JP2010270296A - Thermoplastic resin composition and molded article thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition improving dispersibility of a fluoro-polymer relative to a thermoplastic resin and also improving light transmittance, especially near-infrared light transmittance and also flame-retardancy. <P>SOLUTION: The thermoplastic resin composition includes the thermoplastic resin, the fluoro-polymer and a fluoro-polymer dispersing agent, and is characterized in that the fluoro-polymer dispersing agent includes a polycarbosilane compound. Since the polycarbosilane compound having a silicon-carbon bond in a main chain contains an organic component (organic residual group) in the main chain, the organic property is strong. Therefore, compatibility and dispersibility of the fluoro-polymer to the thermoplastic resin can be effectively improved. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a thermoplastic resin composition and a molded body thereof. Specifically, a thermoplastic resin blended with a fluoropolymer for the purpose of improving the melt characteristics of the thermoplastic resin and the surface properties such as slidability, scratch resistance, water repellency, oil repellency, stain resistance, and fingerprint resistance. In the composition, a thermoplastic resin composition having improved compatibility and dispersibility of the fluoropolymer with respect to the thermoplastic resin, improved light transmittance, particularly near infrared light transmittance, and further flame retardancy, and The present invention relates to a thermoplastic resin molded article formed by molding a thermoplastic resin composition.

  Conventionally, fluoropolymers have been fluoropolymerized for the purpose of improving the melting properties of thermoplastic resins and for improving surface properties such as slidability, scratch resistance, water repellency, oil repellency, stain resistance, and fingerprint resistance. Techniques for blending polymers have been performed.

  Among them, the fluoroolefin polymer having the ability to form fibrils can effectively modify the melting characteristics of the thermoplastic resin, and particularly when blended with a flame retardant thermoplastic resin composition. It exhibits excellent blending effects such as improving the drip prevention property and preventing the spread of fire when the thermoplastic resin molded body burns.

  In addition, when imparting flame retardancy to a thermoplastic resin, in general, even when only a fluoropolymer is added, the anti-drip property is not improved, although the anti-drip property is improved as described above. (For example, refer to Patent Documents 1 and 2).

  On the other hand, in recent years, in the fields of automobiles, electrical machinery / electronics, and other precision equipment, a method of so-called welding of a thermoplastic resin molded body with a laser in the near infrared region (so-called laser welding) has been actively tried. The laser welding method has great industrial merit because it is non-contact, does not generate wear powder and burrs, and has little damage to the product.

  As a laser used in such laser welding, generally, light in the near infrared region having a wavelength of 800 to 1200 nm is preferably used for safety and cost reasons. Therefore, in the field of laser welding, a thermoplastic resin composition having a high light transmittance in the near infrared region is used (see, for example, Patent Documents 3 to 4).

  Furthermore, it is representative of various automotive sensor devices such as face orientation detection devices and rain sensors, various security devices such as face authentication devices, fingerprint authentication devices and vein authentication devices, various information and communication devices such as remote controllers and infrared communication devices, etc. Many thermoplastic resin compositions are used in sensor device members. The wavelength of infrared light used in such a field is appropriately selected depending on each device and apparatus, but light in the near infrared region of 800 to 1500 nm is usually used. Therefore, also in such a field, a thermoplastic resin composition having a high light transmittance in the near infrared region is required.

Japanese Patent Laid-Open No. 11-181265 JP 2000-239509 A JP 2006-199861 A Japanese Patent Laid-Open No. 2007-131692

However, since the fluoropolymer has extremely low compatibility and dispersibility with the thermoplastic resin, there is a problem that even when it is blended in a small amount, the light transmittance is remarkably lowered or an appearance defect is caused.
In particular, due to recent demands for improving safety against fires, there is a tendency to use flame-retardant thermoplastic resin compositions in electrical and electronic equipment parts and sensor equipment parts manufactured by laser welding as described above. However, when a thermoplastic resin composition containing a fluoropolymer is used in such a field, the light transmittance, particularly the light transmittance in the near-infrared region, is significantly reduced, and its use is limited. It had a fatal drawback.

  For example, if the light transmittance in the near-infrared region of the thermoplastic resin composition for laser welding decreases, the laser light transmittance is low, so it must be dealt with by thinning, and the product thickness design margin is narrow. It tends to cause a decrease in product strength. Also, increasing the laser output may cause problems such as melting, smoke generation, and bubbles due to abnormal heat generation at the bonding interface, which may make welding impossible; poor appearance and reduced strength Cause problems.

  Similarly, in various sensor devices, when the light transmittance in the near infrared region of the thermoplastic resin composition constituting the sensor device is lowered, the sensitivity of the sensor is significantly lowered. If thinning is attempted to increase the infrared light transmittance, the product strength will decrease and the transmittance at wavelengths other than the wavelength used will also increase at the same time, so the sensor sensitivity will also decrease, possibly leading to malfunctions. There is.

  For these reasons, there has been a strong demand for a technique for improving the light transmittance in the near-infrared region by improving the compatibility and dispersibility of fluoropolymers with thermoplastic resins.

  Therefore, the present invention is blended with a fluoropolymer for the purpose of improving the melt characteristics of the thermoplastic resin and the surface characteristics such as slidability, scratch resistance, water repellency, oil repellency, stain resistance, and fingerprint resistance. In the thermoplastic resin composition, the dispersibility of the fluoropolymer in the thermoplastic resin is improved, and the light transmittance, particularly near infrared light transmittance, as well as the problem of flame retardancy, poor appearance and reduced strength are improved. It is an object of the present invention to provide a thermoplastic resin composition and a thermoplastic resin molded article obtained by molding this thermoplastic resin composition.

  As a result of intensive investigations in view of the above-mentioned problems, the present inventors effectively blended a polycarbosilane compound into a thermoplastic resin composition containing a fluoropolymer, so that the polycarbosilane compound effectively functions as a fluoropolymer dispersant, By improving the compatibility and dispersibility of the fluoropolymer with respect to the thermoplastic resin, it improves the light transmittance in the near infrared region of the thermoplastic resin composition, further improves the flame retardancy, The present inventors have found that the problem of strength reduction can be improved and completed the present invention.

  That is, the thermoplastic resin composition of the present invention is a thermoplastic resin composition containing a thermoplastic resin, a fluoropolymer, and a fluoropolymer dispersant, and the fluoropolymer dispersant is made of a polycarbosilane compound. (Claim 1).

  In the present invention, the polycarbosilane compound preferably has a main chain structure composed of at least one structural unit of the structural units represented by the following formulas (1) to (3) and a hydrocarbon residue. (Claim 2). The hydrocarbon residue is preferably a divalent hydrocarbon group (claim 3).

(In formulas (1) to (3), R ¹ , R ² , and R ³ each independently represent a monovalent hydrocarbon group, a hydrogen atom, or a silyl group, and a, b, and c are each independently , 0 or 1. The plurality of R ¹ , R ² and R ³ contained in the main chain structure may be the same or different.

  More specifically, the polycarbosilane compound used in the present invention has a number average molecular weight of 100 to 20000 having a repeating unit represented by the following formula (4), particularly the following formula (5), especially the following formula (6). The polycarbosilane compound is preferably (Claims 4 to 6).

(In the formula (4), R ¹ , R ² , a and b are as defined in the formula (1), A ¹ represents a divalent hydrocarbon group having 1 to 12 carbon atoms, p, q Each independently represents an integer of 1 to 8. R ¹ , R ² and A ¹ may be the same or different in all repeating units.

(In the formula ^{(5), R 1, R} 2 have the same meanings as in the formula (4), ^{A 2} is ^.R 1, ^{R 2} and ^{A 2} which represents an alkylene group having 1 to 12 carbon atoms, each and every In the repeating unit, they may be the same or different.)

  In this invention, it is preferable to contain 0.001-3 mass parts of fluoropolymers and 0.005-10 mass parts of fluoropolymer dispersing agents with respect to 100 mass parts of thermoplastic resins.

  The fluoropolymer is preferably a fluoroolefin polymer having a fibril-forming ability (claim 8).

  The thermoplastic resin composition of the present invention may further contain a flame retardant (Claim 9). In this case, the flame retardant contains 0.001 to 30 parts by mass with respect to 100 parts by mass of the thermoplastic resin. (Claim 10).

  The flame retardant is preferably a metal salt compound, more preferably an alkali metal salt of an organic sulfonic acid, an alkali metal salt of a fluorinated aliphatic sulfonic acid, an alkali metal salt of an aromatic sulfonic acid. Particularly preferred is at least one selected from the group consisting of alkali metal salts of perfluoroalkanesulfonic acid (claims 11 to 14).

  Moreover, as a thermoplastic resin, a polycarbonate resin is preferable (Claim 15).

  The thermoplastic resin molded article of the present invention is formed by molding such a thermoplastic resin composition of the present invention (claim 16).

  Polycarbosilane compounds function effectively as a dispersant for fluoropolymers blended in thermoplastic resins, and improve compatibility and dispersibility of fluoropolymers in thermoplastic resin compositions, resulting in poor appearance and reduced strength. And can improve light transmittance, particularly near infrared light transmittance, and also flame retardancy.

  Therefore, a thermoplastic resin molded article formed by molding such a thermoplastic resin composition of the present invention can be melted, slidable, scratch-resistant, water-repellent, oil-repellent, and oil-resistant by blending with a fluoropolymer. Improved surface properties such as dirtiness and fingerprint resistance, high light transmittance, especially high near infrared light transmittance, and excellent flame resistance. Automotive, electrical / electronic, and other precision equipment fields , Near infrared laser welding members, various automotive sensor devices such as face detection devices, rain sensors, various security devices such as face authentication devices, fingerprint authentication devices, vein authentication devices, remote controllers, infrared communication devices, etc. It is extremely useful industrially as a sensor device member represented by various information / communication devices.

  Hereinafter, the present invention will be described in detail with reference to embodiments and examples, but the present invention is not limited to the embodiments and examples described below, and may be arbitrarily selected without departing from the scope of the present invention. It can be implemented by changing.

[1. Overview]
The thermoplastic resin composition of the present invention contains at least a thermoplastic resin, a fluoropolymer, and a polycarbosilane compound as a fluoropolymer dispersant. Moreover, the thermoplastic resin composition of this invention may contain a flame retardant and other components as needed.

  Here, the polycarbosilane compound has two or more repeating units having a silicon-carbon bond (Si—C bond) in the main chain, and the polycarbosilane compound used in the present invention has the main chain as described above. By having a Si-C bond in the resin, it is excellent in the effect of improving the compatibility and dispersibility of the fluoropolymer with respect to the thermoplastic resin, and the light transmittance of the conventional fluoropolymer-containing thermoplastic resin composition, particularly the transmission of near infrared rays. It is possible to improve the problems of rate reduction, appearance defect, and strength reduction.

[2. Thermoplastic resin]
Although there is no restriction | limiting in particular as a thermoplastic resin used for the thermoplastic resin composition of this invention, For example, the following are mentioned.

