aliphatic saturated polyhydric alcohols having 30 or less carbon atoms are more preferable. In addition, an aliphatic includes an alicyclic compound here.

  Specific examples of such alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol, and the like. Is mentioned.

  In addition, said ester may contain aliphatic carboxylic acid and / or alcohol as an impurity. Moreover, although said ester may be a pure substance, it may be a mixture of a plurality of compounds. Furthermore, the aliphatic carboxylic acid and alcohol which combine and comprise one ester may each be used only by 1 type, and may use 2 or more types together by arbitrary combinations and ratios.

  Specific examples of esters of aliphatic carboxylic acids and alcohols include beeswax (a mixture based on myricyl palmitate), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, glycerin monostearate Examples thereof include rate, glycerol distearate, glycerol tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate and the like.

  Examples of the aliphatic hydrocarbon having a number average molecular weight of 200 to 15,000 include liquid paraffin, paraffin wax, microwax, polyethylene wax, Fischer-Tropsch wax, and α-olefin oligomer having 3 to 12 carbon atoms. Here, the aliphatic hydrocarbon includes alicyclic hydrocarbons. Further, these hydrocarbons may be partially oxidized.

Among these, paraffin wax, polyethylene wax, or a partial oxide of polyethylene wax is preferable, and paraffin wax and polyethylene wax are more preferable.
The number average molecular weight of the aliphatic hydrocarbon is preferably 5,000 or less.
The aliphatic hydrocarbon may be a single substance, but even a mixture of various constituent components and molecular weights can be used as long as the main component is within the above range.

In addition, the mold release agent mentioned above may be contained only by 1 type, and 2 or more types may be contained by arbitrary combinations and ratios.
The content of the release agent is usually based on 100 parts by mass in total of the polycarbonate resin component (A), the polyester resin (B), the polyarylate resin (C), and other resin components blended as necessary. It is 0.001 part by mass or more, preferably 0.01 part by mass or more, and usually 2 parts by mass or less, preferably 1 part by mass or less, more preferably 0.6 parts by mass or less. When the content of the release agent is not more than the lower limit of the above range, the effect of releasability may not be sufficient, and when the content of the release agent exceeds the upper limit of the above range, hydrolysis resistance And mold contamination during injection molding may occur.

<Heat stabilizer>
Examples of the heat stabilizer include phosphorus compounds. Any known phosphorous compound can be used. Specific examples include phosphorus oxo acids such as phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, and polyphosphoric acid; acidic pyrophosphate metal salts such as acidic sodium pyrophosphate, acidic potassium pyrophosphate, and acidic calcium pyrophosphate; phosphoric acid Group 1 or Group 2B metal phosphates such as potassium, sodium phosphate, cesium phosphate and zinc phosphate; organic phosphate compounds, organic phosphite compounds, organic phosphonite compounds, etc. Particularly preferred.

Organic phosphite compounds include triphenyl phosphite, tris (monononylphenyl) phosphite, tris (monononyl / dinonyl phenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, monooctyl Diphenyl phosphite, dioctyl monophenyl phosphite, monodecyl diphenyl phosphite, didecyl monophenyl phosphite, tridecyl phosphite, trilauryl phosphite, tristearyl phosphite, 2,2-methylene bis (4,6-di- tert-butylphenyl) octyl phosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, and the like.
Specific examples of such organic phosphite compounds include, for example, “ADEKA STAB 1178”, “ADEKA STAB 2112”, “ADEKA STAB HP-10” manufactured by ADEKA, “JP-351” manufactured by Johoku Chemical Industry Co., Ltd., “ JP-360 "," JP-3CP "," Irgaphos 168 "manufactured by BASF," Doverphos S-9228 "manufactured by Dover Chemical, and the like.
In addition, the heat stabilizer may be contained only by 1 type and 2 or more types may be contained by arbitrary combinations and ratios.

  The content of the heat stabilizer is usually based on a total of 100 parts by mass of the polycarbonate resin component (A), the polyester resin (B), the polyarylate resin (C), and other resin components blended as necessary. 0.001 part by mass or more, preferably 0.005 part by mass or more, more preferably 0.01 part by mass or more, and usually 1 part by mass or less, preferably 0.5 part by mass or less, more preferably 0.00. 3 parts by mass or less. If the content of the heat stabilizer is less than the lower limit value of the range, the heat stability effect may be insufficient, and if the content of the heat stabilizer exceeds the upper limit value of the range, the effect reaches a peak. And may become less economical.

