JP7479943B2 - Thermoplastic resin composition and method for producing molded article - Google Patents

Description

The present invention relates to a method for producing a thermoplastic resin composition and a molded article, and more specifically, to a glass-reinforced thermoplastic resin composition filled with a glass filler such as glass fiber, which has improved transparency, and a method for producing a molded article with excellent transparency using this thermoplastic resin composition.

Polycarbonate resins are widely used in many fields as resins excellent in heat resistance, impact resistance, transparency, etc. Among them, glass-reinforced polycarbonate resin compositions filled with glass fillers such as glass fibers are widely used in industrial fields such as cameras, office automation equipment, communication equipment, precision instruments, electric and electronic parts, automobile parts, and general machine parts because of their excellent properties such as dimensional stability, rigidity (flexural strength), and heat resistance.
However, glass-reinforced polycarbonate resin compositions have the drawback of significantly reducing transparency due to the difference in refractive index between glass and polycarbonate resin.

Patent Document 1 proposes a polycarbonate resin composition that combines a polycarbonate resin having aliphatic carbonate repeating units derived from an aliphatic dihydroxy compound with glass fibers of a specific glass composition to reduce the difference between the refractive index of the polycarbonate resin and the refractive index of the glass fibers, thereby improving transparency. However, the polycarbonate resin composition of Patent Document 1 has the disadvantage that specific polycarbonate resins and glass fibers must be used, limiting the materials that can be used.

Patent Document 2 describes a thermoplastic resin composition that is excellent in transparency, impact strength, and surface hardness, and contains polycarbonate resin, poly(1,4-cyclohexylene dimethylene terephthalate) copolyester resin, and a phosphorus-based antioxidant in specific ratios. However, this patent document 2 only shows that the incorporation of poly(1,4-cyclohexylene dimethylene terephthalate) copolyester resin improves surface hardness, and makes no mention of the incorporation of glass fiber, nor does it suggest that poly(1,4-cyclohexylene dimethylene terephthalate) copolyester resin has the effect of improving the reduced transparency of polycarbonate resin caused by the incorporation of glass fiber.

The heat-insulating mold and heat-and-cool molding method used in the manufacturing method of the molded product of the present invention are known (for example, see Patent Documents 3 and 4 for heat-insulating molds and Patent Document 5 for heat-and-cool molding), but it was not known that the adoption of these methods could improve the transparency of glass-reinforced thermoplastic resin molded products.

Patent No. 6131264 JP 2016-216556 A JP 2001-300941 A JP 2014-46590 A Japanese Patent Application Laid-Open No. 60-54828

The present invention aims to provide a thermoplastic resin composition and molded article thereof that have improved transparency in a glass-reinforced thermoplastic resin composition in which a polycarbonate resin is filled with a glass filler such as glass fiber, and a method for producing a molded article with excellent transparency using this thermoplastic resin composition.

Means for Solving the Problems The present inventors have conducted extensive research to solve the above problems and have found that blending a specific polycondensate with a polycarbonate resin in a prescribed ratio makes it possible to bring the refractive index of the resin matrix closer to the refractive index of the glass fiber, thereby improving the transparency of glass-reinforced thermoplastic resin molded products.
The present inventors have also found that the transparency can be further improved by injection molding the glass-reinforced thermoplastic resin composition using a polycarbonate resin and a polycondensate in combination in this manner using a specific method.
The present invention relates to the following thermoplastic resin composition, molded article, and method for producing a molded article.

[1] A thermoplastic resin composition containing 10 to 50 parts by mass of a glass filler (C) per 100 parts by mass of a total of 40 to 75 parts by mass of a polycarbonate resin (A) and 25 to 60 parts by mass of a polycondensate (B), wherein the polycondensate (B) is selected from at least one resin selected from the group consisting of a polyester resin (B1), a polycarbonate resin other than the polycarbonate resin (A) (B2), and a polyester carbonate resin (B3), and the diol residue thereof contains a residue of a diol represented by the following general formula (1):
[In formula (1), R ¹ and R ² each independently represent an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms.]
[2] The thermoplastic resin composition according to the above [1], wherein the residues of the diol represented by the general formula (1) account for 10 to 100 mol % of all diol residues in the polyester resin (B1).
[3] The thermoplastic resin composition according to the above [1] or [2], wherein the polyester resin (B1) further contains at least one diol residue selected from an ethylene glycol residue, a 1,4-cyclohexanedimethanol residue, and a residue of a diol represented by the following general formula (2):
[In formula (2), R ³ to R ⁵ each independently represent an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms.]

[4] The thermoplastic resin composition according to the above [1], wherein the residues of the diol represented by the general formula (1) account for 1 to 100 mol % of all diol residues in the polycarbonate resin (B2).
[5] The thermoplastic resin composition according to the above [1] or [4], wherein the polycarbonate resin (B2) further contains a 1,4-cyclohexanedimethanol residue and/or a residue of a diol represented by general formula (2).
[6] The thermoplastic resin composition according to the above [1], wherein the diol residues of the general formula (1) account for 1 to 100 mol % of all diol residues in the polyester carbonate resin (B3).
[7] The thermoplastic resin composition according to the above [1] or [6], wherein the polyester carbonate resin (B3) further contains a 1,4-cyclohexanedicarboxylic acid residue.
[8] The thermoplastic resin composition according to any one of the above [1] to [7], wherein the glass filler (C) is a glass fiber having a cross-sectional shape with an aspect ratio of 1.5 to 8 and/or a glass flake having an average thickness of 0.1 to 10 μm.
[9] A molded article obtained by injection molding the thermoplastic resin composition according to any one of [1] to [8] above.
[10] The molded article according to the above [9], wherein the area of the molded article surface having a surface roughness Ra of 0.1 μm or less accounts for 30% or more of the total surface of the molded article.
[11] A sheet made of the thermoplastic resin composition according to any one of [1] to [8] above.
[12] The sheet according to the above [11], characterized in that the thickness is 0.2 to 2 mm.
[13] A method for producing a molded article, comprising injection molding the thermoplastic resin composition according to any one of [1] to [8] above into a mold having a ceramic layer on a cavity surface.
[14] A method for producing a molded article, comprising injection molding the thermoplastic resin composition according to any one of [1] to [8] above into a mold having a cavity having a metal layer and then a thermosetting resin layer from the cavity surface side.
[15] A method for producing a molded article by injection molding the thermoplastic resin composition according to any one of [1] to [8] above, comprising using a rapid heating and cooling mold, carrying out an injection step when the mold cavity surface temperature is 130°C or higher, and carrying out a mold opening step when the mold cavity surface temperature is 80°C or lower.

According to the present invention, it is possible to provide a glass reinforced thermoplastic resin composition and molded articles thereof that have excellent transparency, high rigidity, and a low coefficient of linear expansion, by significantly improving the transparency, which was a drawback of glass reinforced thermoplastic resin compositions in which dimensional stability, rigidity (flexural strength), heat resistance, etc. are enhanced by filling polycarbonate resin with a glass filler such as glass fiber.

In the thermoplastic resin composition of the present invention, by mixing the polycondensate (B) containing a residue of a diol represented by the general formula (1) with the polycarbonate resin (A) in a predetermined ratio, the refractive index of the resin matrix can be made close to the refractive index of glass, and the problem of reduced transparency caused by the difference between the refractive index of the resin matrix and the refractive index of the glass filler (C) can be alleviated.
That is, the polycarbonate resin (A) has a refractive index larger than that of glass, and in a glass-reinforced polycarbonate resin composition in which the polycarbonate resin (A) is filled with a glass filler (C), the transparency is significantly reduced due to this refractive index difference. However, by blending a polycondensate (B) having a small refractive index with such a polycarbonate resin (A) in a predetermined ratio, the refractive index of the resin matrix formed of the polycarbonate resin (A) and the polycondensate (B) can be made close to the refractive index of the glass filler (C) used, and the transparency can be significantly improved.
Since the thermoplastic resin composition of the present invention has excellent transparency, high rigidity and a low coefficient of linear expansion, the range of applications of the glass-reinforced thermoplastic resin composition can be significantly expanded to include glass replacement materials, including windows for automobiles and buildings, and other applications requiring transparency.

The thermoplastic resin composition of the present invention is a thermoplastic resin composition containing 10 to 50 parts by mass of a glass filler (C) per 100 parts by mass in total of (A) and (B) containing 40 to 75 parts by mass of a polycarbonate resin (A) and 25 to 60 parts by mass of a polycondensate (B), wherein the polycondensate (B) is selected from at least one resin selected from the group consisting of a polyester resin (B1), a polycarbonate resin (B2) other than the polycarbonate resin (A), and a polyester carbonate resin (B3), and the diol residue thereof contains a residue of a diol represented by the following general formula (1):
[In formula (1), R ¹ and R ² each independently represent an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms.]

[Polycarbonate resin (A)]
The polycarbonate resin (A) used in the present invention is preferably an aromatic polycarbonate resin in terms of transparency, impact resistance, heat resistance, etc.
The aromatic polycarbonate resin is a thermoplastic polymer or copolymer, which may be branched, obtained by reacting an aromatic dihydroxy compound or a small amount of a polyhydroxy compound with phosgene or a carbonic acid diester.
The method for producing the aromatic polycarbonate resin is not particularly limited, and it is possible to use a resin produced by a conventionally known phosgene method (interfacial polymerization method) or melting method (ester exchange method). When the melting method is used, it is possible to use an aromatic polycarbonate resin in which the amount of OH groups in the terminal groups is adjusted.