Polycarbonate resins (PC resins) such as aromatic polycarbonate resins and aliphatic polycarbonate resins;
Thermoplastics such as polyethylene terephthalate resin (PET resin), polytrimethylene terephthalate (PTT resin), polybutylene terephthalate resin (PBT resin), polylactic acid (PLA), polybutylene succinate resin (PBS), polycaprolactone (PCL) Polyester resin;
Polystyrene resin (PS resin), high impact polystyrene resin (HIPS), acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-styrene-acrylic rubber copolymer (ASA) Resin), styrene resin such as acrylonitrile-ethylene propylene rubber-styrene copolymer (AES resin);
Polyolefin resins such as polyethylene resin (PE resin), polypropylene resin (PP resin), cyclic cycloolefin resin (COP resin), cyclic cycloolefin copolymer (COC resin);

  Polyamide resin (PA resin); Polyimide resin (PI resin); Polyetherimide resin (PEI resin); Polyurethane resin (PU resin); Polyphenylene ether resin (PPE resin); Polyphenylene sulfide resin (PPS resin); Polysulfone resin (PSU) Resin); polymethyl methacrylate resin (PMMA resin); etc.

  In the thermoplastic resin composition of this invention, 1 type of these thermoplastic resins may contain, and 2 or more types may contain it by arbitrary combinations and a ratio.

  In particular, in the present invention, among these thermoplastic resins, it is preferable to use a polycarbonate resin because it is excellent in optical properties such as transparency, heat resistance, mechanical properties, electrical properties and the like. It is preferable to use a resin, and 50% by weight or more, particularly 70% by weight or more of the thermoplastic resin contained in the thermoplastic resin composition of the present invention is preferably a polycarbonate resin, particularly an aromatic polycarbonate resin. One type of polycarbonate resin may be used, or two or more types may be used in any combination and in any ratio.

  The polycarbonate resin is a polymer having a basic structure having a carbonic acid bond represented by the following formula (7).

In formula (7), X ¹ is generally a hydrocarbon group, but X ¹ into which a hetero atom or a hetero bond is introduced may be used for imparting various properties.

  The polycarbonate resin can be classified into an aromatic polycarbonate resin in which carbon directly bonded to a carbonic acid bond is aromatic carbon and an aliphatic polycarbonate resin in which aliphatic carbon is aliphatic carbon, either of which can be used. Of these, aromatic polycarbonate resins are preferred from the viewpoints of heat resistance, mechanical properties, electrical characteristics, and the like.

  Although there is no restriction | limiting in the specific kind of polycarbonate resin, For example, the polycarbonate polymer formed by making a dihydroxy compound and a carbonate precursor react is mentioned. At this time, in addition to the dihydroxy compound and the carbonate precursor, a polyhydroxy compound or the like may be reacted. Alternatively, a method of reacting with cyclic ether using carbon dioxide as a carbonate precursor may be used. Here, the polycarbonate polymer may be linear or branched. Further, the polycarbonate polymer may be a homopolymer composed of one type of repeating unit or a copolymer having two or more types of repeating units. In the case of a copolymer, various copolymerization forms such as a random copolymer and a block copolymer can be selected. In general, such a polycarbonate polymer is a thermoplastic resin.

[2-1. Dihydroxy compound]
Among the dihydroxy compounds used as the raw material for the polycarbonate resin, examples of the aromatic dihydroxy compound used as the raw material for the aromatic polycarbonate resin include the following.

1,2-dihydroxybenzene,
1,3-dihydroxybenzene (ie, resorcinol),
1,4-dihydroxybenzene,
Dihydroxybenzenes such as;

2,5-dihydroxybiphenyl,
2,2′-dihydroxybiphenyl,
4,4′-dihydroxybiphenyl,
Dihydroxybiphenyls such as

2,2′-dihydroxy-1,1′-binaphthyl,
1,2-dihydroxynaphthalene,
1,3-dihydroxynaphthalene,
2,3-dihydroxynaphthalene,
1,6-dihydroxynaphthalene,
2,6-dihydroxynaphthalene,
1,7-dihydroxynaphthalene,
2,7-dihydroxynaphthalene,
Dihydroxynaphthalenes such as

2,2′-dihydroxydiphenyl ether,
3,3′-dihydroxydiphenyl ether,
4,4′-dihydroxydiphenyl ether,
4,4′-dihydroxy-3,3′-dimethyldiphenyl ether,
1,4-bis (3-hydroxyphenoxy) benzene,
1,3-bis (4-hydroxyphenoxy) benzene,
Dihydroxy diaryl ethers such as

2,2-bis (4-hydroxyphenyl) propane (ie, bisphenol A),
1,1-bis (4-hydroxyphenyl) propane,
2,2-bis (3-methyl-4-hydroxyphenyl) propane,
2,2-bis (3-methoxy-4-hydroxyphenyl) propane,
2- (4-hydroxyphenyl) -2- (3-methoxy-4-hydroxyphenyl) propane,
1,1-bis (3-tert-butyl-4-hydroxyphenyl) propane,
2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane,
2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane,
2- (4-hydroxyphenyl) -2- (3-cyclohexyl-4-hydroxyphenyl) propane,
α, α′-bis (4-hydroxyphenyl) -1,4-diisopropylbenzene,
1,3-bis [2- (4-hydroxyphenyl) -2-propyl] benzene,
Bis (4-hydroxyphenyl) methane,
Bis (4-hydroxyphenyl) cyclohexylmethane,
Bis (4-hydroxyphenyl) phenylmethane,
Bis (4-hydroxyphenyl) (4-propenylphenyl) methane,
Bis (4-hydroxyphenyl) diphenylmethane,
Bis (4-hydroxyphenyl) naphthylmethane,
1,1-bis (4-hydroxyphenyl) ethane,
1,2-bis (4-hydroxyphenyl) ethane,
1,1-bis (4-hydroxyphenyl) -1-phenylethane,
1,1-bis (4-hydroxyphenyl) -1-naphthylethane,
1,1-bis (4-hydroxyphenyl) butane,
2,2-bis (4-hydroxyphenyl) butane,
2,2-bis (4-hydroxyphenyl) pentane,
1,1-bis (4-hydroxyphenyl) hexane,
2,2-bis (4-hydroxyphenyl) hexane,
1,1-bis (4-hydroxyphenyl) octane,
2,2-bis (4-hydroxyphenyl) octane,
1-bis (4-hydroxyphenyl) hexane,
2-bis (4-hydroxyphenyl) hexane,
4,4-bis (4-hydroxyphenyl) heptane,
2,2-bis (4-hydroxyphenyl) nonane,
1,10-bis (4-hydroxyphenyl) decane,
1,1-bis (4-hydroxyphenyl) dodecane,
Bis (hydroxyaryl) alkanes such as;

1,1-bis (4-hydroxyphenyl) cyclopentane,
1,1-bis (4-hydroxyphenyl) cyclohexane,
1,4-bis (4-hydroxyphenyl) cyclohexane,
1,1-bis (4-hydroxyphenyl) -3,3-dimethylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3,4-dimethylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3,5-dimethylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane,
1,1-bis (4-hydroxy-3,5-dimethylphenyl) -3,3,5-trimethylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3-propyl-5-methylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3-tert-butyl-cyclohexane,
1,1-bis (4-hydroxyphenyl) -4-tert-butyl-cyclohexane,
1,1-bis (4-hydroxyphenyl) -3-phenylcyclohexane,
1,1-bis (4-hydroxyphenyl) -4-phenylcyclohexane,
Bis (hydroxyaryl) cycloalkanes such as;

9,9-bis (4-hydroxyphenyl) fluorene,
9,9-bis (4-hydroxy-3-methylphenyl) fluorene,
Bisphenols containing cardo structure such as

4,4′-dihydroxydiphenyl sulfide,
4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfide,
Dihydroxydiaryl sulfides such as;

4,4′-dihydroxydiphenyl sulfoxide,
4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfoxide,
Dihydroxydiaryl sulfoxides such as;

4,4′-dihydroxydiphenyl sulfone,
4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfone,
Dihydroxydiaryl sulfones such as:

  Among these, bis (hydroxyaryl) alkanes are preferable, and bis (4-hydroxyphenyl) alkanes are preferable, and 2,2-bis (4-hydroxyphenyl) propane (ie, from the viewpoint of impact resistance and heat resistance). Bisphenol A) is preferred.

  In addition, 1 type may be used for an aromatic dihydroxy compound and it may use 2 or more types together by arbitrary combinations and a ratio.

  Moreover, when the example of the aliphatic dihydroxy compound used as the raw material of aliphatic polycarbonate resin is given, the following will be mentioned.

Ethane-1,2-diol,
Propane-1,2-diol,
Propane-1,3-diol,
2,2-dimethylpropane-1,3-diol,
2-methyl-2-propylpropane-1,3-diol,
Butane-1,4-diol,
Pentane-1,5-diol,
Hexane-1,6-diol,
Decane-1,10-diol,
Alkanediols such as

Cyclopentane-1,2-diol,
Cyclohexane-1,2-diol,
Cyclohexane-1,4-diol,
1,4-cyclohexanedimethanol,
4- (2-hydroxyethyl) cyclohexanol,
2,2,4,4-tetramethyl-cyclobutane-1,3-diol,
Cycloalkanediols such as

2,2′-oxydiethanol (ie, ethylene glycol),
Diethylene glycol,
Triethylene glycol,
Propylene glycol,
Spiroglycol,
Glycols such as

1,2-benzenedimethanol,
1,3-benzenedimethanol,
1,4-benzenedimethanol,
1,4-benzenediethanol,
1,3-bis (2-hydroxyethoxy) benzene,
1,4-bis (2-hydroxyethoxy) benzene,
2,3-bis (hydroxymethyl) naphthalene,
1,6-bis (hydroxyethoxy) naphthalene,
4,4′-biphenyldimethanol,
4,4′-biphenyldiethanol,
1,4-bis (2-hydroxyethoxy) biphenyl,
Bisphenol A bis (2-hydroxyethyl) ether,
Bisphenol S bis (2-hydroxyethyl) ether,
Aralkyldiols such as

1,2-epoxyethane (ie ethylene oxide),
1,2-epoxypropane (ie, propylene oxide),
1,2-epoxycyclopentane,
1,2-epoxycyclohexane,
1,4-epoxycyclohexane,
1-methyl-1,2-epoxycyclohexane,
2,3-epoxynorbornane,
1,3-epoxypropane,
Cyclic ethers such as

  In addition, 1 type may be used for an aliphatic dihydroxy compound, and it may use 2 or more types together by arbitrary combinations and a ratio.

[2-2. Carbonate precursor]
Among the monomers used as the raw material for the polycarbonate resin, carbonyl halides, carbonate esters 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 carbonate ester 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

[2-3. Production method of polycarbonate resin]
The method for producing the polycarbonate resin is not particularly limited, and any method can be adopted. 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. Hereinafter, a particularly preferable one of these methods will be specifically described.

<Interfacial polymerization method>
First, the case where a polycarbonate resin is produced by an interfacial polymerization method will be described. In the interfacial polymerization method, a dihydroxy compound and a carbonate precursor (preferably phosgene) are reacted in the presence of an organic solvent inert to the reaction and an aqueous alkaline solution, usually at a pH of 9 or higher. Polycarbonate resin is obtained by interfacial polymerization in the presence. In the reaction system, a molecular weight adjusting agent (terminal terminator) may be present if necessary, and an antioxidant may be present for the purpose of preventing oxidation of the dihydroxy compound.

  The dihydroxy compound and carbonate precursor used are as described above. Of the carbonate precursors, phosgene is preferably used, and a method using phosgene is particularly called a phosgene method.

  Examples of the organic solvent inert to the reaction include chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, monochlorobenzene and dichlorobenzene; aromatic hydrocarbons such as benzene, toluene and xylene; It is done. In addition, 1 type may be used for an organic solvent and it may use 2 or more types together by arbitrary combinations and a ratio.