<Antioxidant>
Examples of the antioxidant include hindered phenol-based antioxidants. Specific examples thereof include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl). ) Propionate, thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexane-1,6-diylbis [3- (3,5-di-) tert-butyl-4-hydroxyphenyl) propionamide], 2,4-dimethyl-6- (1-methylpentadecyl) phenol, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] ] Methyl] phosphoate, 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-tert-butyl-a, a ′, a ″-(me Citylene-2,4,6-triyl) tri-p-cresol, 4,6-bis (octylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4- Hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris (3,5-di-tert- Butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-tert-butyl-4- (4,6-bis ( Octylthio) -1,3,5-triazin-2-ylamino) phenol, 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4,6-di-t rt- pentylphenyl acrylate.

Of these, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate are preferable. . Specific examples of such a phenolic antioxidant include “Irganox 1010”, “Irganox 1076” manufactured by BASF, “Adekastab AO-50”, “Adekastab AO-60” manufactured by ADEKA, and the like. Is mentioned.
In addition, antioxidant may be contained only by 1 type and 2 or more types may be contained by arbitrary combinations and ratios.

  The content of the antioxidant is usually based on 100 parts by mass in total of the polycarbonate resin component (A), the polyester resin (B), the polyarylate resin (C), and other resin components blended as necessary. It is 0.001 part by mass or more, preferably 0.01 part by mass or more, and usually 1 part by mass or less, preferably 0.5 part by mass or less. When the content of the antioxidant is less than the lower limit of the range, the effect as an antioxidant may be insufficient, and when the content of the antioxidant exceeds the upper limit of the range, There is a possibility that the effect reaches its peak and is not economical.

<Ultraviolet absorber>
Examples of ultraviolet absorbers include inorganic ultraviolet absorbers such as cerium oxide and zinc oxide; organics such as benzotriazole compounds, benzophenone compounds, salicylate compounds, cyanoacrylate compounds, triazine compounds, oxanilide compounds, malonic ester compounds, and hindered amine compounds. Examples include ultraviolet absorbers. In these, an organic ultraviolet absorber is preferable and a benzotriazole compound is more preferable. By selecting the organic ultraviolet absorbent, the transparency and mechanical properties of the thermoplastic resin composition are improved.

  Specific examples of the benzotriazole compound include, for example, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis (α, α-dimethylbenzyl). ) Phenyl] -benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butyl-phenyl) -benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5 ′) -Methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butyl-phenyl) -5-chlorobenzotriazole), 2- (2'-hydroxy-3 ', 5'-di-tert-amyl) -benzotriazole, 2- (2'-hydroxy-5'-tert-octylphenyl) benzotriazole, 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], among others, 2- (2′-hydroxy -5'-tert-octylphenyl) benzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol] 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole is particularly preferable.

The content of the UV absorber is usually based on 100 parts by mass in total of the polycarbonate resin component (A), the polyester resin (B), the polyarylate resin (C), and other resin components blended as necessary. It is 0.001 part by mass or more, preferably 0.005 part by mass or more, more preferably 0.01 part by mass or more, and usually 1 part by mass or less, preferably 0.5 part by mass or less. When the content of the UV absorber is less than the lower limit of the above range, the effect of improving the weather resistance is poor, and when the content of the UV absorber exceeds the upper limit of the above range, mold deposits or the like occur and mold contamination Easy to cause.
In addition, an ultraviolet absorber may be contained only by 1 type and 2 or more types may be contained by arbitrary combinations and ratios.

[Method for producing thermoplastic resin composition]
There is no restriction | limiting in the manufacturing method of a thermoplastic resin composition, The manufacturing method of a well-known thermoplastic resin composition can be employ | adopted widely, Polycarbonate resin (A1), (A2), Polyester resin (B), Polyarylate resin (C) , And other ingredients to be blended as necessary, for example, by using various mixers such as a tumbler and a Henschel mixer, then Banbury mixer, roll, Brabender, single screw kneading extruder, twin screw kneading extrusion And a melt kneading method using a mixer such as a kneader or a kneader.
The temperature for melt kneading is not particularly limited, but is usually in the range of 220 to 320 ° C.