Examples of aromatic dihydroxy compounds used as raw materials include 2,2-bis(4-hydroxyphenyl)propane (i.e., bisphenol A), tetramethylbisphenol A, bis(4-hydroxyphenyl)-p-diisopropylbenzene, hydroquinone, resorcinol, and 4,4-dihydroxydiphenyl, with bisphenol A being preferred. Compounds in which one or more tetraalkylphosphonium sulfonates are bonded to the above aromatic dihydroxy compounds can also be used.

To obtain a branched aromatic polycarbonate resin, a part of the aromatic dihydroxy compound may be replaced with a branching agent, i.e., a polyhydroxy compound such as phloroglucine, 4,6-dimethyl-2,4,6-tri(4-hydroxyphenyl)heptene-2,4,6-dimethyl-2,4,6-tri(4-hydroxyphenyl)heptane, 2,6-dimethyl-2,4,6-tri(4-hydroxyphenyl)heptene-3,1,3,5-tri(4-hydroxyphenyl)benzene, 1,1,1-tri(4-hydroxyphenyl)ethane, or a compound such as 3,3-bis(4-hydroxyaryl)oxindole (=isatin bisphenol), 5-chloruisatin, 5,7-dichloruisatin, or 5-bromoisatin. The amount of these replacing compounds used is usually 0.01 to 10 mol %, preferably 0.1 to 2 mol %, based on the aromatic dihydroxy compound.

Among the above-mentioned aromatic polycarbonate resins, polycarbonate resins derived from 2,2-bis(4-hydroxyphenyl)propane or polycarbonate copolymers derived from 2,2-bis(4-hydroxyphenyl)propane and other aromatic dihydroxy compounds are preferred. In addition, copolymers mainly made of polycarbonate resins, such as copolymers with polymers or oligomers having a siloxane structure, may also be used.

The aromatic polycarbonate resins described above may be used alone or in combination of two or more.

To adjust the molecular weight of aromatic polycarbonate resins, monovalent aromatic hydroxy compounds may be used. Examples of such monovalent aromatic hydroxy compounds include m- and p-methylphenol, m- and p-propylphenol, p-tert-butylphenol, and p-long-chain alkyl-substituted phenol.

The molecular weight of the polycarbonate resin (A) used in the present invention is preferably 13,000 to 30,000, more preferably 14,000 to 28,000, as calculated from the solution viscosity measured at 25°C using methylene chloride as a solvent. If the viscosity average molecular weight of the polycarbonate resin (A) is smaller than the lower limit, the strands cannot be taken up stably during the production of the thermoplastic resin composition, making pelletization difficult, whereas if it is larger than the upper limit, the melt viscosity increases and injection moldability decreases.

As the polycarbonate resin (A), two or more types of polycarbonate resins having different viscosity average molecular weights may be mixed and used. In this case, polycarbonate resins having a viscosity average molecular weight outside the above range may be mixed. In this case, it is preferable to use the mixture so that the viscosity average molecular weight is within the above range.

[Polycondensation product (B)]
The polycondensate (B) used in the present invention is selected from at least one resin selected from the group consisting of polyester resin (B1), polycarbonate resin (B2), and polyester carbonate resin (B3), and is characterized in that the diol residue thereof contains a residue of a diol represented by the following general formula (1). Any of the polycondensates (B) can be produced by a conventional method.
[In formula (1), R ¹ and R ² each independently represent an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms.]

[Polyester resin (B1)]
The polyester resin (B1) used in the present invention contains a residue of a diol represented by the above general formula (1) in the diol residue.
In the above general formula (1), ^R1 and ^R2 are each independently a hydrocarbon group selected from the group consisting of an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, and an aromatic hydrocarbon group having 6 to 10 carbon atoms, and are preferably a methylene group, an ethylene group, a propylene group, a butylene group, or a structural isomer thereof, such as a dimethylethylenyl group, an isopropylene group, or an isobutylene group.
As the diol compound having a cyclic acetal skeleton of the general formula (1), 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane in which R ¹ and R ² are dimethylethylenyl groups is particularly preferred.

The diol-derived structural units represented by the above general formula (1) preferably account for 10 to 100 mol %, more preferably 10 to 80 mol %, and particularly preferably 30 to 75 mol % of all diol structural units in the polyester resin (B1).

It is also preferred that the polyester resin (B1) used in the present invention further contains, in addition to the residue of the diol compound represented by the general formula (1), one or more diol residues selected from an ethylene glycol residue, a 1,4-cyclohexanedimethanol residue, or a residue of a diol represented by the following general formula (2):
[In formula (2), R ³ to R ⁵ each independently represent an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms.]

In the above general formula (2), ^R3 is the same as ^R1 in general formula (1), and is preferably a methylene group, an ethylene group, a propylene group, a butylene group, or a structural isomer thereof, such as a dimethylethylenyl group, an isopropylene group, or an isobutylene group. ^R4 is preferably a methyl group, an ethyl group, a propyl group, a butyl group, or a structural isomer thereof, such as an isopropyl group, or an isobutyl group. ^R5 is preferably a methylene group, an ethylene group, a propylene group, a butylene group, or a structural isomer thereof, such as an isopropylene group, or an isobutylene group.
As the diol compound of the general formula (2), 5-methylol-5-ethyl-2-(1,1-dimethyl-2-hydroxyethyl)-1,3-dioxane in which R ³ is a dimethylethylenyl group, R ⁴ is an ethyl group, and R ⁵ is a methylene group is particularly preferred.

The combined mole percentage of the 1,4-cyclohexanedimethanol-derived structural units and/or the diol-derived structural units represented by the above general formula (2) is preferably 0 to 50 mole percent, and particularly preferably 0 to 30 mole percent, of the total diol structural units of the polycondensate (B).

In addition, the constituent units derived from ethylene glycol and diols other than the diols represented by the above general formula (1), 1,4-cyclohexanedimethanol, and general formula (2) in the polyester resin (B1) are not particularly limited, and include aliphatic diols such as trimethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, propylene glycol, and neopentyl glycol; 1,3-cyclohexanedimethanol, 1,2-decahydronaphthalenedimethanol, 1,3-decahydronaphthalenedimethanol, 1,4-decahydronaphthalenedimethanol, 1,5-decahydronaphthalenedimethanol, 1,6-decahydronaphthalenedimethanol, 2,7-decahydronaphthalenedimethanol, tetralin dimethanol, norbornane dimethanol, trimethylol dimethanol, tetra ... Examples of structural units derived from diols include alicyclic diols such as cyclodecane dimethanol and pentacyclododecane dimethanol; polyether compounds such as polyethylene glycol, polypropylene glycol, and polybutylene glycol; bisphenols such as 4,4'-(1-methylethylidene)bisphenol, methylene bisphenol (bisphenol F), 4,4'-cyclohexylidene bisphenol (bisphenol Z), and 4,4'-sulfonyl bisphenol (bisphenol S); alkylene oxide adducts of the above bisphenols; aromatic dihydroxy compounds such as hydroquinone, resorcin, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether, and 4,4'-dihydroxydiphenyl benzophenone; and alkylene oxide adducts of the above aromatic dihydroxy compounds.

The constituent units derived from ethylene glycol, 1,4-cyclohexanedimethanol, and diols other than the diols represented by the general formulas (1) and (2) above preferably account for 0 to 10 mol % of all diol constituent units in the polyester resin (B1).

The carboxylic acid constituent unit of the polyester resin (B1) is preferably a carboxylic acid unit selected from at least one of a terephthalic acid residue, an isophthalic acid residue, and a 1,4-cyclohexanedicarboxylic acid residue.

The carboxylic acid constituent unit of the polyester resin (B1) is preferably a carboxylic acid unit selected from at least one of terephthalic acid residue, isophthalic acid residue, and 1,4-cyclohexanedicarboxylic acid residue, but may contain other carboxylic acid constituent units other than these, such as phthalic acid; halogen-substituted phthalic acids such as tetrabromophthalic acid and tetrabromoterephthalic acid, and alkyl-substituted phthalic acids such as methylisophthalic acid; naphthalene dicarboxylic acids such as 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, and 1,5-naphthalene dicarboxylic acid; diphenyl dicarboxylic acids such as 4,4'-diphenyl dicarboxylic acid and 3,4'-diphenyl dicarboxylic acid; aromatic dicarboxylic acids such as 4,4'-diphenoxyethane dicarboxylic acid; aliphatic or alicyclic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, azelaic acid, and decadicarboxylic acid; and oxycarboxylic acids such as ε-oxycaproic acid, hydroxybenzoic acid, and hydroxyethoxybenzoic acid.

These copolymerization components can be used alone or in combination, and the proportion is preferably 20 mol % or less, and especially 10 mol % or less, based on the total dicarboxylic acids (half of which is calculated as carboxylic acid).

The polyester resin (B1) can be produced by a conventional method. For example, a melt polymerization method such as a transesterification method or a direct esterification method, or a solution polymerization method can be mentioned.

When producing the polyester resin (B1), a conventionally known catalyst can be used. For example, sodium and magnesium alkoxides; fatty acid salts, carbonates, phosphates, hydroxides, chlorides, and oxides of zinc, lead, cerium, cadmium, manganese, cobalt, lithium, sodium, potassium, calcium, nickel, magnesium, vanadium, aluminum, titanium, germanium, antimony, tin, and the like; and metallic magnesium can be mentioned. These can be used alone or in combination.
Among the above catalysts, the fatty acid salts, carbonates, phosphates, hydroxides, chlorides and oxides of titanium and germanium are preferred.