  Examples of the alkali compound contained in the alkaline aqueous solution include alkali metal compounds and alkaline earth metal compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and sodium hydrogen carbonate, among which sodium hydroxide and water Potassium oxide is preferred. In addition, 1 type may be used for an alkali compound and it may use 2 or more types together by arbitrary combinations and a ratio.

  Although there is no restriction | limiting in the density | concentration of the alkali compound in alkaline aqueous solution, Usually, in order to control pH of a reaction system to 10-12, it is used at 5-10 mass%. For example, when phosgene is blown, the molar ratio of the dihydroxy compound and the alkali compound is usually 1: 1.9 or more in order to control the pH of the aqueous phase to be 10 to 12, preferably 10 to 11. Among these, it is preferable that the ratio is 1: 2.0 or more, usually 1: 3.2 or less, and more preferably 1: 2.5 or less.

  Examples of the polymerization catalyst include aliphatic tertiary amines such as trimethylamine, triethylamine, tributylamine, tripropylamine, and trihexylamine; alicyclic rings such as N, N′-dimethylcyclohexylamine and N, N′-diethylcyclohexylamine. Tertiary amines; aromatic tertiary amines such as N, N′-dimethylaniline and N, N′-diethylaniline; quaternary ammonium salts such as trimethylbenzylammonium chloride, tetramethylammonium chloride and triethylbenzylammonium chloride; Pyridine; guanine; guanidine salt; and the like. In addition, 1 type may be used for a polymerization catalyst and it may use 2 or more types together by arbitrary combinations and a ratio.

  Examples of the molecular weight modifier include aromatic phenols having a monovalent phenolic hydroxyl group; aliphatic alcohols such as methanol and butanol; mercaptans; phthalimides and the like. Of these, aromatic phenols are preferred. Specific examples of such aromatic phenols include alkyl groups such as m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, p-tert-butylphenol, and p-long chain alkyl-substituted phenol. Examples thereof include substituted phenols; vinyl group-containing phenols such as isopropanyl phenol; epoxy group-containing phenols; carboxyl group-containing phenols such as o-oxinebenzoic acid and 2-methyl-6-hydroxyphenylacetic acid; In addition, a molecular weight regulator may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

  The usage-amount of a molecular weight modifier is 0.5 mol or more normally with respect to 100 mol of dihydroxy compounds, Preferably it is 1 mol or more, and is 50 mol or less normally, Preferably it is 30 mol or less. By making the usage-amount of a molecular weight modifier into this range, the thermal stability and hydrolysis resistance of the polycarbonate resin composition obtained can be improved.

  In the reaction, the order of mixing the reaction substrate, reaction medium, catalyst, additive and the like is arbitrary as long as a desired polycarbonate resin is obtained, and an appropriate order may be arbitrarily set. For example, when phosgene is used as the carbonate precursor, the molecular weight modifier can be mixed at any time as long as it is from the time of the reaction (phosgenation) of the dihydroxy compound and phosgene to the start of the polymerization reaction.

  In addition, reaction temperature is 0-40 degreeC normally, and reaction time is normally several minutes (for example, 10 minutes)-several hours (for example, 6 hours).

<Melted ester exchange method>
Next, a case where a polycarbonate resin is produced by a melt transesterification method will be described. In the melt transesterification method, for example, a transesterification reaction between a carbonic acid diester and a dihydroxy compound is performed.

  The dihydroxy compound used is as described above.

  On the other hand, examples of the carbonic acid diester include dialkyl carbonate compounds such as dimethyl carbonate, diethyl carbonate, and di-tert-butyl carbonate; diphenyl carbonate; substituted diphenyl carbonate such as ditolyl carbonate, and the like. Among these, diphenyl carbonate and substituted diphenyl carbonate are preferable, and diphenyl carbonate is more preferable. In addition, carbonic acid diester may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

  The ratio of the dihydroxy compound and the carbonic acid diester is arbitrary as long as the desired polycarbonate resin can be obtained, but it is preferable to use an equimolar amount or more of the carbonic acid diester with respect to 1 mol of the dihydroxy compound. Is more preferable. The upper limit is usually 1.30 mol or less. By setting it as such a range, the amount of terminal hydroxyl groups can be adjusted to a suitable range.

  In the polycarbonate resin, the amount of terminal hydroxyl groups tends to have a great influence on thermal stability, hydrolysis stability, color tone and the like. For this reason, you may adjust the amount of terminal hydroxyl groups as needed by a well-known arbitrary method. In the transesterification reaction, a polycarbonate resin in which the terminal hydroxyl group amount is adjusted can be usually obtained by adjusting the mixing ratio of the carbonic acid diester and the dihydroxy compound; the degree of vacuum during the transesterification reaction, and the like. In addition, the molecular weight of the polycarbonate resin usually obtained can also be adjusted by this operation.

  When adjusting the amount of terminal hydroxyl groups by adjusting the mixing ratio of the carbonic acid diester and the dihydroxy compound, the mixing ratio is as described above.

  Further, as a more aggressive adjustment method, there may be mentioned a method in which a terminal terminator is mixed separately during the reaction. Examples of the terminal terminator at this time include monohydric phenols, monovalent carboxylic acids, carbonic acid diesters, and the like. In addition, 1 type may be used for a terminal terminator and it may use 2 or more types together by arbitrary combinations and a ratio.

  When producing a polycarbonate resin by the melt transesterification method, a transesterification catalyst is usually used. Any transesterification catalyst can be used. Among them, it is preferable to use, for example, an alkali metal compound and / or an alkaline earth metal compound. In addition, auxiliary compounds such as basic boron compounds, basic phosphorus compounds, basic ammonium compounds, and amine compounds may be used in combination. In addition, 1 type may be used for a transesterification catalyst and it may use 2 or more types together by arbitrary combinations and a ratio.

  In the melt transesterification method, the reaction temperature is usually 100 to 320 ° C. The pressure during the reaction is usually a reduced pressure condition of 2 mmHg or less. As a specific operation, a melt polycondensation reaction may be performed under the above-mentioned conditions while removing a by-product such as an aromatic hydroxy compound.

  The melt polycondensation reaction can be performed by either a batch method or a continuous method. When performing by a batch type, the order which mixes a reaction substrate, a reaction medium, a catalyst, an additive, etc. is arbitrary as long as a desired aromatic polycarbonate resin is obtained, What is necessary is just to set an appropriate order arbitrarily. However, considering the stability of the obtained polycarbonate resin and polycarbonate resin composition, the melt polycondensation reaction is preferably carried out continuously.

  In the melt transesterification method, a catalyst deactivator may be used as necessary. As the catalyst deactivator, a compound that neutralizes the transesterification catalyst can be arbitrarily used. Examples thereof include sulfur-containing acidic compounds and derivatives thereof. In addition, 1 type may be used for a catalyst deactivator and it may use 2 or more types together by arbitrary combinations and a ratio.

  The amount of the catalyst deactivator used is usually 0.5 equivalents or more, preferably 1 equivalent or more, and usually 10 equivalents or less, relative to the alkali metal or alkaline earth metal contained in the transesterification catalyst. Preferably it is 5 equivalents or less. Furthermore, it is 1 ppm or more normally with respect to polycarbonate resin, and is 100 ppm or less normally, Preferably it is 20 ppm or less.

[2-4. Other matters concerning polycarbonate resin]
The molecular weight of the polycarbonate resin used in the present invention is arbitrary and may be appropriately selected and determined, but the viscosity average molecular weight [Mv] converted from the solution viscosity is usually 10,000 or more, preferably 16000 or more, more preferably 18000 or more. Moreover, it is 40000 or less normally, Preferably it is 30000 or less. By setting the viscosity average molecular weight to be equal to or higher than the lower limit of the above range, the mechanical strength of the thermoplastic resin composition of the present invention can be further improved, and more preferable when used for applications requiring high mechanical strength. Become. On the other hand, by making the viscosity average molecular weight not more than the upper limit of the above range, it is possible to suppress and improve the fluidity drop of the thermoplastic resin composition of the present invention, and to improve the molding processability and facilitate the molding process. Become. Two or more types of polycarbonate resins having different viscosity average molecular weights may be mixed and used, and in this case, a polycarbonate resin having a viscosity average molecular weight outside the above-mentioned preferred range may be mixed.

The viscosity average molecular weight [Mv] is obtained by using methylene chloride as a solvent and obtaining an intrinsic viscosity [η] (unit: dl / g) at a temperature of 20 ° C. using an Ubbelohde viscometer. , Η = 1.23 × 10 ⁻⁴ Mv ^0.83 . The intrinsic viscosity [η] is a value calculated from the following equation by measuring the specific viscosity [η _sp ] at each solution concentration [C] (g / dl).

  The terminal hydroxyl group concentration of the polycarbonate resin is arbitrary and may be appropriately selected and determined, but is usually 1000 ppm or less, preferably 800 ppm or less, more preferably 600 ppm or less. When the terminal hydroxyl group concentration is less than or equal to this upper limit value, the residence heat stability and color tone of the thermoplastic resin composition of the present invention can be further improved. In addition, the lower limit is usually 10 ppm or more, preferably 30 ppm or more, more preferably 40 ppm or more, particularly for polycarbonate resins produced by the melt transesterification method. When the terminal hydroxyl group concentration is at least the lower limit value, it is possible to suppress the decrease in molecular weight and further improve the mechanical properties of the thermoplastic resin composition of the present invention.

  The unit of the terminal hydroxyl group concentration is the weight of the terminal hydroxyl group expressed in ppm relative to the weight of the polycarbonate resin. The measurement method is a colorimetric determination method (method described in Macromol. Chem. 88 215 (1965)) by the titanium tetrachloride / acetic acid method.

  The polycarbonate resin is a polycarbonate resin alone (the polycarbonate resin alone is not limited to an embodiment including only one type of polycarbonate resin, and includes, for example, an embodiment including a plurality of types of polycarbonate resins having different monomer compositions, molecular weights, physical properties, and the like. May be used in the sense), or may be used as an alloy (mixture) by combining a polycarbonate resin and another thermoplastic resin. Further, for example, for the purpose of further improving flame retardancy and impact resistance, a polycarbonate resin is copolymerized with an oligomer or polymer having a siloxane structure; for the purpose of further improving thermal oxidation stability and flame retardancy A monomer, oligomer or polymer having a copolymer; a copolymer with a monomer, oligomer or polymer having a dihydroxyanthraquinone structure for the purpose of improving thermal oxidation stability; Copolymers with oligomers or polymers having an olefinic structure; copolymers with polyester resin oligomers or polymers for the purpose of improving chemical resistance; Good.

  Further, in order to improve the appearance of the molded product and improve the fluidity, the polycarbonate resin may contain a polycarbonate oligomer. The viscosity average molecular weight [Mv] of this polycarbonate oligomer is usually 1500 or more, preferably 2000 or more, and is usually 9500 or less, preferably 9000 or less. In this case, the polycarbonate oligomer contained in the thermoplastic resin composition of the present invention is preferably 30% by mass or less of the polycarbonate resin (including the polycarbonate oligomer).

  Further, the polycarbonate resin may be not only a virgin raw material but also a polycarbonate resin regenerated from a used product (so-called material-recycled polycarbonate resin). Examples of the used products include optical recording media such as optical discs; light guide plates; vehicle window glass, vehicle headlamp lenses, windshields and other vehicle transparent members; water bottles and other containers; eyeglass lenses; Examples include building materials such as windows and corrugated sheets. Also, non-conforming products, pulverized products obtained from sprues, runners, etc., or pellets obtained by melting them can be used.