The thermoplastic resin composition of the present invention is characterized by particularly excellent transparency, chemical resistance and hardness.
That is, the thermoplastic resin composition of the present invention has a high degree of transparency such that the haze at a thickness of 1 mm is preferably 10% or less. Here, the haze is a value obtained by measuring a 1 mm-thick molded article of the thermoplastic resin composition according to ISO14782 and ISO13468-1, and the specific measurement method is described in the examples. The haze is more preferably 7% or less.
Further, the thermoplastic resin composition of the present invention preferably has a very hard surface hardness such that the pencil hardness is F or higher than F. Here, the pencil hardness is measured according to JIS 5600-5-4. The specific measurement method is described in the Examples. The pencil hardness is preferably H or higher, particularly 2H or higher.

[Molding]
The above-mentioned thermoplastic resin composition (pellet) is molded by various molding methods into a molded product.
The shape of the molded product is not particularly limited and can be appropriately selected according to the use and purpose of the molded product. For example, a plate shape, a plate shape, a rod shape, a sheet shape, a film shape, a cylindrical shape, an annular shape, Examples include a circular shape, an elliptical shape, a polygonal shape, an irregular shape, a hollow shape, a frame shape, a box shape, and a panel shape.

The method for molding the molded body is not particularly limited, and a conventionally known molding method can be employed.For example, an injection molding method, an injection compression molding method, an extrusion molding method, a profile extrusion method, a transfer molding method, a hollow molding method, Gas assisted hollow molding method, blow molding method, extrusion blow molding, IMC (in-mold coating molding) molding method, rotational molding method, multilayer molding method, two-color molding method, insert molding method, sandwich molding method, foam molding method And a pressure molding method.
Among these, the molding is preferably performed by an injection molding method. For example, the molding is performed using a known injection molding machine such as an injection molding machine, an ultra-high speed injection molding machine, or an injection compression molding machine. The cylinder temperature of the injection molding machine at the time of injection molding is preferably 220 to 340 ° C, more preferably 260 to 300 ° C. The injection speed during injection molding is preferably 10 to 1,000 mm / second, more preferably 10 to 500 mm / second.

[Molded body]
The molded article of the thermoplastic resin composition of the present invention is suitably used for interior parts for vehicles, electrical and electronic equipment, OA equipment, information terminal equipment, machine parts, home appliances, various containers, lighting equipment, and the like. Among these, it is particularly suitable for use in vehicle interior parts.

  As an interior part for vehicles, it can be used suitably for car navigation and car audio equipment, for example. Among them, the molded article is excellent in transparency and chemical resistance, and has a high surface hardness. Therefore, the molded article is particularly suitable as a member for liquid crystal display panels such as car navigation and car audio, particularly as a cover member for a touch panel.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples, and can be arbitrarily modified and implemented without departing from the gist of the present invention.

The components used in Examples and Comparative Examples are as shown in Table 1 below.

In Table 1, the polycarbonate resin (A1) used as the polycarbonate resin (A1) was produced by the following Production Example 1.
<Production Example 1: Production of polycarbonate resin (A1)>
2,2-bis (3-methyl-4-hydroxyphenyl) propane (hereinafter referred to as “BPC”) 26.14 mol (6.75 kg) and diphenyl carbonate 26.79 mol (5.74 kg) The reactor was placed in a SUS reactor (with an internal volume of 10 liters) equipped with a stirrer and a distillation condenser, and after the inside of the reactor was replaced with nitrogen gas, the temperature was raised to 220 ° C. over 30 minutes in a nitrogen gas atmosphere.
Next, the reaction solution in the reactor is stirred, and cesium carbonate (Cs ₂ CO ₃ ) is used as a transesterification reaction catalyst in the molten reaction solution so that the amount becomes 1.5 × 10 ⁻⁶ mol per 1 mol of BPC. In addition, the reaction solution was stirred and brewed at 220 ° C. for 30 minutes in a nitrogen gas atmosphere. Next, under the same temperature, the pressure in the reactor was reduced to 100 Torr over 40 minutes, and the reaction was further performed for 100 minutes to distill phenol.

Next, the temperature in the reactor was raised to 284 ° C. over 60 minutes and the pressure was reduced to 3 Torr, and phenol corresponding to almost the entire distillation amount was distilled. Next, the pressure in the reactor was kept below 1 Torr at the same temperature, and the reaction was further continued for 60 minutes to complete the polycondensation reaction. At this time, the stirring rotation speed of the stirrer was 38 rotations / minute, the reaction liquid temperature just before the completion of the reaction was 289 ° C., and the stirring power was 1.00 kW.
Next, the reaction solution in a molten state is fed into a twin screw extruder, and 4-fold molar amount of butyl p-toluenesulfonate is supplied from the first supply port of the twin screw extruder with respect to cesium carbonate, After kneading with the reaction solution, the reaction solution was extruded in a strand shape through a die of a twin screw extruder and cut with a cutter to obtain carbonate resin pellets.