[Polycarbonate resin (B2)]
The polycarbonate resin (B2) used in the present invention contains a residue of a diol represented by the above general formula (1) in the diol residue.
In the above general formula (1), ^R1 and ^R2 are each independently a hydrocarbon group selected from the group consisting of an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, and an aromatic hydrocarbon group having 6 to 10 carbon atoms, and are preferably a methylene group, an ethylene group, a propylene group, a butylene group, or a structural isomer thereof, such as a dimethylethylenyl group, an isopropylene group, or an isobutylene group.
As the diol compound having a cyclic acetal skeleton of the general formula (1), 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane in which R ¹ and R ² are dimethylethylenyl groups is particularly preferred.

The diol-derived structural units represented by the above general formula (1) may be contained in an amount of more than 0 mol%, preferably 1 to 100 mol%, for example 1 mol%, 2 mol%, 5 mol%, 10 mol%, 15 mol%, 20 mol%, 25 mol%, 30 mol%, 35 mol%, 40 mol%, 45 mol%, 50 mol%, 55 mol%, 60 mol%, 65 mol%, 70 mol%, 75 mol%, 80 mol%, 85 mol%, 90 mol%, 95 mol%, 98 mol%, 99 mol%, or 100 mol% of all diol structural units in the polycarbonate resin (B2).

The polycarbonate resin (B2) used in the present invention preferably contains, in addition to the residue of the diol compound of general formula (1), a 1,4-cyclohexanedimethanol residue and/or a residue of a diol represented by the following general formula (2):
[In formula (2), R ³ to R ⁵ each independently represent an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms.]

In the above general formula (2), ^R3 is the same as ^R1 in general formula (1), and is preferably a methylene group, an ethylene group, a propylene group, a butylene group, or a structural isomer thereof, such as a dimethylethylenyl group, an isopropylene group, or an isobutylene group. ^R4 is preferably a methyl group, an ethyl group, a propyl group, a butyl group, or a structural isomer thereof, such as an isopropyl group, or an isobutyl group. ^R5 is preferably a methylene group, an ethylene group, a propylene group, a butylene group, or a structural isomer thereof, such as an isopropylene group, or an isobutylene group.
As the diol compound of the general formula (2), 5-methylol-5-ethyl-2-(1,1-dimethyl-2-hydroxyethyl)-1,3-dioxane in which R ³ is a dimethylethylenyl group, R ⁴ is an ethyl group, and R ⁵ is a methylene group is particularly preferred.

The combined mole percentage of the 1,4-cyclohexanedimethanol-derived structural units and/or the diol-derived structural units represented by the above general formula (2) is less than 100 mole% of the total diol structural units of the polycondensate (B), and may be, for example, 99 mole%, 98 mole%, 95 mole%, 90 mole%, 85 mole%, 80 mole%, 75 mole%, 70 mole%, 65 mole%, 60 mole%, 55 mole%, 50 mole%, 45 mole%, 40 mole%, 35 mole%, 30 mole%, 25 mole%, 20 mole%, 15 mole%, 10 mole%, 5 mole%, 2 mole%, 1 mole%, or 0 mole%.

[Polyester carbonate resin (B3)]
The polyester carbonate resin (B3) used in the present invention contains a residue of a diol represented by the above general formula (1) in the diol residue.
In the above general formula (1), ^R1 and ^R2 are each independently a hydrocarbon group selected from the group consisting of an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, and an aromatic hydrocarbon group having 6 to 10 carbon atoms, and are preferably a methylene group, an ethylene group, a propylene group, a butylene group, or a structural isomer thereof, such as a dimethylethylenyl group, an isopropylene group, or an isobutylene group.
As the diol compound having a cyclic acetal skeleton of the general formula (1), 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane in which R ¹ and R ² are dimethylethylenyl groups is particularly preferred.

The polyester carbonate resin (B3) used in the present invention may further contain an alicyclic dicarboxylic acid or a diester thereof.

In one embodiment of the present invention, the alicyclic dicarboxylic acid or diester thereof may be, but is not limited to, 1,4-cyclohexanedicarboxylic acid, dimethyl 1,4-cyclohexanedicarboxylate, diethyl 1,4-cyclohexanedicarboxylate, dimethyl 1,3-cyclopentanedicarboxylate, or dimethyl 1,4-cycloheptanedicarboxylate.

In one embodiment of the present invention, the alicyclic dicarboxylic acid or its diester is 1,4-cyclohexanedicarboxylic acid or dimethyl 1,4-cyclohexanedicarboxylate.

In one embodiment of the present invention, the diol-derived structural unit represented by the above general formula (1) may be contained in an amount of 100 to 1 mol% of all diol structural units of the polyester carbonate resin (B3), for example, 100 mol%, 99 mol%, 98 mol%, 95 mol%, 90 mol%, 85 mol%, 80 mol%, 75 mol%, 70 mol%, 65 mol%, 60 mol%, 55 mol%, 50 mol%, 45 mol%, 40 mol%, 35 mol%, 30 mol%, 25 mol%, 20 mol%, 15 mol%, 10 mol%, 5 mol%, 2 mol%, or 1 mol%.

In one embodiment of the present invention, the structural units derived from the alicyclic dicarboxylic acid or its diester may be contained in an amount of 1 to 100 mol% of all dicarboxylic acid structural units of the polyester carbonate (B3), for example, 1 mol%, 2 mol%, 5 mol%, 10 mol%, 15 mol%, 20 mol%, 25 mol%, 30 mol%, 35 mol%, 40 mol%, 45 mol%, 50 mol%, 55 mol%, 60 mol%, 65 mol%, 70 mol%, 75 mol%, 80 mol%, 85 mol%, 90 mol%, 95 mol%, 98 mol%, 99 mol%, or 100 mol%.

<Ratio of Polycarbonate Resin (A) and Polycondensate (B)>
The thermoplastic resin composition of the present invention contains 40 to 75 parts by mass of the polycarbonate resin (A) and 25 to 60 parts by mass of the polycondensate (B) based on a total of 100 parts by mass of the polycarbonate resin (A) and the polycondensate (B). If the amount of polycarbonate resin (A) is more and the amount of polycondensate (B) is less than this range, or conversely, if the amount of polycondensate (B) is more and the amount of polycarbonate resin (A) is less than this range, the refractive index of the resin matrix cannot be made close to the refractive index of the glass filler (C), and a molded product having excellent transparency cannot be obtained.
In particular, it is preferable that the composition contains 60 to 70 parts by mass of the polycarbonate resin (A) and 30 to 40 parts by mass of the polycondensate (B).

It is preferable to design the mixing ratio of the polycarbonate resin (A) and the polycondensate (B) so that the refractive index of the glass filler (C) used is close to that of the resin matrix. Therefore, it is preferable to appropriately adjust the mixing ratio of the polycarbonate resin (A) and the polycondensate (B) according to the refractive index of the glass filler (C) used.

[Glass filler (C)]
The form of the glass filler (C) used in the present invention is not particularly limited, and various forms such as glass fiber, glass powder, glass flakes, milled fiber, glass beads, etc. can be used. These may be used alone or in combination of two or more. From the viewpoints of transparency and reinforcing effect, it is preferable to use glass fiber and/or glass flakes.
The glass composition of the glass filler (C) is not particularly limited, but is preferably an alkali-free glass (E glass).

The glass fibers used as the glass filler (C) are preferably glass fibers having a flat cross-sectional shape (a cross-section perpendicular to the fiber length direction of the glass fibers) rather than a circular cross-sectional shape (hereinafter, may be referred to as "flat cross-sectional glass fibers"), since such glass fibers have excellent orientation during molding, are excellent in improving the dimensional stability, and are also effective in improving the transparency of molded products.
Here, the cross-sectional shape of the glass fiber can be represented by an aspect ratio, which is the major axis/minor axis ratio (D2/D1) where D2 is the major axis of the cross section perpendicular to the longitudinal direction of the fiber and D1 is the minor axis. The average aspect ratio of the glass fiber used in the present invention is preferably 1.5 to 8, and more preferably 3 to 8.

The average cross-sectional major axis D1 of the flat cross-section glass fiber used in the present invention is usually 10 to 50 μm, preferably 15 to 40 μm, more preferably 20 to 35 μm, even more preferably 24 to 30 μm, and particularly preferably 25 to 30 μm.

The cross-sectional shape of the flat cross-section glass fiber includes not only flat (approximately rectangular) but also non-circular shapes such as ellipse, cocoon, trefoil, and similar shapes, but flat or ellipse is preferred, and flat is particularly preferred.

The ratio of the average fiber length to the average fiber diameter (aspect ratio) of the glass fibers used in the present invention is usually 2 to 1000, preferably 2.5 to 700, and more preferably 3 to 600. If the aspect ratio of the glass fibers is 2 or more, it is effective in improving the mechanical strength, and if it is 600 or less, it is possible to suppress warping and anisotropy and prevent deterioration of the appearance of the molded product.

The average fiber diameter of glass fibers refers to the diameter of glass fibers with a circular cross section, but for glass fibers with other cross sections, it refers to the number average fiber diameter when the cross section is converted into a perfect circle of the same area. The average fiber length of glass fibers refers to the number average value of the length in the longitudinal direction of the fibers. The average fiber length and average fiber diameter of glass fibers can be calculated as the average fiber length and fiber diameter measured for approximately 100 arbitrarily selected glass fibers by observation with a SEM (scanning electron microscope), but for commercially available products, catalog values can be used.

Glass flakes are typically scaly glass powders with an average particle size of 10 to 4000 μm, an average thickness of 0.1 to 10 μm, and an aspect ratio (ratio of average maximum diameter/average thickness) of approximately 2 to 1000. The glass flakes used in the present invention preferably have an average particle size of 2000 μm or less, particularly 100 to 1500 μm, an average thickness of 0.1 to 10 μm, particularly 0.4 to 6 μm, and an aspect ratio of 10 to 800, particularly 50 to 600.