  However, the recycled polycarbonate resin is preferably 80% by mass or less, more preferably 50% by mass or less, among the polycarbonate resins contained in the thermoplastic resin composition of the present invention. The recycled polycarbonate resin is likely to have undergone deterioration such as heat deterioration and aging deterioration, so if such polycarbonate resin is used more than the above upper limit, the hue and mechanical properties may be reduced. It is because there is sex.

[3. Fluoropolymer]
The thermoplastic resin composition of the present invention has a thermoplastic resin melting characteristics (for example, anti-drip property during combustion), slidability, scratch resistance, water repellency, oil repellency, stain resistance, fingerprint resistance, etc. In order to improve the surface properties of the polymer, a fluoropolymer is included.

As the fluoropolymer used in the present invention, a fluoroolefin resin is particularly preferable.
The fluoroolefin resin is usually a polymer or copolymer containing a fluoroethylene structure, and specific examples include difluoroethylene resin, tetrafluoroethylene resin, tetrafluoroethylene / hexafluoropropylene copolymer resin, Of these, tetrafluoroethylene resin is preferred.
As the fluoropolymer, those having fibril forming ability are particularly preferable, and specific examples thereof include fluoroolefin resins having fibril forming ability. Thus, it has the tendency to improve dripping prevention property at the time of combustion by having fibril formation ability.

  Commercially available fluoroolefin resins having fibril-forming ability include, for example, “Teflon (registered trademark) 6J” manufactured by Mitsui DuPont Fluorochemical Co., Ltd., “Polyflon (registered trademark) F201L” manufactured by Daikin Chemical Industries, Ltd. (Trademark) F103 ". Furthermore, as a commercial item of the aqueous dispersion of fluoroolefin resin, for example, “Teflon (registered trademark) 30J” manufactured by Mitsui DuPont Fluorochemical Co., Ltd., “Fluon (registered trademark) D-1” manufactured by Daikin Chemical Industries, Ltd. and the like can be mentioned. .

  As the fluoropolymer, an organic polymer-coated fluoroolefin resin can also be suitably used. By using the organic polymer-coated fluoroolefin resin, dispersibility is improved, the surface appearance of the molded body is improved, and surface foreign matter tends to be suppressed. The organic polymer-coated fluoroolefin resin can be produced by various known methods. For example, (1) a polyfluoroethylene particle aqueous dispersion and an organic polymer particle aqueous dispersion are mixed and coagulated or spray-dried. (2) A method of polymerizing a monomer constituting an organic polymer in the presence of an aqueous dispersion of polyfluoroethylene particles, and then pulverizing or producing the powder by solidification or spray drying. (3) After emulsion polymerization of a monomer having an ethylenically unsaturated bond in a dispersion obtained by mixing an aqueous dispersion of polyfluoroethylene particles and an aqueous dispersion of organic polymer particles, powder is obtained by coagulation or spray drying. And the like, and the like.

  The organic polymer for coating the fluoroolefin resin is not particularly limited, and specific examples of the monomer for producing such an organic polymer include the following. .

Styrene, α-methylstyrene, p-methylstyrene, o-methylstyrene, tert-butylstyrene, o-ethylstyrene, p-chlorostyrene, o-chlorostyrene, 2,4-dichlorostyrene, p-methoxystyrene, o -Aromatic vinyl monomers such as methoxystyrene and 2,4-dimethylstyrene;
Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, dodecyl acrylate, dodecyl methacrylate, tridecyl acrylate, (Meth) acrylic acid ester monomers such as tridecyl methacrylate, octadecyl acrylate, octadecyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate;
Vinyl cyanide monomers such as acrylonitrile and methacrylonitrile;
Α, β-unsaturated carboxylic acids such as maleic anhydride;
Maleimide monomers such as N-phenylmaleimide, N-methylmaleimide, N-cyclohexylmaleimide;
Glycidyl group-containing monomers such as glycidyl methacrylate;
Vinyl ether monomers such as vinyl methyl ether and vinyl ethyl ether;
Vinyl carboxylate monomers such as vinyl acetate and vinyl butyrate;
Olefinic monomers such as ethylene, propylene, isobutylene;
Diene monomers such as butadiene, isoprene, dimethylbutadiene, etc.

  In addition, these monomers can be used individually or in mixture of 2 or more types.

  In particular, as a monomer for producing an organic polymer that coats a fluoroolefin resin, when the thermoplastic resin is a polycarbonate resin, it is compatible with the polycarbonate resin from the viewpoint of dispersibility when blended with the polycarbonate resin. Those having high properties are preferred, and aromatic vinyl monomers, (meth) acrylic acid ester monomers, and vinyl cyanide monomers are more preferred.

  The content ratio of the fluoroolefin resin in the organic polymer-coated fluoroolefin resin is usually 30% by mass or more, preferably 35% by mass or more, more preferably 40% by mass or more, and particularly preferably 45% by mass or more. Usually, it is 95 mass% or less, Preferably it is 90 mass% or less, More preferably, it is 80 mass% or less, Most preferably, it is 75 mass% or less. It is preferable that the content ratio of the fluoroolefin resin in the organic polymer-coated fluoroolefin resin is in the above-described range because the balance between the flame retardancy and the appearance of the molded body tends to be excellent.

  Specifically, commercially available products of such an organic polymer-coated fluoroolefin resin include “Metablene (registered trademark) A-3800” manufactured by Mitsubishi Rayon Co., Ltd. and “Blendex (registered trademark) 449” manufactured by GE Specialty Chemical. And “Poly TS AD001” manufactured by PIC.

  In addition, 1 type may contain fluoropolymer and 2 or more types may contain it by arbitrary combinations and a ratio.

  The content of the fluoropolymer in the thermoplastic resin composition of the present invention is usually 0.001 part by mass or more, preferably 0.005 part by mass or more, more preferably 0.01 parts by mass with respect to 100 parts by mass of the thermoplastic resin. Part by mass or more, particularly preferably 0.02 part 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, particularly preferably 0.5 parts by mass or less. . When the content of the fluoropolymer is below the lower limit of the above range, the effect of blending the fluoropolymer may be insufficient, and when the content of the fluoropolymer exceeds the upper limit of the above range, There is a possibility that a molded article obtained by molding this thermoplastic resin composition may have a poor appearance or a decrease in mechanical strength, or may have a significantly reduced transmittance or transparency in the near infrared region.

[4. Polycarbosilane compound]
The thermoplastic resin composition of the present invention contains a polycarbosilane compound, that is, a silicon compound having a silicon-carbon bond in the main chain, as a fluoropolymer dispersant. In the present invention, by containing this polycarbosilane compound, the compatibility and dispersibility of the fluoropolymer in the thermoplastic resin composition of the present invention are improved, and light transmittance, particularly near infrared light transmittance, Improves flammability and improves poor appearance and reduced strength.

  This is because the polycarbosilane compound having a silicon-carbon bond in the main chain contains an organic component (organic residue) in the main chain, and thus has a strong organic property. Therefore, the fluoropolymer to the thermoplastic resin This is because the compatibility and dispersibility can be effectively improved.

  The polycarbosilane compound in the present invention may contain a bond between a silicon atom and an atom other than carbon in the main chain as long as the object of the present invention is not impaired. Examples of such bonds include silicon-silicon (Si-Si) bonds, silicon-oxygen (Si-O) bonds, silicon-nitrogen (Si-N) bonds, silicon-boron (Si-B) bonds, silicon -A phosphorus (Si-P) bond, a silicon-titanium (Si-Ti) bond, etc. are mentioned. Such bonds may be introduced unintentionally by oxidation or the like in addition to being introduced from components such as raw materials and catalysts in the production of silicon compounds consisting essentially of silicon-carbon bonds. There is.

  The polycarbosilane compound used in the present invention is not particularly limited in its chemical structure and form as long as it has two or more repeating units having a silicon-carbon bond (Si-C bond) in the main chain. A silicon compound having a main chain structure in which silicon-silicon bond units and hydrocarbon residues are alternately continuous, among them, at least one of the structural units represented by the following formulas (1) to (3) What has the principal chain structure which consists of a seed | species structural unit and a hydrocarbon residue is preferable.

(In formulas (1) to (3), R ¹ , R ² , and R ³ each independently represent a monovalent hydrocarbon group, a hydrogen atom, or a silyl group, and a, b, and c are each independently , 0 or 1. The plurality of R ¹ , R ² and R ³ contained in the main chain structure may be the same or different.

  As such a polycarbosilane compound, for example, a linear or cyclic polycarbosilane compound comprising the structural unit represented by the above formula (1) and a hydrocarbon residue, the above formula (2) or (3 ), A branched or reticulated polycarbosilane compound composed of a structural unit and a hydrocarbon residue, a combination of structural units represented by the above formulas (1) to (3), for example, the formula (1) and Examples include formula (2), formula (1) and formula (3), formula (2) and formula (3), formula (1) to (3), and a polycarbosilane compound composed of a hydrocarbon residue. . Among these, a linear polycarbosilane compound having a main chain structure composed of the structural unit represented by the above formula (1) and a divalent hydrocarbon residue can be dispersed in a thermoplastic resin such as a polycarbonate resin. Although it is preferable because it tends to be excellent, the linear polycarbosilane compound may be branched or network-like.

  The linear polycarbosilane compound having a main chain structure composed of the structural unit represented by the above formula (1) and a divalent hydrocarbon residue is represented by the following formula (4). Those having a repeating unit are preferred.

(In the formula (4), R ¹ , R ² , a and b are as defined in the formula (1), A ¹ represents a divalent hydrocarbon group having 1 to 12 carbon atoms, p, q Each independently represents an integer of 1 to 8. R ¹ , R ² and A ¹ may be the same or different in all repeating units.

  In the above formula (4), p and q each represent an integer of 1 to 8, but p and q are each preferably 1 to 4, more preferably 1 or 2, and more preferably 1. It is preferable.

  As such a linear polycarbosilane compound, those having a repeating unit represented by the following formula (5) are preferable. By having such a linear structure, the dispersibility in the polycarbonate resin is improved, and the transparency and mechanical properties of the thermoplastic resin composition of the present invention tend to be improved.

(In the formula ^{(5), R 1, R} 2 have the same meanings as in the formula (4), ^{A 2} is ^.R 1, ^{R 2} and ^{A 2} which represents an alkylene group having 1 to 12 carbon atoms, each and every In the repeating unit, they may be the same or different.)

In the formulas (1) to (5), the groups represented by R ¹ , R ² , and R ³ represent at least one selected from a monovalent hydrocarbon group, a hydrogen atom, and a silyl group. Examples of the monovalent hydrocarbon group include an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, an aralkyl group, and the like. Among them, an alkyl group and an aryl group are preferable, and an alkyl group is particularly preferable. Preferably, a methyl group is more preferable. Incidentally, the substituent represented by R ^1, R ^2, and R ³ may be different 2 or more may be the same in each and every repeating unit.

  Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, and a dodecyl group. An alkyl group having 1 to 12 carbon atoms is preferable, and an alkyl group having 1 to 6 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, pentyl group, and hexyl group is preferable. A methyl group is particularly preferred.

  Examples of the cycloalkyl group include cycloalkyl groups having 5 to 14 carbon atoms such as a cyclopentyl group and a cyclohexyl group. Among them, a cycloalkyl group having 5 to 8 carbon atoms is preferable.