The physical properties of the obtained polycarbonate resin (A1) were as follows.
Pencil hardness: 2H
Viscosity average molecular weight (Mv): 26,000

(Examples 1-7, Comparative Examples 1-10)
Each component described in Table 1 above was blended in the proportions shown below in Table 2 below (all expressed in parts by mass) and uniformly mixed with a tumbler mixer, and then a single screw extruder with a vent with a screw diameter of 40 mm ( Using “VS-40” manufactured by Tanabe Plastics Co., Ltd., melt kneading was performed at a cylinder temperature of 290 ° C. and a screw rotation speed of 70 rpm, and the extruded strand was cut to obtain pellets of a polycarbonate resin composition.

<Transparency evaluation (haze)>
After drying the above pellets at 100 ° C. for 5 hours, using an S-2000i molding machine manufactured by FANUC, under the conditions of a cylinder set temperature of 290 ° C., a mold temperature of 100 ° C., and an injection speed of 30 mm / second, 100 mm × 100 mm Flat plate test pieces of × 1 mm thickness and 100 mm × 50 mm × 2 mm thickness were injection molded.

  About the flat test piece of 1 mm thickness obtained above, according to ISO14782 and ISO13468-1, the haze (unit:%) was measured with the Nippon Denshoku Industries Co., Ltd. NDH-2000 type | mold haze meter.

<Surface hardness>
About the 2 mm-thick flat-plate-shaped test piece obtained above, pencil hardness was calculated | required by the 750g load using the pencil hardness tester (made by Toyo Seiki Co., Ltd.) based on JISK5600-5-4.

<Chemical resistance>
After drying the above pellets at 100 ° C. for 5 hours, using an S-2000i molding machine manufactured by FANUC, under the conditions of a cylinder set temperature of 290 ° C., a mold temperature of 100 ° C., and an injection speed of 30 mm / second, 100 mm × 100 mm A flat test piece having a thickness of 2 mm was injection molded.
A gauze cut to 10 mm × 10 mm was placed on the surface of the obtained flat test piece of 100 mm × 100 mm × 2 mm thickness, and 5 mg of an isopropyl alcohol solution of 10% N, N-diethyl-3-methylbenzamide was dropped on the gauze. And kept at 23 ° C. for 2 minutes. After the test, the gauze was removed, the surface of the molded product was washed with isopropyl alcohol, and the appearance was evaluated according to the following criteria.
○: No surface roughness Δ: Partial surface roughness ×: Surface roughness The above evaluation results are shown in Table 2 below.

  Since the thermoplastic resin composition of the present invention is a resin material that is excellent in both transparency and chemical resistance and has a high surface hardness, it is particularly suitable for members such as interior parts for vehicles. Some are highly available.

Claims (6)

To 100 parts by mass of a polycarbonate resin component (A) comprising 100 to 80% by mass of a polycarbonate resin (A1) having a structural unit represented by the following general formula (1) and 0 to 20% by mass of a bisphenol A type polycarbonate resin (A2) On the other hand, the amorphous polyester resin (B) having a structural unit derived from an alicyclic diol and the polyarylate resin (C) are contained in a total of 25 to 400 parts by mass, and the amorphous polyester resin (B) and the polyarylate resin are contained. A mass ratio (B / C) of the content of (C) is 0.8 to 3.5.
(In general formula (1), R ¹ represents a methyl group, R ² and R ³ each independently represents a hydrogen atom or a methyl group, and X represents an alkylene group or an alkylidene group.)   The thermoplastic resin composition according to claim 1, wherein the content of the amorphous polyester resin (B) is 15 to 280 parts by mass with respect to 100 parts by mass of the polycarbonate resin component (A).   The thermoplastic resin composition according to claim 1 or 2, wherein the content of the polyarylate resin (C) is 10 to 200 parts by mass with respect to 100 parts by mass of the polycarbonate resin component (A).   The thermoplastic resin composition according to any one of claims 1 to 3, wherein the amorphous polyester resin (B) is an amorphous polyester resin having a structural unit derived from tetramethylcyclobutanediol.   The thermoplastic resin composition according to claim 4, wherein the amorphous polyester resin (B) is further an amorphous polyester resin having a structural unit derived from cyclohexanedimethanol.   The molded product which shape | molded the thermoplastic resin composition in any one of Claims 1-5.