The glass filler (C) is preferably either or both of glass fibers having a cross-sectional shape with an aspect ratio of 1.5 to 8 and glass flakes having an average thickness of 0.1 to 10 μm.

The glass filler (C) used in the present invention may be surface-treated with a surface treatment agent such as a silane coupling agent in order to improve adhesion to the resin matrix and suppress decomposition of the polycarbonate resin (A). However, since most commercially available glass fibers and glass flakes are already surface-treated with a surface treatment agent, when using a surface-treated product, it is not necessary to use a surface treatment agent.

The content of the glass filler (C) is 10 to 50 parts by mass per 100 parts by mass of the total of the polycarbonate resin (A) and the polycondensate (B). If the content of the glass filler (C) is less than 10 parts by mass, the effect of improving rigidity and the like due to the incorporation of the glass filler (C) cannot be fully obtained, and if the content of the glass filler (C) exceeds 50 parts by mass, the high incorporation of the glass filler (C) causes problems such as a decrease in transparency and appearance of the molded product due to surface lifting of the glass filler (C), and a decrease in impact resistance, and melt extrusion (pelletization) of the thermoplastic resin composition may become difficult. The content of the glass filler (C) is preferably 10 to 45 parts by mass, and more preferably 10 to 40 parts by mass.

[Other resin components]
The thermoplastic resin composition of the present invention may contain, as a thermoplastic resin component, a thermoplastic resin other than the above-mentioned polycarbonate resin (A) and polycondensate (B), as long as the effects of the present invention are not impaired.
Examples of other thermoplastic resins that may be contained in the thermoplastic resin composition of the present invention include polyolefin resins such as polyethylene resins and polypropylene resins, polyamide resins, polyimide resins, polyetherimide resins, polyurethane resins, polyphenylene ether resins, polyphenylene sulfide resins, polysulfone resins, polymethacrylate resins, phenolic resins, epoxy resins, polyester resins other than the polycondensate (B), and thermoplastic elastomers, etc. The content ratio of these other thermoplastic resins is preferably 10 parts by mass or less, particularly 5 parts by mass or less, per 100 parts by mass of the total of the polycarbonate resin (A) and the polycondensate (B), in order to effectively obtain the effect of the present invention by using the polycarbonate resin (A) and the polycondensate (B) in combination, i.e., the effect of improving transparency.

[Other additives]
The thermoplastic resin composition of the present invention may further contain various additives within a range that does not impair the effects of the present invention. Examples of such additives include stabilizers such as phosphorus-based heat stabilizers, release agents, ultraviolet absorbers, antistatic agents, dyes and pigments, antifogging agents, lubricants, antiblocking agents, flow improvers, sliding property improvers, impact resistance improvers, plasticizers, dispersants, antibacterial agents, flame retardants, and drip prevention agents. These may be used in combination of two or more. Hereinafter, an example of an additive suitable for the thermoplastic resin composition of the present invention will be specifically described.

<Stabilizer (D)>
Examples of the stabilizer (D) include the following phosphorus-based heat stabilizers, phenol-based antioxidants, and organic phosphate ester compounds.

(Phosphorus-based heat stabilizer)
The thermoplastic resin composition of the present invention may contain a phosphorus-based heat stabilizer. Phosphorus-based heat stabilizers are generally effective in improving retention stability at high temperatures when melt-kneading resin components and heat resistance stability when using resin molded products.

Phosphorus-based heat stabilizers include phosphorous acid, phosphoric acid, phosphite esters, and phosphate esters (excluding the organic phosphate ester compounds described below), among which phosphites, phosphonites, and other phosphites are preferred because they contain trivalent phosphorus and are more likely to exhibit discoloration inhibition effects.

Examples of phosphites include triphenyl phosphite, tris(nonylphenyl)phosphite, dilauryl hydrogen phosphite, triethyl phosphite, tridecyl phosphite, tris(2-ethylhexyl)phosphite, tris(tridecyl)phosphite, tristearyl phosphite, diphenyl monodecyl phosphite, monophenyl didecyl phosphite, diphenyl mono(tridecyl)phosphite, tetraphenyl dipropylene glycol diphosphite, tetraphenyl tetra(tridecyl)pentaerythritol tetraphosphite, hydrogenated bisphenol A phenol phosphite polymer, diphenyl hydrogen phosphite, 4,4'-butylidene-bis(3-methyl-6-tert-butylphenyl di(tridecyl)phosphite), tetra(tridecyl) 4,4'-isopropyl Lidenediphenyl diphosphite, bis(tridecyl)pentaerythritol diphosphite, bis(nonylphenyl)pentaerythritol diphosphite, dilauryl pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tris(4-tert-butylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite, hydrogenated bisphenol A pentaerythritol phosphite polymer, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite, bis(2,4-dicumylphenyl)pentaerythritol diphosphite, etc.

Examples of phosphonites include tetrakis(2,4-di-iso-propylphenyl)-4,4'-biphenylene diphosphonite, tetrakis(2,4-di-n-butylphenyl)-4,4'-biphenylene diphosphonite, tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite, tetrakis(2,4-di-tert-butylphenyl)-4,3'-biphenylene diphosphonite, and tetrakis(2,4-di-tert-butylphenyl)-3,3'-biphenylene diphosphona Examples of such compounds include tetrakis(2,6-di-iso-propylphenyl)-4,4'-biphenylene diphosphonite, tetrakis(2,6-di-n-butylphenyl)-4,4'-biphenylene diphosphonite, tetrakis(2,6-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite, tetrakis(2,6-di-tert-butylphenyl)-4,3'-biphenylene diphosphonite, and tetrakis(2,6-di-tert-butylphenyl)-3,3'-biphenylene diphosphonite.

Among the phosphite esters, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl)phosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl)octylphosphite, and bis(2,4-dicumylphenyl)pentaerythritol diphosphite are preferred, with tris(2,4-di-tert-butylphenyl)phosphite being particularly preferred due to its good heat resistance and resistance to hydrolysis.

Phosphorus-based heat stabilizers may be used alone or in combination of two or more types.

When a phosphorus-based heat stabilizer is contained, the content is usually 0.01 to 3 parts by mass, particularly 0.02 to 1 part by mass, and especially 0.03 to 0.5 parts by mass, per 100 parts by mass of the polycarbonate resin (A) and polycondensate (B) combined. By having the amount of phosphorus-based heat stabilizer equal to or greater than the above lower limit, the effect of improving thermal stability by incorporating the phosphorus-based heat stabilizer can be sufficiently obtained. However, if the amount of phosphorus-based heat stabilizer is too high, the effect will plateau and it will not be economical, so the amount is set to equal to or less than the above upper limit.

(Phenol-based antioxidant)
The thermoplastic resin composition of the present invention may contain a phenol-based antioxidant. By containing a phenol-based antioxidant, deterioration in color and deterioration of mechanical properties during heat retention can be suppressed.

Examples of phenol-based antioxidants include hindered phenol-based antioxidants. Specific examples include pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenylpropionamide], 2,4-dimethyl-6-(1-methylpentadecyl)phenol, diethyl[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphate, 3,3',3'',5,5',5''-hexyl Examples of such compounds include tert-butyl-a,a',a''-(mesitylene-2,4,6-triyl)tri-p-cresol, 4,6-bis(octylthiomethyl)-o-cresol, ethylene bis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate], hexamethylene bis[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, and 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazin-2-ylamino)phenol.

Among these, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate are preferred. Examples of commercially available phenolic antioxidants include "Irganox 1010" and "Irganox 1076" manufactured by BASF, and "Adekastab AO-60" and "Adekastab AO-50" manufactured by ADEKA.

The phenolic antioxidants may be used alone or in combination of two or more.

When a phenolic antioxidant is contained, the content is usually 0.02 to 3 parts by mass, particularly 0.03 to 1 part by mass, and especially 0.04 to 0.5 parts by mass, per 100 parts by mass of the polycarbonate resin (A) and polycondensate (B) combined. By having the amount of the phenolic antioxidant be equal to or greater than the above lower limit, the above-mentioned effects of incorporating the phenolic antioxidant can be effectively obtained. However, if the amount of the phenolic antioxidant is too high, the effect will plateau and it will not be economical, so the amount is set to be equal to or less than the above upper limit.

In addition, it is preferable that the thermoplastic resin composition of the present invention contains both a phosphorus-based heat stabilizer and a phenol-based antioxidant. In this case, it is preferable that the phosphorus-based heat stabilizer and the phenol-based antioxidant are contained in a total amount of 0.04 to 2 parts by mass per 100 parts by mass of the polycarbonate resin (A) and the polycondensate (B) in a mass ratio of phosphorus-based heat stabilizer:phenol-based antioxidant = 1:0.2 to 3.

(Organophosphate Compounds)
The thermoplastic resin composition of the present invention may contain an organic phosphate ester compound represented by the following general formula (3) in order to improve thermal stability.
(RO) _n P(O)(OH) _3-n ... (3)
(In the formula, R represents an alkyl group having a total of 2 to 25 carbon atoms which may have a substituent, and n represents 1 or 2. However, when n is 2, the two R's may be the same or different from each other.)