  Examples of the alkenyl group include alkenyl groups having 2 to 8 carbon atoms such as vinyl group and allyl group. Examples of the cycloalkenyl group include cycloalkenyl groups having 5 to 12 carbon atoms such as cyclopentyl group and cyclohexyl group. Is mentioned.

  Examples of the alkynyl group include alkynyl groups having 2 to 8 carbon atoms such as ethynyl group and propynyl group, and arylalkynyl groups such as ethynylbenzene group.

Examples of the aryl group include aryl groups having 6 to 20 carbon atoms such as a phenyl group, a methylphenyl (that is, tolyl) group, a dimethylphenyl (that is, xylyl) group, and a naphthyl group. -10 aryl groups are preferred, and phenyl groups are particularly preferred.
Examples of the aralkyl group include aralkyl groups having 6 to 20 carbon atoms such as benzyl group, phenethyl group, and phenylpropyl group. Among them, aralkyl groups having 6 to 10 carbon atoms are preferable, and benzyl group is particularly preferable. preferable.

  Examples of the silyl group include silyl groups having 1 to 10 silicon atoms such as a silyl group, a disilanyl group, and a trisilanyl group. Among them, a silyl group having 1 to 6 silicon atoms is preferable. In the case of the silyl group, at least one of the hydrogen atoms may be substituted with a functional group such as an alkyl group, an aryl group, or an alkoxy group.

In the above formulas (1) to (5), the substituents represented by R ¹ , R ² and R ³ are each independently more preferably a monovalent hydrocarbon group or a hydrogen atom. , An alkyl group, or a hydrogen atom is more preferable, and a methyl group or a hydrogen atom is particularly preferable.

  In the above formulas (1) to (4), a, b, and c represent 0 or 1. When a, b, and c are 0, the silicon atom of the polycarbosilane compound is substituted with an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, an aralkyl group, or a silyl group. Means a group or is unsubstituted (has a hydrogen atom), and when a, b and c are 1, the silicon atom of the polycarbosilane compound is substituted with an alkoxy group, a cyclo It means having an alkyloxy group, an alkenyloxy group, a cycloalkenyloxy group, an alkynyloxy group, an aryloxy group, an aralkyloxy group, or a hydroxyl group. From the viewpoint of heat resistance of the polycarbosilane compound, a, b, and c are preferably 0, but are intentionally intended to improve the affinity with the resin, or unintentionally by oxidation action or the like. In addition, it may be 1.

  On the other hand, the hydrocarbon residue constituting the main chain structure of the polycarbosilane compound bonded to the structural units represented by the above formulas (1) to (3) is not particularly limited, May have a branched chain or a cyclic structure, and may contain not only a saturated bond but also an unsaturated bond. Moreover, in addition to carbon atoms and hydrogen atoms, hetero atoms such as oxygen atoms, nitrogen atoms, sulfur atoms, phosphorus atoms, and fluorine atoms may be contained. Of these, a divalent to tetravalent hydrocarbon group is preferable, and a divalent hydrocarbon group is particularly preferable.

  As the divalent hydrocarbon residue constituting the main chain structure of the polycarbosilane compound bonded to the structural units represented by the formulas (1) to (3), specifically, the following linear or Examples thereof include branched divalent hydrocarbon residues.

  1 to 12 carbon atoms such as methylene group, ethylene group, trimethylene group, propylene group, isopropylidene group, tetramethylene group, isobutylene group, tert-butylene group, isobutylene group, pentamethylene group, hexamethylene group, octamethylene group, etc. An alkylene group;

  An alkylidene group having 2 to 12 carbon atoms such as an ethylidene group, a propylidene group, a butylidene group, a sec-butylidene group, and an isohexylidene group;

  A cycloalkylene group having 3 to 12 carbon atoms such as a cyclopentylene group, a cyclohexylene group, a methylcyclohexylene group, a trimethylcyclohexylene group, a cyclopeptylene group, a cyclooctylene group, a cyclononylene group, and a cyclodecylene group;

  Vinylene group, propenylene group, 1-butenylene group, 2-butenylene group, 1,3-butadienylene group, 1-methylpropenylene group, 1-methyl-2-propenylene group, 1-pentenylene group, 2-pentenylene group, 1 , 3-pentadienylene group, 1,4-pentadienylene group, 1-methylbutenylene group, 1-methyl-1,2-butadienylene group, 1-hexenylene group, 2-hexenylene group, 3-hexenylene group, 1-methylpentenylene Group, 2-methyl-2-pentenylene group, 1,1-dimethyl-2-propenylene group, 1-ethyl-2-propenylene group, 1,2-dimethylpropenylene group, 1-methyl-1-butenylene group, 1 -Heptenylene group, 1-methylhexenylene group, 2-methyl-2-hexenylene group, 1,2-dimethylpentenylene group, - octenylene, 2-octenylene, 3-nonenylene group, an alkenylene group having 2 to 12 carbon atoms such as 4-decenylene group;

  An alkenylidene group having 2 to 12 carbon atoms such as vinylidene group, propynylidene group, and arylidene group;

  1-cyclopropenylene group, 2-cyclopentenylene group, 2,4-cyclopentadienylene group, 1-cyclohexenylene group, 2-cyclohexenylene group, 1-cycloheptenylene group, 2-cyclononenylene A cycloalkenylene group having 3 to 12 carbon atoms such as a group, 3-cyclodecenylene group, 2-cyclododecenylene group;

  Ethynylene group, 1,3- (1-propynylene) group, 3,3- (1-propynylene) group, 1,4- (1-butynylene) group, 1,5- (1-pentynylene) group, 1,6 An alkynylene group having 2 to 12 carbon atoms such as a-(1-hexynylene) group and a 1,12- (1-dodecynylene) group;

  Arylene groups having 6 to 12 carbon atoms such as o-phenylene group, m-phenylene group, p-phenylene group, methylphenylene group, dimethylphenylene group, p-xylene-α, α'-diyl group, biphenylene group, and naphthylene group. ;

_{-CH 2 -C 6 H 4 -,} - CH 2 -C 6 H 4 -CH 2 -, - CH 2 CH 2 -C 6 H 4 -, - CH 2 CH 2 -C 6 H 4 -CH 2 -, _{-CH 2 CH 2 CH 2 -C 6} H 4 -, - CH (CH 3) CH 2 -C 6 H 4 -, - CH 2 CH 2 CH 2 CH 2 -C 6 H 4 -, - CH 2 CH 2 C 6-12 aralkylene groups such as CH (CH ₃ ) —C ₆ H ₄ —; etc.

  Moreover, as trivalent hydrocarbon group which couple | bonds with the structural unit represented by said Formula (1)-(3) and comprises the principal chain structure of a polycarbosilane compound, following formula (15)-(16) What is represented.

  Moreover, as a tetravalent hydrocarbon group which comprises the main chain structure of a polycarbosilane compound couple | bonded with the structural unit represented by said Formula (1)-(3), it is represented by following formula (17) Is mentioned.

  As described above, the hydrocarbon residue is preferably a divalent hydrocarbon group, and among them, an alkylene group, an alkenylene group, an alkynylene group, an arylene group is preferable, an alkylene group, an arylene group is particularly preferable, and an alkylene group is preferable. Most preferred. Moreover, as an alkylene group, a C1-C8 alkylene group is more preferable, a C1-C4 alkylene group is especially preferable, and a methylene group is the most preferable.

Incidentally, A ¹ in Formula (4) represents a straight-chain or branched divalent hydrocarbon group having 1 to 12 carbon atoms, and specific examples thereof include the above-mentioned divalent hydrocarbon residue. A ² in the formula (5) represents an alkylene group having 1 to 12 carbon atoms, and specific examples thereof include the aforementioned alkylene groups having 1 to 12 carbon atoms. As the alkylene group for A ¹ and A ^2, an alkylene group having 1 to 8 carbon atoms is more preferable, an alkylene group having 1 to 4 carbon atoms is particularly preferable, and a methylene group is most preferable.

  When the example of the polycarbosilane compound used by this invention is given, what has the repeating unit shown below is mentioned. However, the polycarbosilane compound is not limited to the following examples. Moreover, the thermoplastic resin composition of the present invention may contain only one type of polycarbosilane compound, and may contain two or more types in any combination and in any ratio.

  Especially, the polycarbosilane compound which has a repeating unit represented by following formula (6) is especially preferable. Such a polycarbosilane compound is easily obtained by thermal decomposition of polydimethylsilane and has a high yield, and thus has a great industrial merit.

  In the above exemplary formula, n represents the degree of polymerization of the polycarbosilane compound, and is usually 2 or more, more preferably 3 or more, particularly preferably 5 or more, more preferably 10 or more, and usually 20000 or less, more Preferably it is 5000 or less, Especially preferably, it is 1000 or less, More preferably, it is 500 or less. By setting n to be not less than the lower limit of the above range, outgassing and mold contamination of the thermoplastic resin composition of the present invention can be reduced, which is preferable. On the other hand, by setting n to be not more than the upper limit of the above range, the effect of improving the dispersibility of the fluoropolymer with respect to the thermoplastic resin becomes excellent, and the mechanical properties of the thermoplastic resin composition of the present invention also tend to be improved.

  The molecular weight of the polycarbosilane compound according to the present invention is arbitrary and may be appropriately selected and determined. The number average molecular weight [Mn] is usually 100 or more, preferably 200 or more, more preferably 300 or more, particularly preferably. Is 500 or more, and is usually 20000 or less, preferably 10,000 or less, more preferably 5000 or less, and particularly preferably 3000 or less. By setting the number average molecular weight to be equal to or higher than the lower limit of the above range, the outgas and mold contamination of the thermoplastic resin composition of the present invention can be reduced, which is preferable. On the other hand, by setting the number average molecular weight below the upper limit of the above range, it is possible to suppress and improve the fluidity drop of the thermoplastic resin composition of the present invention, so that the molding processability can be improved and the molding process can be easily performed. In addition, the mechanical properties tend to improve. Two or more types of polycarbosilane compounds having different number average molecular weights may be mixed and used. In this case, a polycarbosilane compound having a number average molecular weight outside the above preferred range may be mixed. Good.

  Here, the number average molecular weight [Mn] is measured by gel permeation chromatography (GPC) (apparatus: Tosho 8020, column: Tosoh TSKgel Multipore Hxl-M) using tetrahydrofuran as a solvent and a temperature of 40 ° C. It is the value.

  Further, the melting point of the polycarbosilane compound according to the present invention is arbitrary and may be appropriately selected and determined, but is usually 20 ° C. or higher, preferably 30 ° C. or higher, more preferably 40 ° C. or higher, particularly preferably 60 ° C. The temperature is usually 500 ° C. or lower, preferably 300 ° C. or lower, more preferably 280 ° C. or lower, and particularly preferably 260 ° C. or lower. By setting the melting point to be equal to or higher than the lower limit of the above range, it is possible to reduce mold contamination of the thermoplastic resin composition of the present invention, which is preferable. On the other hand, by setting the melting point to be equal to or lower than the upper limit of the above range, the effect of improving the dispersibility of the fluoropolymer with respect to the thermoplastic resin becomes excellent, and the mechanical properties of the thermoplastic resin composition of the present invention also tend to be improved. Two or more kinds of polycarbosilane compounds having different melting points may be mixed and used, and in this case, a polycarbosilane compound having a melting point outside the above preferred range may be mixed.

The method for producing the polycarbosilane compound according to the present invention is arbitrary, and may be appropriately selected and determined. Examples thereof include a direct synthesis method and a thermal decomposition method.
Examples of the direct synthesis method include a method of co-condensing at least one dihalogen silane and at least one dihalogen hydrocarbon under a catalyst such as an alkali metal. At this time, the reaction is generally performed in a suspension of a catalyst such as an alkali metal using a solvent. As the solvent used for the suspension, for example, preferably a hydrocarbon solvent is used, and more preferably, toluene, xylene, decalin, and the like. Other components (dihalogen silane, dihalogen hydrocarbon) are introduced into the catalyst suspension and reacted, and then the desired product can be obtained from the reaction mixture by an appropriate method. If the polycarbosilane compound is soluble in, for example, a solvent, other insoluble components may be separated by filtration. The polycarbosilane compound remaining in the solvent can then be purified by washing with water and dried to a powder by removing the solvent. On the other hand, when the synthesized polycarbosilane compound is insoluble in a solvent, the polycarbosilane compound is extracted with an appropriate solvent, subsequently purified by washing with water, and powdered by removing the solvent. Can be dried into a shape.

  Moreover, as a thermal decomposition method, for example, a method of obtaining a polycarbosilane compound by a thermal decomposition transition reaction by heating an alkylsilane such as tetramethylsilane or a polysilane such as polydimethylsilane (polymethylsilylene) at a high temperature. Is mentioned. In addition, generally the heating temperature in this case is 350-1000 degreeC, More preferably, it is 400-800 degreeC. The reaction may be carried out under normal pressure or under high pressure, but it is preferable to carry out the reaction under high pressure because the yield tends to be improved. It is also preferable to add a catalytic amount of a boron compound such as polyborodiphenylsiloxane. The added amount of the boron compound is usually 0.1 parts by mass or more, preferably 0.2 parts by mass or more, more preferably 0.5 parts by mass or more with respect to 100 parts by mass of the alkylsilane or polysilane. Usually 5 parts by mass or less, preferably 3 parts by mass or less, more preferably 2 parts by mass or less. By making the content of the boron compound equal to or higher than the lower limit value of the above range, the yield of the polycarbosilane compound according to the present invention tends to be improved, and the content of the boron compound is set to be not more than the upper limit value of the above range. Thus, it is possible to suppress the oxygen content of the polycarbosilane compound according to the present invention and to suppress a decrease in heat resistance, a decrease in dispersibility in a polycarbonate resin, and the like.

  As a method for producing the polycarbosilane compound according to the present invention, a technique obtained from the polysilane compound by a thermal decomposition method is particularly preferred from the viewpoint of quality and cost. Two or more kinds of polycarbosilane compounds having different production methods may be mixed and used, and in this case, a polycarbosilane compound whose production method is outside the above-mentioned preferred range may be mixed.

The content of the polycarbosilane compound in the thermoplastic resin composition of the present invention is preferably 0.005 parts by mass or more, more preferably 0.01 parts by mass or more, and still more preferably with respect to 100 parts by mass of the thermoplastic resin. 0.02 parts by mass or more, particularly preferably 0.05 parts by mass or more, most preferably 0.75 parts by mass or more, preferably 10 parts by mass or less, more preferably 7.5 parts by mass or less, and further preferably 3 It is 1 part by mass or less, particularly preferably 1.75 parts by mass or less. If the content of the polycarbosilane compound is too small, the effect of improving the compatibility and dispersibility of the fluoropolymer in the thermoplastic resin may be insufficient. In addition, the mechanical strength of the thermoplastic resin composition may be lowered.
In addition, the polycarbosilane compound based on this invention can be used individually or in combination of 2 or more types.

[5. Flame retardants]
The thermoplastic resin composition of the present invention may further contain a flame retardant, and by including the flame retardant, extremely excellent flame retardancy can be obtained when used in combination with a fluoropolymer.
The flame retardant is not particularly limited as long as it is a known one, and may be appropriately selected and used. For example, halogen flame retardant, phosphorus flame retardant, nitrogen flame retardant, boron flame retardant, metal salt-based flame retardant A flame retardant, a silicone type flame retardant, an inorganic compound type flame retardant, etc. are mentioned. Among them, a metal salt flame retardant (hereinafter referred to as “metal”), which hardly causes a decrease in light transmittance of the thermoplastic resin composition, in particular, near-infrared light transmittance and mechanical properties, and has little influence on the environment and the human body. It may be referred to as a “salt compound”). By containing the metal salt compound together with a thermoplastic resin that can be suitably used in the present invention, it is possible to effectively exhibit flame retardancy.

As a kind of metal which a metal salt compound has, lithium (Li), sodium (Na), potassium (K), rubidium (Rb), alkali metals such as cesium (Cs); magnesium (Mg), calcium (Ca), Alkaline earth metals such as strontium (Sr) and barium (Ba); and aluminum (Al), titanium (Ti), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc ( Zn), zirconium (Zr), molybdenum (Mo) and the like can be mentioned, among which alkali metals or alkaline earth metals are preferable.
This promotes the formation of a carbonized layer at the time of combustion of the thermoplastic resin composition of the present invention, can further enhance the flame retardancy, and mechanical properties such as impact resistance of the polycarbonate resin, heat resistance, This is because the properties such as the mechanical characteristics can be maintained well. Accordingly, the metal salt compound is preferably at least one metal salt compound selected from the group consisting of alkali metal salts and alkaline earth metal salts, more preferably alkali metal salt compounds, sodium salt compounds, potassium salts. Particularly preferred are compounds and cesium salt compounds.

  Examples of the metal salt compound include an organic metal salt compound and an inorganic metal salt compound, and an organic metal salt compound is preferable from the viewpoint of good dispersibility in a thermoplastic resin.

  Examples of the organic metal salt compound include organic sulfonic acid metal salts, organic sulfonamide metal salts, organic carboxylic acid metal salts, organic boric acid metal salts, and organic phosphoric acid metal salts. Among these, from the viewpoint of thermal stability when mixed with a polycarbonate resin, an organic sulfonic acid metal salt, an organic sulfonamide metal salt, and an organic phosphoric acid metal salt are preferable, and an organic sulfonic acid metal salt is particularly preferable.

  Examples of organic sulfonic acid metal salts include organic sulfonic acid lithium (Li) salt, organic sulfonic acid sodium (Na) salt, organic sulfonic acid potassium (K) salt, organic sulfonic acid rubidium (Rb) salt, organic sulfonic acid Examples thereof include a cesium (Cs) salt, an organic magnesium sulfonate (Mg) salt, an organic calcium sulfonate (Ca) salt, an organic sulfonic acid strontium (Sr) salt, and an organic sulfonic acid barium (Ba) salt. Among these, organic sulfonic acid alkali metal salts such as organic sulfonic acid sodium (Na) salt, organic sulfonic acid potassium (K) salt compound, and organic sulfonic acid cesium (Cs) salt compound are particularly preferable.

  Among the metal salt compounds, preferred examples include a metal salt of a fluorine-containing aliphatic sulfonic acid, a metal salt of a fluorine-containing aliphatic sulfonic acid imide, a metal salt of an aromatic sulfonic acid, and a metal salt of an aromatic sulfonamide. It is done. Specific examples of preferable ones are as follows.

<< Metal salt of fluorine-containing aliphatic sulfonic acid >>
Potassium perfluorobutanesulfonate, lithium perfluorobutanesulfonate, sodium perfluorobutanesulfonate, cesium perfluorobutanesulfonate, lithium trifluoromethanesulfonate, sodium trifluoromethanesulfonate, potassium trifluoromethanesulfonate, perfluoroethanesulfone Alkali metal salts of fluorine-containing aliphatic sulfonic acids having at least one C—F bond in the molecule, such as potassium acid and potassium perfluoropropanesulfonate;

  At least one CF in the molecule, such as magnesium perfluorobutane sulfonate, calcium perfluorobutane sulfonate, barium perfluorobutane sulfonate, magnesium trifluoromethane sulfonate, calcium trifluoromethane sulfonate, barium trifluoromethane sulfonate, etc. An alkaline earth metal salt of a fluorine-containing aliphatic sulfonic acid having a bond;

  Disodium perfluoromethane disulfonate, dipotassium perfluoromethane disulfonate, sodium perfluoroethane disulfonate, dipotassium perfluoroethane disulfonate, dipotassium perfluoropropane disulfonate, dipotassium perfluoroisopropane disulfonate, dipotassium perfluorobutane disulfonate Alkali metal salts of fluorine-containing aliphatic disulfonic acids having at least one C—F bond in the molecule, such as sodium, dipotassium perfluorobutane disulfonate, and dipotassium perfluorooctane disulfonate;

<< Metal salt of fluorine-containing aliphatic sulfonic acid imide >>
Bis (perfluoropropanesulfonyl) imide lithium, bis (perfluoropropanesulfonyl) imide sodium, bis (perfluoropropanesulfonyl) imide potassium, bis (perfluorobutanesulfonyl) imide lithium, bis (perfluorobutanesulfonyl) imide sodium, At least 1 in the molecule, such as potassium bis (perfluorobutanesulfonyl) imide, potassium trifluoromethane (pentafluoroethane) sulfonylimide, sodium trifluoromethane (nonafluorobutane) sulfonylimide, potassium trifluoromethane (nonafluorobutane) sulfonylimide An alkali metal salt of a fluorine-containing aliphatic sulfonic acid imide having two C—F bonds;

  Cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide lithium, cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide sodium, cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide potassium An alkali metal salt of a cyclic fluorine-containing aliphatic sulfonic acid imide having at least one C—F bond in the molecule;

<< Metal salt of aromatic sulfonic acid >>
Diphenylsulfone-3,3′-disulfonate dipotassium, diphenylsulfone-3-sulfonate potassium, sodium benzenesulfonate, sodium (poly) styrenesulfonate, sodium paratoluenesulfonate, sodium (branched) dodecylbenzenesulfonate, tri Sodium chlorobenzenesulfonate, potassium benzenesulfonate, potassium styrenesulfonate, potassium (poly) styrenesulfonate, potassium paratoluenesulfonate, potassium (branched) dodecylbenzenesulfonate, potassium trichlorobenzenesulfonate, cesium benzenesulfonate, ( Poly) cesium styrene sulfonate, cesium p-toluenesulfonate, cesium (branched) dodecylbenzene sulfonate, cesium trichlorobenzene sulfonate An alkali metal salt of an aromatic sulfonic acid having at least one aromatic group in the molecule;

  Magnesium paratoluenesulfonate, calcium paratoluenesulfonate, strontium paratoluenesulfonate, barium paratoluenesulfonate, magnesium (branched) dodecylbenzenesulfonate, calcium (branched) calcium dodecylbenzenesulfonate in the molecule An alkaline earth metal salt of an aromatic sulfonic acid having an aromatic group of

<< Aromatic sulfonic acid amide metal salt >>
Sodium salt of saccharin, potassium salt of N- (p-tolylsulfonyl) -p-toluenesulfimide, potassium salt of N- (N′-benzylaminocarbonyl) sulfanilimide, potassium of N- (phenylcarboxyl) -sulfanilimide An alkali metal salt of an aromatic sulfonamide having at least one aromatic group in the molecule, such as a salt;

  Among the examples described above, fluorine-containing aliphatic sulfonic acid metal salts and aromatic sulfonic acid metal salts are more preferable, and fluorine-containing aliphatic sulfonic acid metal salts are particularly preferable.

  The fluorine-containing aliphatic sulfonic acid metal salt is more preferably an alkali metal salt of a fluorine-containing aliphatic sulfonic acid having at least one C—F bond in the molecule, and particularly preferably an alkali metal salt of perfluoroalkanesulfonic acid. Specifically, potassium perfluorobutane sulfonate is preferred.