The unsubstituted alkyl group represented by R in the above general formula (1) includes octyl, 2-ethylhexyl, isooctyl, nonyl, isononyl, decyl, isodecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, hexadecyl, octadecyl, and stearyl. Examples of substituted alkyl groups include those in which a chain-like hydrocarbon group such as a butyl group, allyl group, or methallyl group is bonded to the alkyl group via an ether bond or an ester bond. It is preferable to use an alkyl group having these substituents as R. It is also preferable that the total number of carbon atoms in R, including the carbon of the substituent, is 5 or more.

The organic phosphate ester compound may be a mixture of compounds having different R and n in general formula (1).

When the thermoplastic resin composition of the present invention contains an organic phosphate ester compound, the content is usually 0.02 to 3 parts by mass, particularly 0.03 to 1 part by mass, and especially 0.04 to 0.5 parts by mass, per 100 parts by mass of the total of the polycarbonate resin (A) and the polycondensate (B). By making the amount of the organic phosphate ester compound equal to or greater than the above lower limit, the effect of improving thermal stability by incorporating the organic phosphate ester compound can be sufficiently obtained. However, if the amount of the organic phosphate ester compound is too large, the effect will plateau and it will not be economical, so the amount is set to equal to or less than the above upper limit.

<Release Agent (E)>
The releasing agent (E) may be at least one compound selected from the group consisting of aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15,000, and polysiloxane-based silicone oils.

Examples of aliphatic carboxylic acids include saturated or unsaturated aliphatic mono-, di-, or tri-carboxylic acids. Here, aliphatic carboxylic acids also include alicyclic carboxylic acids. Among these, preferred aliphatic carboxylic acids are mono- or di-carboxylic acids having 6 to 36 carbon atoms, and more preferred are saturated aliphatic mono-carboxylic acids having 6 to 36 carbon atoms. Specific examples of such aliphatic carboxylic acids include palmitic acid, stearic acid, caproic acid, capric acid, lauric acid, arachic acid, behenic acid, lignoceric acid, cerotic acid, melissic acid, tetralinic acid, montanic acid, adipic acid, and azelaic acid.

The aliphatic carboxylic acid in the ester of an aliphatic carboxylic acid and an alcohol can be the same as the aliphatic carboxylic acid described above. On the other hand, the alcohol can be a saturated or unsaturated monohydric or polyhydric alcohol. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these, a monohydric or polyhydric saturated alcohol having 30 or less carbon atoms is preferred, and an aliphatic saturated monohydric or polyhydric alcohol having 30 or less carbon atoms is more preferred. Here, the term "aliphatic" also includes alicyclic compounds. 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, etc.

The above ester compounds may contain aliphatic carboxylic acids and/or alcohols as impurities, and may be mixtures of multiple compounds.

Specific examples of esters of aliphatic carboxylic acids and alcohols include beeswax (a mixture mainly composed of myricyl palmitate), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, glycerin monostearate, glycerin distearate, glycerin tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate, etc.

Examples of aliphatic hydrocarbons 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 oligomers having 3 to 12 carbon atoms. Here, the aliphatic hydrocarbons also include alicyclic hydrocarbons. These hydrocarbon compounds may be partially oxidized. Among these, paraffin wax, polyethylene wax, or partial oxides of polyethylene wax are preferred, with paraffin wax and polyethylene wax being more preferred. The number average molecular weight is preferably 200 to 5,000. These aliphatic hydrocarbons may be a single substance or a mixture of substances with various constituent components and molecular weights, as long as the main component is within the above range.

Examples of polysiloxane-based silicone oils include dimethyl silicone oil, phenylmethyl silicone oil, diphenyl silicone oil, and fluorinated alkyl silicone. Two or more of these may be used in combination.

When a release agent (E) is used, its content is usually 0.05 to 2 parts by mass, and preferably 0.1 to 1 part by mass, per 100 parts by mass of the total of the polycarbonate resin (A) and the polycondensate (B). When the content of the release agent is equal to or greater than the lower limit, the effect of improving the release properties can be sufficiently obtained, and when the content is equal to or less than the upper limit, problems such as a decrease in hydrolysis resistance due to excessive incorporation of the release agent and mold contamination during injection molding can be prevented.

<Ultraviolet absorbing agent>
The thermoplastic resin composition of the present invention may contain an ultraviolet absorber. By containing an ultraviolet absorber, the weather resistance of the thermoplastic resin composition of the present invention can be improved, and the improved weather resistance can prevent a decrease in transparency.

Examples of ultraviolet absorbers include inorganic ultraviolet absorbers such as cerium oxide and zinc oxide; and organic ultraviolet absorbers such as benzotriazole compounds, benzophenone compounds, salicylate compounds, cyanoacrylate compounds, triazine compounds, oxanilide compounds, malonic acid ester compounds, and hindered amine compounds. Among these, organic ultraviolet absorbers are preferred, and benzotriazole compounds are more preferred. By selecting an organic ultraviolet absorber, the transparency and mechanical properties of the thermoplastic resin composition of the present invention can be 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-butyl-phenyl)-5-chlorobenzotriazole, -amyl)-benzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2N-benzotriazol-2-yl)phenol] and the like, among which 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole and 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2N-benzotriazol-2-yl)phenol] are preferred, and 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole is particularly preferred.
Specific examples of such benzotriazole compounds include "Seesorb 701", "Seesorb 705", "Seesorb 703", "Seesorb 702", "Seesorb 704", and "Seesorb 709" manufactured by Shipro Chemical Co., Ltd., "Biosorb 520", "Biosorb 582", "Biosorb 580", and "Biosorb 583" manufactured by Kyodo Pharmaceutical Co., Ltd., "Chemisorb 71" and "Chemisorb 72" manufactured by Chemipro Chemical Co., Ltd., "Cyasorb UV5411" manufactured by Cytec Industries, Inc., "LA-32", "LA-38", "LA-36", "LA-34", and "LA-31" manufactured by ADEKA, and "Tinuvin P", "Tinuvin 234", "Tinuvin 326", "Tinuvin 327", and "Tinuvin 328" manufactured by BASF.

Specific examples of the benzophenone compound include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-n-dodecyloxybenzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2,2'-dihydroxy-4-methoxybenzophenone, and 2,2'-dihydroxy-4,4'-dimethoxybenzophenone.
Specific examples of such benzophenone compounds include "Seesorb 100", "Seesorb 101", "Seesorb 101S", "Seesorb 102", and "Seesorb 103" manufactured by Shipro Chemicals, "Biosorb 100", "Biosorb 110", and "Biosorb 130" manufactured by Kyodo Pharmaceuticals, and "Chemisorb 10", "Chemisorb 11", "Chemisorb 11S", and "Chemisorb 12" manufactured by Chemipro Chemicals. , "CHEMISORB 13", "CHEMISORB 111", "Ubinul 400" manufactured by BASF, "Ubinul M-40" manufactured by BASF, "Ubinul MS-40" manufactured by BASF, "Cyasorb UV9", "Cyasorb UV284", "Cyasorb UV531", "Cyasorb UV24" manufactured by Cytec Industries, "ADEKA STAB 1413" and "ADEKA STAB LA-51" manufactured by ADEKA Corporation, and the like.

Specific examples of salicylate compounds include phenyl salicylate and 4-tert-butylphenyl salicylate. Specific examples of such salicylate compounds include Seesorb 201 and Seesorb 202 manufactured by Shipro Chemicals, and Chemisorb 21 and Chemisorb 22 manufactured by Chemipro Chemicals.

Specific examples of cyanoacrylate compounds include ethyl-2-cyano-3,3-diphenylacrylate, 2-ethylhexyl-2-cyano-3,3-diphenylacrylate, etc., and specific examples of such cyanoacrylate compounds include "Seesorb 501" manufactured by Shipro Kasei Co., Ltd., "Biosorb 910" manufactured by Kyodo Pharmaceutical Co., Ltd., "Ubisolator 300" manufactured by Daiichi Kasei Co., Ltd., "Ubinur N-35" and "Ubinur N-539" manufactured by BASF Corporation.

Specific examples of oxalinide compounds include 2-ethoxy-2'-ethyl oxalinic acid bis-arylamide, and specific examples of such oxalinide compounds include "Sandubor VSU" manufactured by Clariant.

As the malonic acid ester compound, 2-(alkylidene)malonic acid esters are preferred, and 2-(1-arylalkylidene)malonic acid esters are more preferred. Specific examples of such malonic acid ester compounds include "PR-25" manufactured by Clariant Japan and "B-CAP" manufactured by BASF.

A single type of UV absorber may be used alone, or two or more types may be used in combination.

When the thermoplastic resin composition of the present invention contains an ultraviolet absorber, the content is usually 0.001 to 3 parts by mass, preferably 0.01 to 1 part by mass, more preferably 0.1 to 0.5 parts by mass, and even more preferably 0.1 to 0.4 parts by mass, per 100 parts by mass of the total of the polycarbonate resin (A) and the polycondensate (B). When the content of the ultraviolet absorber is equal to or greater than the lower limit of the above range, the effect of improving weather resistance can be sufficiently obtained, and when the content is equal to or less than the upper limit, mold contamination due to mold deposits, etc. can be prevented.

<Antistatic Agent>
The thermoplastic resin composition of the present invention may contain an antistatic agent if desired. The antistatic agent is not particularly limited, but a preferred example is a sulfonate phosphonium salt represented by the following general formula (4).

(In the formula, R ³ is an alkyl group or an aryl group having 1 to 40 carbon atoms, which may have a substituent, and R ⁴ to R ⁷ are each independently a hydrogen atom, an alkyl group or an aryl group having 1 to 10 carbon atoms, which may be the same or different.)