  As the aromatic sulfonic acid metal salt, an alkali metal salt of an aromatic sulfonic acid is more preferable, and an alkali metal of diphenyl sulfone-sulfonic acid such as dipotassium diphenylsulfone-3,3′-disulfonic acid dipotassium or diphenylsulfone-3-sulfonic acid potassium. Salts; alkali metal salts of paratoluenesulfonic acid such as sodium paratoluenesulfonate, potassium paratoluenesulfonate, cesium paratoluenesulfonate; and the like, more preferably alkali metal salts of paratoluenesulfonic acid.

  In addition, 1 type may be used for a metal salt compound, and it may use 2 or more types together by arbitrary combinations and a ratio.

The content of the flame retardant in the thermoplastic resin composition of the present invention is preferably 0.001 part by mass or more, more preferably 0.02 part by mass or more, and still more preferably 0.001 part by mass with respect to 100 parts by mass of the thermoplastic resin. It is 05 parts by mass or more, preferably 30 parts by mass or more, more preferably 20 parts by mass or less, and even more preferably 10 parts by mass or less.

  In the present invention, when the flame retardant in the thermoplastic resin composition of the present invention is the above metal salt compound, it is preferably 0.001 part by mass or more, more preferably 0.02 part by mass or more, and further preferably 0.03. It is at least part by mass, particularly preferably at least 0.05 part by mass, preferably at most 30 parts by mass, more preferably at most 20 parts by mass, even more preferably at most 10 parts by mass, particularly preferably at most 1 part by mass.

  If the content of the metal salt compound is too small, the effect of improving the flame retardancy of the thermoplastic resin composition by blending it cannot be sufficiently obtained. Conversely, if the content is too large, the heat of the thermoplastic resin composition There is a possibility that a decrease in stability, a poor appearance of the molded body, and a decrease in mechanical strength may occur.

[6. Other ingredients]
The thermoplastic resin composition of the present invention may include various resin additives as other components in addition to those described above, as long as the desired physical properties are not significantly impaired.

  Examples of the resin additive include a heat stabilizer, an antioxidant, a release agent, an ultraviolet absorber, a dye / pigment, a fibrous reinforcing material, an optical function adjusting material, a flame retardant, an antistatic agent, an antifogging agent, a lubricant, Antiblocking agents, fluidity improvers, slidability modifiers, plasticizers, dispersants, antibacterial agents and the like can be mentioned. In addition, 1 type may contain resin additive and 2 or more types may contain it by arbitrary combinations and a ratio.

  Hereinafter, the example of the resin additive suitable for the thermoplastic resin composition of this invention is demonstrated concretely.

(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 Examples of the phosphates of Group 1 or 2B metals of the periodic table such as potassium, sodium phosphate, cesium phosphate, and zinc phosphate; organic phosphate compounds, organic phosphite compounds, and organic phosphonite compounds.

  Among these, organic phosphite compounds represented by the following formulas (18) to (20), organic phosphonite compounds represented by the following formula (21), and organic phosphate compounds represented by the following formula (22) are preferable.

In the above formulas (18) to (22), R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ are alkyl groups or aryl groups. To express. Among them, R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ usually have 1 or more carbon atoms, preferably 2 or more, The alkyl group is usually 30 or less, preferably 25 or less, or more preferably an aryl group having usually 6 or more carbon atoms and usually 30 or less. Furthermore, R ¹⁸ , R ¹⁹ , R ²⁰ , R ²² and R ²³ are preferably aryl groups rather than alkyl groups, and R ²¹ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ are alkyl groups rather than aryl groups. Groups are preferred. R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ may be the same or different.

In the formulas (19) and (21), X ⁶ and X ⁷ represent an aryl residue having 6 to 30 carbon atoms, and in the formula (22), d is usually 0 or more, preferably 1 or more. In general, it represents an integer of 2 or less.

  Examples of the organic phosphite compound represented by the above formula (18) 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, etc. . Specific examples of such organic phosphite compounds include, for example, “Adeka Stub 1178” and “Adeka Stub 2112” manufactured by Adeka, “JP-351”, “JP-360”, and “JP” manufactured by Johoku Chemical Industry Co., Ltd. -3CP "," Irgafos 168 "manufactured by Ciba Specialty Chemicals, and the like.

  Examples of the organic phosphite compound represented by the formula (19) include 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite. Specific examples of such an organic phosphite compound include “Adeka Stub HP-10” manufactured by Adeka Corporation.

  Examples of the organic phosphite compound represented by the formula (20) include distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, and bis (2,6-di-). tert-butyl-4-methylphenyl) pentaerythritol diphosphite and the like. Specific examples of such an organic phosphite compound include, for example, “ADK STAB PEP-8”, “ADK STAB PEP-24G”, “ADK STAB PEP-36” manufactured by Adeka Corporation, and “JPP-” manufactured by Johoku Chemical Industry Co., Ltd. 2000 "and the like.

  Examples of the organic phosphonite compound represented by the formula (21) include tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylene-di-phosphonite. Specific examples of such an organic phosphonite compound include “sand stub P-EPQ” manufactured by Sandoz.

  Examples of the organic phosphate compound represented by the formula (22) include mono-stearic acid phosphate, di-stearic acid phosphate, mono-2-ethylhexyl acid phosphate, di-2-ethylhexyl acid phosphate, monooleic acid phosphate, and di-oleic acid. A phosphate etc. are mentioned. Specific examples of such an organic phosphate compound include “ADEKA STAB AX-71” manufactured by Adeka Corporation, “JP-508”, “JP-518-O” manufactured by Johoku Chemical Industry Co., Ltd. and the like.

  In addition, 1 type may contain the heat stabilizer and 2 or more types may contain it by arbitrary combinations and a ratio.

  The content of the heat stabilizer in the thermoplastic resin composition of the present invention is usually 0.001 parts by mass or more, preferably 0.01 parts by mass or more, more preferably 0.001 parts by mass with respect to 100 parts by mass of the thermoplastic resin. It is 03 parts by mass or more, and is usually 1 part by mass or less, preferably 0.7 parts by mass or less, more preferably 0.5 parts by mass or less. If the content of the heat stabilizer is less than or equal to the lower limit of the above range, the heat stabilization effect may be insufficient, and if the content of the heat stabilizer exceeds the upper limit of the above range, the effect will reach its 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-hydroxyphenylpropionamide), 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 ″-(mesi Tylene-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 and the like.

  Among them, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate preferable. Specific examples of such phenolic antioxidants include, for example, “Irganox 1010” and “Irganox 1076” manufactured by Ciba Specialty Chemicals, “Adekastab AO-50” and “Adekastab” manufactured by Adeka. AO-60 "etc. are mentioned.

  In addition, 1 type may contain antioxidant and 2 or more types may contain it by arbitrary combinations and a ratio.

  The content of the antioxidant in the thermoplastic resin composition of the present invention is usually 0.001 part by mass or more, preferably 0.01 part by mass or more with respect to 100 parts by mass of the thermoplastic resin, and usually 1 part by mass or less, preferably 0.5 part by mass or less. When the content of the antioxidant is not more than the lower limit of the above range, the effect as the antioxidant may be insufficient, and when the content of the antioxidant exceeds the upper limit of the above range, There is a possibility that the effect reaches its peak and is not economical.

(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 15000, polysiloxane silicone oils, and the like.

  Examples of the aliphatic carboxylic acid include saturated or unsaturated aliphatic monovalent, divalent, or trivalent carboxylic acids. 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 monovalent 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 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

  The ester of an aliphatic carboxylic acid and an alcohol includes a full ester in which all of the carboxyl groups of the aliphatic carboxylic acid are esterified, and a partial ester in which a part thereof is esterified. The ester of the aliphatic carboxylic acid and alcohol used in 1 may be a full ester or a partial ester.

  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 15000 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 5000 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.

  Examples of the polysiloxane silicone oil include dimethyl silicone oil, methylphenyl silicone oil, diphenyl silicone oil, and fluorinated alkyl silicone.

  In addition, 1 type may contain the release agent mentioned above, and 2 or more types may contain it by arbitrary combinations and a ratio.

  The content of the release agent in the thermoplastic resin composition of the present invention is usually 0.001 part by mass or more, preferably 0.01 part by mass or more, and usually 100 parts by mass with respect to 100 parts by mass of the thermoplastic resin. 2 parts by mass or less, preferably 1 part by mass or less. If the content of the release agent is below the lower limit of the above range, the effect of releasability may not be sufficient, and if the content of the release agent exceeds the upper limit of the above range, hydrolysis resistance And mold contamination during injection molding may occur.

(UV 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 absorber, the thermoplastic resin composition of the present invention has good transparency and mechanical properties.

  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-butylphenyl) -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- (2N-benzotriazol-2-yl) phenol], among others, 2- (2'-hydroxy -5'-tert-octylphenyl) benzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol] 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole is particularly preferable.

  Examples of commercially available products of such benzotriazole compounds include “Seesorb 701”, “Seesorb 705”, “Seesorb 703”, “Seesorb 702”, “Seesorb 704” and “Seesorb 709” manufactured by Sipro Kasei Co., Ltd. “Biosorb 520”, “Biosorb 582”, “Biosorb 580”, “Biosorb 583”, Chemipro Kasei “Chemisorb 71”, “Chemisorb 72”, Cytec Industries “Siasorb UV5411”, Adeka “LA” -32 "," LA-38 "," LA-36 "," LA-34 "," LA-31 "," Tinubin P "," Tinubin 234 "," Tinubin 326 "," Ciba Specialty Chemicals " Tinuvin 327 "," Tinubin 328 ", etc. are mentioned.

  Specific examples of the benzophenone compound include, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-n-octoxy Benzophenone, 2-hydroxy-n-dodecyloxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4 , 4′-dimethoxybenzophenone and the like.

  Examples of commercially available products of such benzophenone compounds include “SEASOB 100”, “SEASOLV 101”, “SEASORB 101S”, “SEASORB 102”, “SEASORB 103” manufactured by Sipro Kasei Co., Ltd., and “BioSORB 100” manufactured by Kyodo Pharmaceutical. , “Biosorb 110”, “Biosorb 130”, “Chemisorb 10”, “Chemsorb 11”, “Chemsorb 11S”, “Chemsorb 12”, “Chemsorb 13”, “Chemsorb 111”, and “UBINUL” manufactured by BASF "400", BASF "Ubinur M-40", BASF "Ubinur MS-40", Cytec Industries "Thiasorb UV9", "Thiasorb UV284", "Thiasorb UV531," "Thiasorb UV24", Adeka "Adekasta 1413 "," ADEKA STAB LA-51 ", and the like.

  Specific examples of the salicylate compound include, for example, phenyl salicylate, 4-tert-butylphenyl salicylate and the like. Examples of commercially available salicylate compounds include, for example, “Seesorb 201” and “Seesorb 202” manufactured by Sipro Kasei Co., Ltd. “, Chemisorb 21”, “Chemisorb 22” manufactured by Chemipro Kasei Co., Ltd., and the like.

  Specific examples of the cyanoacrylate compound include, for example, ethyl-2-cyano-3,3-diphenyl acrylate, 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate, and the like. Examples of commercially available products include “Seasorb 501” manufactured by Sipro Kasei Co., Ltd., “Biosorb 910” manufactured by Kyodo Pharmaceutical Co., Ltd., “Ubisolator 300” manufactured by Daiichi Kasei Co., Ltd., “Ubinur N-35”, “Ubinur N-539” manufactured by BASF. Or the like.