R ³ in the above general formula (4) is an alkyl group or aryl group having 1 to 40 carbon atoms, but an aryl group is preferred from the viewpoints of transparency, heat resistance, and compatibility with the polycarbonate resin (A) and the polycondensate (B), and a group derived from an alkylbenzene or alkylnaphthalene ring substituted with an alkyl group having 1 to 34 carbon atoms, preferably 5 to 20 carbon atoms, and particularly preferably 10 to 15 carbon atoms. Furthermore, R ⁴ to R ⁷ in the general formula (2) are each independently a hydrogen atom, an alkyl group or an aryl group having 1 to 10 carbon atoms, but are preferably an alkyl group having 2 to 8 carbon atoms, more preferably an alkyl group having 3 to 6 carbon atoms, and particularly preferably a butyl group.

Specific examples of such sulfonate phosphonium salts include tetrabutyl phosphonium dodecyl sulfonate, tetrabutyl phosphonium dodecyl benzene sulfonate, tributyl octyl phosphonium dodecyl benzene sulfonate, tetraoctyl phosphonium dodecyl benzene sulfonate, tetraethyl phosphonium octadecyl benzene sulfonate, tributyl methyl phosphonium dibutyl benzene sulfonate, triphenyl phosphonium dibutyl naphthyl sulfonate, trioctyl methyl phosphonium diisopropyl naphthyl sulfonate, etc. Among these, tetrabutyl phosphonium dodecyl benzene sulfonate is preferred in terms of compatibility with polycarbonate and easy availability.
These may be used alone or in combination of two or more.

When the thermoplastic resin composition of the present invention contains an antistatic agent, the content is preferably 0.1 to 5.0 parts by mass, more preferably 0.2 to 3.0 parts by mass, even more preferably 0.3 to 2.0 parts by mass, and particularly preferably 0.5 to 1.8 parts by mass, per 100 parts by mass of the total of the polycarbonate resin (A) and the polycondensate (B). If the content of the antistatic agent is less than 0.1 parts by mass, the antistatic effect cannot be obtained, and if it exceeds 5.0 parts by mass, the transparency and mechanical strength decrease, and silvering or peeling occurs on the surface of the molded product, easily causing a poor appearance.

<Coloring Agent>
The thermoplastic resin composition of the present invention may contain various dyes and pigments as colorants as desired. By containing a dye or pigment, the hiding power and weather resistance of the thermoplastic resin composition of the present invention can be improved. In addition, by containing a colorant, the design of a molded product obtained by molding the thermoplastic resin composition of the present invention can be improved.

Examples of dyes and pigments include inorganic pigments, organic pigments, and organic dyes.

Examples of inorganic pigments include sulfide pigments such as carbon black, cadmium red, and cadmium yellow; silicate pigments such as ultramarine; oxide pigments such as titanium oxide, zinc white, red iron oxide, chromium oxide, iron black, titanium yellow, zinc-iron brown, titanium-cobalt green, cobalt green, cobalt blue, copper-chromium black, and copper-iron black; chromate pigments such as yellow lead and molybdate orange; and ferrocyanide pigments such as iron blue.

Examples of organic pigments and dyes include phthalocyanine-based pigments such as copper phthalocyanine blue and copper phthalocyanine green; azo-based pigments such as nickel azo yellow; condensed polycyclic pigments such as thioindigo, perinone, perylene, quinacridone, dioxazine, isoindolinone, quinoline, and quinophthalone; cyanine, anthraquinone, heterocyclic, and methyl-based pigments.

Among these, titanium oxide, carbon black, cyanine-based, quinoline-based, anthraquinone-based, and phthalocyanine-based compounds are preferred from the viewpoint of thermal stability.

The above colorants may be contained in one type or in any combination and ratio of two or more types.

The colorant may be used in the form of a masterbatch with polycarbonate resin (A) or other resins in order to improve handling during extrusion and improve dispersibility in the resin composition.

When the thermoplastic resin composition of the present invention contains a colorant, its content may be appropriately selected according to the required design, but is usually 0.001 parts by mass or more, preferably 0.005 parts by mass or more, more preferably 0.01 parts by mass or more, and usually 3 parts by mass or less, preferably 2 parts by mass or less, more preferably 1 part by mass or less, and even more preferably 0.5 parts by mass or less, per 100 parts by mass of the total of the polycarbonate resin (A) and the polycondensate (B). If the content of the colorant is less than the above lower limit, the coloring effect may not be sufficient. If the content of the colorant exceeds the above upper limit, mold deposits, etc. may occur, causing mold contamination.

[Method of producing thermoplastic resin composition]
The kneading conditions for producing the thermoplastic resin composition of the present invention vary depending on the type and blending ratio of each component used in the thermoplastic resin composition and cannot be generally stated, but when glass fiber is used as the glass filler (C), it is preferable to melt-knead it separately from other components. In particular, when melt-kneading using an extruder, it is preferable to feed the glass fiber from the middle of the extruder to the melt-kneaded product in which the polycarbonate resin (A) and the polycondensate (B) and other components are sufficiently melt-kneaded using a side feed method, so that the glass fiber can be prevented from being cut or bent during melt-kneading and the shape of the glass fiber can be maintained.

In this case, it is preferable that the glass fibers are fed when the resin components are sufficiently melted and kneaded. In this respect, it is preferable to side feed the glass fibers downstream of the extruder. However, if the side feed position is too far downstream, the glass fibers will be extruded before they are sufficiently dispersed in the resin composition. From this perspective, it is preferable to side feed the glass fibers from the upstream (hopper) of the extruder to a downstream position about 1/5 to 4/5 of the barrel length L. There is no particular restriction on the L/D (barrel length/screw diameter) of the extruder used for melt extrusion, and it is usually about 25 to 50. It is also preferable to set the screw rotation speed to 150 to 600 rpm and the cylinder temperature to about 250 to 300°C.

The strands molten and extruded from the extruder are quenched in a water tank and cut using a pelletizer to obtain pellets of the thermoplastic resin composition of the present invention.

[Thermoplastic resin molded products]
The method for producing a molded article from the thermoplastic resin composition of the present invention is not particularly limited, and molding methods generally used for thermoplastic resins, namely, general injection molding, ultra-high speed injection molding, injection compression molding, multi-color injection molding, gas-assisted injection molding, molding using a heat-insulating mold, molding using a rapid heating and cooling mold, foam molding (including supercritical fluid), insert molding, IMC (in-mold coating molding) molding, extrusion molding, sheet molding, thermoforming, rotational molding, lamination molding, press molding, etc., can be adopted. In addition, among various injection molding methods, a molding method using a hot runner system can also be selected.

The thermoplastic resin composition of the present invention can also be multicolor composite molded with other thermoplastic resin compositions to produce composite molded products.

The thermoplastic resin composition of the present invention can also be made into a composite molded product with a metal member by inserting the metal member into a mold and injection molding the resin into the mold.

The thermoplastic resin composition of the present invention can also be made into a composite molded product with a glass member by inserting a glass member into a mold and injection molding the resin into the mold.

The molded article of the present invention preferably has a surface smoothness in which the surface roughness Ra of the molded article surface occupying 30% or more of the total surface area is 0.1 μm or less. By having such surface smoothness, light scattering on the molded article surface is prevented, and better transparency can be obtained. From the viewpoint of improving transparency by preventing this light scattering, the smooth surface with a surface roughness Ra of 0.1 μm or less is preferably the design surface of the molded article.
The area of the smooth surface having a surface roughness Ra of 0.1 μm or less is preferably as large as possible from the viewpoint of transparency, and more preferably is 50% or more of the total surface area of the molded article. From the viewpoint of transparency, this area varies depending on the shape and use of the molded article, but it is sufficient if it is 70% or more of the total surface area of the molded article, and the upper limit is usually 100%.

In order to obtain a molded article with better transparency, it is preferable to produce a molded article by injection molding the thermoplastic resin composition of the present invention according to the method for producing a molded article of the present invention as described below, using an insulated mold or by heat and cool injection molding using a rapid heating and cooling mold.

[Method for manufacturing molded products]
One embodiment of the method for producing a molded article of the present invention is characterized in that the thermoplastic resin composition of the present invention is injection molded into a heat-insulating mold, i.e., a mold having a ceramic layer on the cavity surface, or a mold having a metal layer and then a thermosetting resin layer from the cavity surface side.
Another aspect of the method for producing a molded product of the present invention is characterized in that, using a rapid heating and cooling mold, the injection step is performed when the mold cavity surface temperature is 130°C or higher, and the mold opening step is performed when the mold cavity surface temperature is 80°C or lower (hereinafter, this method is referred to as "heat and cool molding").

In any of the above-mentioned methods for producing a molded article, floating of the glass filler (C) on the surface of the molded article is prevented, and a smooth surface is formed, thereby suppressing light scattering on the surface of the molded article and improving transparency.
That is, when a heat-insulating mold is used, heat radiation from the molten resin injected into the mold is prevented, and the resin, which is more fluid than the glass filler (C), flows in the surface layer portion of the molded product, thereby preventing the glass filler (C) from floating on the surface.
Also in the case of heat and cool molding, it becomes possible to slowly cool the molten resin injected into the cavity, and thus it is possible to prevent the glass filler (C) from floating on the surface.

[Molding method using a thermally insulated mold]
The insulated mold is a mold having a ceramic layer on the cavity surface (hereinafter may be referred to as a "ceramic insulated mold"), or a mold in which a metal layer and then a thermosetting resin layer are formed from the cavity side (hereinafter may be referred to as a "resin insulated mold").

An example of a ceramic insulating mold is one in which a ceramic covering plate (inserted) is provided on the cavity surface of a metal mold body. The ceramic material is not particularly limited as long as it has excellent insulation, heat resistance, and stability, but ceramics with a thermal conductivity of 5 W/m·K or less are preferred, and examples of such materials include zirconium oxide ( _ZrO2 : zirconia). Here, the zirconia may be partially stabilized zirconia containing one or more of calcia (calcium oxide, _{CaO), yttria (yttrium oxide, Y2O3 )} , magnesia (magnesium oxide, MgO), silica (silicon oxide, _SiO2 ) and _ceria (cerium oxide, _CeO2 ) as a partial stabilizer, or may be conductive zirconia containing one or more of _Fe2O3 , NiO, _Co3O4 , _{Cr2O3 , TiO2} , _TiN , TiC, WC, TaC, etc. as a conductivity imparting agent.

The thickness of the ceramic layer is not particularly limited as long as it is thick enough to obtain the required thermal insulation, but is usually 0.1 to 10 mm, preferably 0.5 to 10 mm, more preferably 1 to 7 mm, and even more preferably 2 to 5 mm. If the ceramic layer is too thin, sufficient thermal insulation cannot be obtained, and the improvement in transparency is smaller than when a normal mold is used. If the ceramic layer is too thick, the thermal insulation effect becomes too great, and it takes time to cool the molten resin in the cavity, lengthening the molding cycle.

An example of a resin insulated mold is one in which a metal layer is provided on the cavity surface of a metal mold body via a thermosetting resin layer. Here, the thermosetting resin layer functions as an insulating layer and also as an adhesive layer between the mold body and the metal layer. Examples of thermosetting resins include epoxy acrylate resin, phenolic resin, epoxy resin, melamine resin, urea resin, unsaturated polyester resin, alkyd resin, polyurethane, and thermosetting polyimide. The thermal conductivity of these thermosetting resins is usually around 0.3 to 3 W/m·K.

This thermosetting resin may contain inorganic particles such as glass beads as a reinforcing agent. The inorganic particles are preferably spherical in shape and have an average particle size of about 1 to 100 μm. The content of inorganic particles in the thermosetting resin layer is preferably 60 to 90% by mass.

The thickness of the thermosetting resin layer varies depending on the heat insulating properties (thermal conductivity) of the thermosetting resin, but is preferably about 0.2 to 1.5 mm.

Specific examples of materials that can be used for the metal layer that forms the cavity surface include steel materials such as alloy tool steel, die steel, tool steel, and martensitic stainless steel, as well as thin films of chromium, zinc, nickel, diamond, and the like. Steel materials that have been subjected to processing such as hardening are preferable. The thickness of the metal layer is usually about 0.2 to 1.5 mm.

A metal layer can be formed on the surface of the thermosetting resin layer by plating or the like, but a thin plate of hardened steel or the like can also be bonded with a thermosetting resin.

If necessary, a reinforcing layer made of ceramics may be formed between the metal layer and the thermosetting resin layer.

When injection molding the thermoplastic resin composition of the present invention using an insulated mold such as a ceramic insulated mold or a resin insulated mold, the molding conditions can be the same as when using a normal mold, and injection molding conditions of a cylinder temperature of 280 to 320°C and a mold temperature of 60 to 100°C can be used.

[Heat and cool molding method]
The rapid heating and cooling mold used in the heat and cool molding method is one in which the heat transfer medium and refrigerant circulating through the medium passage of the mold can be instantly switched by a mold temperature control device.The heat and cool molding method uses such a rapid heating and cooling mold to supply a heat transfer medium to the medium passage of the mold at least from after the mold is opened until before the molten resin is completely filled, and supply a refrigerant to the medium passage of the mold at least from after the molten resin is completely filled until before the mold is opened, thereby performing the injection process at or above a predetermined mold cavity temperature, and simultaneously with the end of the injection process, switching the heat transfer medium to the refrigerant and performing the mold opening process at or below the predetermined mold cavity temperature.

In the heat and cool molding method of the present invention, an injection process is performed in which molten resin is injected when the mold cavity temperature reaches 130°C or higher, preferably 130 to 160°C, using a heat transfer medium having a temperature of about 200 to 320°C. Simultaneously with the completion of this injection process, the heat transfer medium is switched to a refrigerant having a temperature of about 40 to 60°C, and the mold is opened when the mold cavity temperature reaches 80°C or lower, preferably 50 to 80°C.
In particular, it is preferable to switch the heat medium to a refrigerant medium simultaneously with the end of the injection process, so that the holding time from the end of the injection process to the opening of the mold is 50 seconds or less, and particularly 15 to 40 seconds.
In addition, the cylinder temperature of the injection molding machine when injection molding the thermoplastic resin composition may be set at a normal temperature condition of 280 to 320°C.

[Application]
The thermoplastic resin composition of the present invention and its injection molded article can be excellent in transparency after obtaining various properties such as excellent dimensional stability, rigidity (bending strength), and heat resistance due to the incorporation of the glass filler (C). Therefore, it can be suitably used for various products such as cameras, office equipment, AV equipment, communication equipment, information terminal equipment such as mobile phones and tablets, precision equipment, electric and electronic parts, vehicle parts such as automobiles, general machine parts, building materials, leisure goods, miscellaneous goods, various containers, protective housings, lighting equipment, etc. Among them, it is suitable for cameras, office equipment, AV equipment, information terminal equipment such as mobile phones and tablets, electric and electronic parts, automobile parts, railway vehicle parts, aircraft parts, building materials, and protective housings, where transparency is important. Specific examples of applications of office equipment, AV equipment, and information terminal equipment include covers for touch panel displays.

[Seat]
The sheet of the present invention is made of the thermoplastic resin composition of the present invention.

Here, "sheet" generally refers to something that is thin and flat, with a thickness smaller than its length and width, while "film" refers to something that is extremely thin compared to its length and width, even thinner than a sheet, and is usually provided in the form of a roll. However, there is no clear distinction between "sheet" and "film," and "sheet" in the present invention includes "film."

The method for producing the sheet of the present invention is not particularly limited, but a melt extrusion method (for example, a T-die molding method) is preferably used. There are also no particular limitations on the sheet molding conditions, but an extrusion molding machine equipped with two mirror-finished cooling rolls near a T-die is used, and the sheet-like molten resin discharged from the T-die is sandwiched between two cooling rolls whose temperatures are adjusted to 100 to 140°C, thereby improving the surface smoothness of the sheet and producing a sheet with higher transparency. The higher the sandwiching pressure between the cooling rolls, the better the surface smoothness of the sheet and the more transparent the sheet can be obtained.

The thickness of the sheet of the present invention is preferably 0.2 to 2 mm, more preferably 0.25 to 1.9 mm, and even more preferably 0.3 to 1.8 mm. By making the thickness equal to or greater than the above lower limit, it is possible to ensure rigidity, and by making the thickness equal to or less than the above upper limit, it is possible to obtain a sheet with excellent transparency.

The sheet of the present invention can be used alone, but can also be laminated to a non-reinforced thermoplastic resin surface layer.

Applications of the sheet of the present invention are not particularly limited, but include sheet members used in cameras, office automation equipment, audiovisual equipment, communication equipment, information terminal devices such as mobile phones and tablets, precision equipment, electrical and electronic parts, vehicle parts such as automobiles, general machine parts, building materials, leisure goods, miscellaneous goods, various containers, protective housings, lighting equipment, etc.

The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to the following examples, and can be modified as desired without departing from the spirit of the present invention.

The components used in the following examples and comparative examples are as shown in Table 1.

[Examples and Comparative Examples of Injection Molded Products]
[Examples (Reference Examples) I-1 to 31, Examples I-32 to 36, Comparative Examples I-1 to 14]
<Production of Thermoplastic Resin Composition Pellets>
Each component other than the glass filler (C) shown in Table 1 above was blended in the ratio (parts by mass) shown in Table 2-7 below, and mixed in a tumbler for 20 minutes. The mixture was then fed from an upstream feeder to a twin-screw extruder (TEM26SX) manufactured by Toshiba Machine Co., Ltd. equipped with one vent, and the glass filler (C) was further fed from the middle of the barrel (a downstream position 3/5 of the barrel length L from the upstream (hopper portion) of the extruder). The mixture was kneaded under conditions of a rotation speed of 250 rpm, a discharge rate of 25 kg/hour, and a barrel temperature of 280° C. The molten resin extruded in the form of strands was quenched in a water tank and pelletized using a pelletizer to obtain pellets of a thermoplastic resin composition.

<Measurement of deflection temperature under load (DTUL)>
The resin composition pellets obtained above were dried at 100°C for 5 hours, and then injection molded using an injection molding machine (NEX80III type) manufactured by Nissei Plastic Industries Co., Ltd. under the conditions of cylinder setting temperature 300°C, mold temperature 80°C, injection time 2 seconds, and molding cycle 40 seconds to obtain ISO multipurpose test pieces (4 mm thick). The deflection temperature under load (unit: °C) was measured under a load of 1.80 MPa in accordance with ISO75-1 and ISO75-2.

<Making a flat plate using a general mold>
The example pellets obtained by the above-mentioned manufacturing method were dried at 100°C for 5 hours, and then injection molded using an injection molding machine (SE50DUZ type) manufactured by Sumitomo Heavy Industries, Ltd. under the condition of a cylinder temperature of 290°C to mold a flat plate having a length of 50 mm, a width of 40 mm, and a thickness of 2 mm. Examples I-1 to 36 and Comparative Examples I-1 to 3, 5, 6, 8, and 10 to 14 were molded at a mold temperature of 100°C. Comparative Examples I-4, 7, and 9 were molded at a mold temperature of 80°C because poor release occurred at a mold temperature of 100°C. As the mold, a mold in which the material of the inserts constituting the fixed cavity and the movable cavity was SUS420J2 was used.

<Making a flat plate using a heat-insulating mold>
The pellets obtained by the above-mentioned manufacturing method were dried at 100°C for 5 hours, and then injection molded using a FANUC injection molding machine (S-2000i150B type) at a cylinder temperature of 290°C to mold a flat plate with a length of 100 mm, a width of 100 mm, and a thickness of 2 mm. Examples I-1 to 36 and Comparative Examples I-1 to 3, 5, 6, 8, and 10 to 14 were molded at a mold temperature of 100°C. Comparative Examples I-4, 7, and 9 were molded at a mold temperature of 80°C because poor release occurred at a mold temperature of 100°C. As the mold, a heat-insulating mold was used with 100 mm x 100 mm x 3 mm zirconium oxide (ZrO ₂ ) plates on the fixed cavity and movable cavity surfaces.

<Making a flat plate using heat and cool molding>
The pellets obtained by the above-mentioned manufacturing method were dried at 100°C for 5 hours, and then injection molded using a Fanuc injection molding machine (S-2000i150B type) under the condition of a cylinder temperature of 290°C to mold a flat plate with a length of 50 mm, a width of 40 mm, and a thickness of 2 mm. At this time, 300°C oil was circulated through the mold flow path by a rapid heating and cooling mold using a Matsui Manufacturing Co., Ltd. MCJ-OM-250AA as a mold temperature control device, and when the mold cavity surface temperature reached 160°C, the circulation of 300°C oil was stopped, and then the injection process was performed. At the same time as the injection process was completed, 40°C oil was circulated through the mold flow path, and when the mold cavity surface temperature reached 80°C, the mold opening process was performed to obtain a molded product with the above-mentioned shape. As the mold, a mold in which the material of the nest constituting the fixed side cavity and the movable side cavity was SUS420J2 was used. The retention time from the end of the injection process to the mold opening was 25 seconds.

<Measurement of haze of injection molded products>
The haze of the plate obtained by the above method was measured using a haze meter NDH4000 manufactured by Nippon Denshoku Industries Co., Ltd. The smaller the haze, the more excellent the transparency.
The measurement results of the haze are shown in Table 2-6. In the table, "Ex" indicates an embodiment, "Reference" indicates a reference example, and "Comparative" indicates a comparative example.
In addition, Comparative Examples I-1, 5, 6, 8, 10, 11, and 13 were cloudy and could not be measured. In the case of an injection molded product molded using a heat-insulating mold and an injection molded product obtained by heat & cool molding, the haze is preferably 15% or less. In the case of an injection molded product molded using a general mold, the haze is preferably 55% or less.

<Measurement of surface roughness Ra of injection molded product>
The surface roughness Ra of the flat plate obtained by the above method was measured using a SURFCOM 3000A manufactured by Tokyo Seimitsu Co., Ltd., with the cutoff wavelength λc set to 0.8 mm, the cutoff type set to Gaussian, λs set to 2.67 μm, and the evaluation length set to 8 mm. The smaller the Ra, the smoother the molded product surface is, and in order to obtain a molded product with excellent transparency, it is preferable to set the Ra to 0.1 μm or less.

[Sheet Examples and Comparative Examples]
[Examples (Reference Examples) II-1 to 12, Comparative Examples II-1 to 4]
<Production of Thermoplastic Resin Composition Pellets>
Pellets of a thermoplastic resin composition were obtained in the same manner as in Example (Reference Example) I-1, except that the thermoplastic resin composition was blended in the proportions (parts by mass) shown in Tables 8-9.

<Preparation of Sheet>
The pellets obtained by the above-mentioned manufacturing method were dried at 100°C for 5 hours, and then a sheet having a thickness of 1.0 mm was molded using a single-screw extruder. A full-flight screw with a diameter of 30 mm and an L/D of 38 was used as the screw of the single-screw extruder. A T-die with a lip width of 300 mm was used. The resin discharged from the T-die was sandwiched between two mirror-finished cooling rolls, and was further cooled by being aligned along one of the cooling rolls. The temperature of the cooling rolls was 120°C in both cases.

<Measurement of Sheet Haze>
The haze of the sheet obtained by the above method was measured using SH7000 manufactured by Nippon Denshoku Industries Co., Ltd. The smaller the haze, the more excellent the transparency.
The measurement results of the haze are shown in Tables 8 and 9. In the tables, " Reference " indicates a reference example, and "Comparative" indicates a comparative example.
In addition, Comparative Examples II-1 and 4 were cloudy and could not be measured.
In Tables 8 and 9, the numbers of the reference examples and comparative examples of injection molded articles having the same thermoplastic resin composition blend are also shown as remarks.

The following can be seen from Tables 2 to 7.
In both Comparative Example I-2, in which the blend amount of polyester resin (B1-1) is too small beyond the range of the present invention, and Comparative Example I-3, in which the blend amount of polyester resin (B1-2) is too large beyond the range of the present invention, the refractive index of the resin matrix cannot be made close to the refractive index of the glass filler (C), and transparency is poor.

In Examples (Reference Examples) I-10 to I-12 and Example (Reference Example) I-16, flat cross section glass fibers with different refractive indices due to different compositions are used even if the flatness is the same. In Example (Reference Example ) I-16, a large amount of polyester resin (B1-2) is blended compared to Examples (Reference Examples) I-10 to I-12, and the haze is almost the same. This shows that it is important to adjust the mixing ratio of polycarbonate resin (A) and polycondensate (B) within the range of the present invention according to the refractive index of the glass filler (C) used.

Since the polyester resin (B1-X1) has a higher refractive index than the polyester resin (B1-1), even if the ratio of the polyester resin (B1-X1) in the total of 100 parts by mass of the polycarbonate resins (A) and (B1-X1) is 25 to 60 parts by mass, the refractive index of the resin matrix cannot be brought close to that of the glass filler (C), and the resin becomes cloudy as shown in Comparative Example I-5. As shown in Comparative Example I-4, by making the ratio of the polyester resin (B1-X1) in the total of 100 parts by mass of the polycarbonate resins (A) and (B1-X1) more than 60 parts by mass, the refractive index of the resin matrix can be brought close to that of the glass filler (C), and good transparency can be obtained, but the DTUL is significantly reduced.

Tables 8 and 9 also show that, in sheets produced by melt extrusion, as in injection molded products, by using the thermoplastic resin composition formulation of the present invention, transparency can be relatively improved compared to types of polycarbonate resin (A) and blends of polycarbonate resin (A), polycondensate (B) and glass filler (C) outside the scope of the present invention.

The thermoplastic resin composition of the present invention has excellent transparency, high rigidity and a low linear expansion coefficient, and can therefore be suitably used in a variety of products, including cameras, office equipment, communication equipment, precision instruments, electrical and electronic parts, automobile parts, information terminal equipment, machine parts, home appliances, building materials, various containers, leisure goods and sundries, lighting equipment, etc.

Claims (13)

A thermoplastic resin composition comprising 100 parts by mass of a total of 100 parts by mass of (A) and (B) including 40 to 75 parts by mass of a polycarbonate resin (A) and 25 to 60 parts by mass of a polycondensate (B), and comprising 10 to 50 parts by mass of a glass filler (C) , wherein the polycondensate (B) is selected from at least one resin selected from a polycarbonate resin (B2) other than the polycarbonate resin (A) and a polyester carbonate resin (B3), and the diol residue thereof contains a residue of a diol represented by the following general formula (1):
[In formula (1), R ¹ and R ² each independently represent an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms.] The thermoplastic resin composition according to claim 1, wherein the residues of the diol of general formula (1) account for 1 to 100 mol % of all diol residues in the polycarbonate resin (B2). The thermoplastic resin composition according to claim 1 or 2 , wherein the polycarbonate resin (B2) further contains a 1,4-cyclohexanedimethanol residue and/or a residue of a diol represented by general formula (2).
[In formula (2), R ³ to R ⁵ each independently represent an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms.] The thermoplastic resin composition according to claim 1, wherein the residues of the diol of general formula (1) account for 1 to 100 mol% of all diol residues in the polyester carbonate resin (B3). The thermoplastic resin composition according to claim 1 or 4, wherein the polyester carbonate resin (B3) further contains a 1,4-cyclohexanedicarboxylic acid residue. The thermoplastic resin composition according to any one of claims 1 to 5 , wherein the glass filler (C) is a glass fiber having a cross-sectional shape with an aspect ratio of 1.5 to 8 and/or a glass flake having an average thickness of 0.1 to 10 µm. A molded article obtained by injection molding the thermoplastic resin composition according to any one of claims 1 to 6 . 8. The molded article according to claim 7 , wherein the area of the surface of the molded article having a surface roughness Ra of 0.1 μm or less occupies 30% or more of the total surface of the molded article. A sheet comprising the thermoplastic resin composition according to any one of claims 1 to 6 . 10. The sheet according to claim 9 , having a thickness of 0.2 to 2 mm. A method for producing a molded product, comprising injection molding the thermoplastic resin composition according to any one of claims 1 to 6 into a mold having a cavity surface provided with a ceramic layer. A method for producing a molded product, comprising injection molding the thermoplastic resin composition according to any one of claims 1 to 6 into a mold having a cavity having a metal layer and then a thermosetting resin layer formed thereon from the cavity surface side. A method for producing a molded article by injection molding the thermoplastic resin composition according to any one of claims 1 to 6 , comprising using a rapid heating and cooling mold, carrying out an injection step when the mold cavity surface temperature is 130°C or higher, and carrying out a mold opening step when the mold cavity surface temperature is 80°C or lower.