  Specific examples of the oxanilide compound include, for example, 2-ethoxy-2′-ethyl oxalinic acid bis-arinide and the like. Examples of commercially available products of such oxalinide compounds include “Sanduboa VSU” manufactured by Clariant Corporation. Or the like.

  As the malonic acid ester compound, 2- (alkylidene) malonic acid esters are preferable, and 2- (1-arylalkylidene) malonic acid esters are more preferable. Examples of such commercially available malonic acid ester compounds include “PR-25” manufactured by Clariant Japan, “B-CAP” manufactured by Ciba Specialty Chemicals, and the like.

  The content of the ultraviolet absorber in the thermoplastic resin composition of the present invention is usually 0.01 parts by mass or more, preferably 0.1 parts by mass or more, and usually 100 parts by mass with respect to the thermoplastic resin. 3 parts by mass or less, preferably 1 part by mass or less. If the content of the UV absorber is below the lower limit of the above range, the effect of improving the weather resistance may be insufficient, and if the content of the UV absorber exceeds the upper limit of the above range, the mold Debogit etc. may occur and cause mold contamination. In addition, 1 type may contain the ultraviolet absorber and 2 or more types may contain it by arbitrary combinations and a ratio.

(Dye and pigment)
Examples of the dye / pigment include inorganic pigments, organic pigments, and organic dyes.

  Examples of the inorganic pigment include carbon black; sulfide pigments such as cadmium red and cadmium yellow; silicate pigments such as ultramarine blue; titanium oxide, zinc white, petal, chromium oxide, iron black, titanium yellow, zinc Oxide pigments such as iron brown, titanium cobalt green, cobalt green, cobalt blue, copper-chromium black and copper-iron black; chromic pigments such as chrome lead and molybdate orange; Examples include Russian pigments.

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

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

  In addition, 1 type may contain the dye / pigment, and 2 or more types may contain it by arbitrary combinations and a ratio. In addition, dyes and pigments may be used as masterbatches with polystyrene resins, polycarbonate resins, and acrylic resins for the purpose of improving handling during extrusion and improving dispersibility in the resin composition. Good.

The content of the dye / pigment in the thermoplastic resin composition of the present invention is usually 5 parts by mass or less, preferably 3 parts by mass or less, more preferably 2 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin. If the content of the dye / pigment is too large, the impact resistance may not be sufficient.
Statement text

(Fibrous reinforcement)
Examples of the fibrous reinforcing material include glass fiber, carbon fiber, various metal fibers, whiskers, and the like that are used as a reinforcing material for thermoplastic resins, and it is preferable to use glass fiber or carbon fiber.

  By blending a fibrous reinforcing material with the thermoplastic resin composition of the present invention, a resin composition that gives a molded product having high mechanical strength required for electrical, electronic equipment, OA equipment, etc. can be obtained. .

  Since the diameter of the fibrous reinforcing material is large and lacks flexibility, and it is difficult to obtain a thin one less than 1 μm, the average diameter of the fibrous reinforcing material (average fiber diameter) is usually 1 to 100 μm, preferably Is 2 to 50 μm, and it is preferable to use a fibrous reinforcing material having an average diameter of 3 to 30 μm, particularly 5 to 20 μm, because it is easily available and has a large effect as a reinforcing material.

  The length of the fibrous reinforcing material is preferably 0.1 mm or more from the viewpoint of the reinforcing effect. The upper limit of the length of the fibrous reinforcing material is usually 20 mm, and even if a longer one is used, it is usually broken and shortened when preparing a resin composition by melt-kneading. Preferably, a fibrous reinforcing material having an average length of 0.3 to 5 mm is used.

  A fibrous reinforcing material is usually used as a chopped strand obtained by cutting a number of these fibers into a predetermined length. In addition, since mixing | blending of carbon fiber provides electroconductivity to a resin composition, when a high resistance resin composition is desired, glass fiber is used.

  When a fibrous reinforcing material is blended in the thermoplastic resin composition of the present invention, the content of the fibrous reinforcing material in the thermoplastic resin composition is usually 5 to 100 parts by mass with respect to 100 parts by mass of the thermoplastic resin. is there. When the content of the fibrous reinforcing material is less than 5 parts by mass, the reinforcing effect is small, and when it exceeds 100 parts by mass, mechanical properties such as impact resistance of the resin composition are lowered. The preferable content of the fibrous reinforcing material in the thermoplastic resin composition of the present invention is 10 to 70 parts by mass, particularly 15 to 50 parts by mass with respect to 100 parts by mass of the thermoplastic resin.

(Optical function adjusting material)
The optical function adjusting material functions to improve the light shielding properties, whiteness, light reflection characteristics and the like of the molded product obtained from the thermoplastic resin composition of the present invention. Specifically, titanium oxide is used.

  The production method, crystal form, average particle size and the like of titanium oxide used in the present invention are not particularly limited, but are preferably as follows.

  There are sulfuric acid method and chlorine method in the production method of titanium oxide, but titanium oxide produced by sulfuric acid method tends to be inferior in whiteness of the composition to which this is added. In order to achieve this effectively, those produced by the chlorine method are suitable.

  Further, the crystal form of titanium oxide includes a rutile type and an anatase type, but a rutile type crystal form is preferable from the viewpoint of light resistance.

The average particle diameter of titanium oxide is usually 0.1 to 0.7 μm, preferably 0.1 to 0.4 μm. When the average particle diameter of titanium oxide is less than 0.1 μm, the resulting molded article has poor light shielding properties. When it exceeds 0.7 μm, the surface of the molded article is roughened, and the mechanical strength of the molded article is reduced. Or Here, the average particle diameter of titanium oxide is an average value of primary particle diameters measured and observed by a transmission electron microscope (TEM).
In the present invention, two or more types of titanium oxide having different average particle diameters may be mixed and used.

The titanium oxide used in the present invention may be surface-treated.
Examples of the surface treatment agent used in this case include an organosiloxane surface treatment agent. Prior to the surface treatment with the organosiloxane surface treatment agent, an alumina surface treatment agent or an alumina surface treatment agent and a silicic acid type surface treatment agent are used. Pretreatment with a surface treatment agent is preferred. Titanium oxide pretreated with an alumina surface treatment agent and, if necessary, a silicic acid surface treatment agent is further surface treated with an organosiloxane surface treatment agent, greatly improving thermal stability. In addition, it is possible to improve the uniform dispersibility in the thermoplastic resin composition and the stability of the dispersed state.

  Here, alumina hydrate is preferably used as the alumina-based surface treatment agent. As the silicic acid-based surface treatment agent, silicic acid hydrate is preferably used. The pretreatment method is not particularly limited, and any method can be used. Pretreatment with an alumina-based surface treatment agent such as alumina hydrate and, if necessary, a silicic acid-based surface treatment agent such as silicic acid hydrate is preferably performed in a range of 1 to 15% by mass with respect to titanium oxide. . That is, when the pretreatment is performed only with the alumina-based surface treatment agent, the alumina-based surface treatment agent is preferably used in an amount of 1 to 15% by mass with respect to the titanium oxide-based additive. When using a silicic acid system surface treating agent together, it is preferable to carry out using these so that these may become 1-15 mass% with respect to a titanium oxide type additive. In addition, when using together an alumina type surface treating agent and a silicic acid type surface treating agent, the use ratio is 35-90 mass of silicic acid type surface treating agents with respect to the sum of an alumina type surface treating agent and a silicic acid type surface treating agent. It is preferable that the amount be about%.

  On the other hand, a polyorganohydrogensiloxane compound is preferably used as the organosiloxane surface treating agent.

Surface treatment methods using an organosiloxane surface treatment agent for titanium oxide include a wet method and a dry method.
The wet method is a method in which a pretreated titanium oxide is added to a mixed liquid of an organosiloxane surface treating agent and a solvent, and after stirring, the solvent is removed, followed by heat treatment at 100 to 300 ° C. The dry method is a method in which pretreated titanium oxide and an organosiloxane surface treatment agent are mixed with a Henschel mixer or the like, and an organic solvent of an organosiloxane surface treatment agent is sprayed on and adhered to the pretreated titanium oxide, The method of heat-processing at 100-300 degreeC etc. are mentioned.

  The degree of surface treatment of the pretreated titanium oxide-based additive with the organosiloxane surface treatment agent is not particularly limited, but considering the reflectivity of titanium oxide, the moldability of the resulting resin composition, etc. The amount of the organosiloxane surface treatment agent for titanium oxide is usually in the range of 1 to 5% by mass.

  In the thermoplastic resin composition of the present invention, when titanium oxide is used as the optical function adjusting material, the blending amount thereof is in the range of 3 to 30 parts by mass with respect to 100 parts by mass of the thermoplastic resin. When the compounding amount of titanium oxide is less than 3 parts by mass, the resulting molded article has insufficient light shielding properties and reflection characteristics, and when it exceeds 30 parts by mass, impact resistance is insufficient. The preferable compounding quantity of a titanium oxide is 3-25 mass parts with respect to 100 mass parts of thermoplastic resins, More preferably, it is 5-20 mass parts. Here, the mass of titanium oxide means a mass including an alumina-based, silicic acid-based, or organosiloxane-based surface treatment agent obtained by surface-treating titanium oxide.

[7. Production method of thermoplastic resin composition]
There is no restriction | limiting in the manufacturing method of the thermoplastic resin composition of this invention, The manufacturing method of a well-known thermoplastic resin composition can be employ | adopted widely.
Specific examples include thermoplastic resins, fluoropolymers, polycarbosilane compounds that are fluoropolymer dispersants, flame retardants blended as necessary, and other components such as tumblers and Henschel mixers. And a method of melt-kneading using a mixer such as a Banbury mixer, roll, Brabender, single-screw kneading extruder, twin-screw kneading extruder, and kneader.

  Also, for example, the thermoplastic resin composition of the present invention is produced without mixing each component in advance, or by mixing only a part of the components in advance and supplying the mixture to an extruder using a feeder and melt-kneading the mixture. You can also

  In addition, for example, a resin composition obtained by mixing some components in advance and supplying to an extruder and melt-kneading is used as a master batch, and this master batch is mixed with the remaining components again and melt-kneaded. Thus, the thermoplastic resin composition of the present invention can also be produced.

  In addition, for example, when mixing a component that is difficult to disperse, the component that is difficult to disperse is dissolved or dispersed in a solvent such as water or an organic solvent in advance, and kneaded with the solution or the dispersion. It can also improve sex.

[8. Thermoplastic resin molded body]
The thermoplastic resin composition of the present invention can be usually molded into an arbitrary shape and used as a thermoplastic resin molded article. There is no restriction | limiting in the shape, pattern, color, dimension, etc. of this molded object, What is necessary is just to set arbitrarily according to the use of the molded object.

  Examples of molded products include electrical and electronic equipment, OA equipment, information terminal equipment, machine parts, home appliances, vehicle parts, building components, various containers, leisure goods and miscellaneous goods, parts for lighting equipment, automobiles, electrical equipment In the field of electronics and other precision equipment, various infrared sensor welding members, various sensor devices for automobiles such as face detection devices, rain sensors, various security devices such as face authentication devices, fingerprint authentication devices, vein authentication devices, Sensor device members typified by various information / communication devices such as a remote control and an infrared communication device.

  The manufacturing method of a molded object is not specifically limited, The molding method generally employ | adopted about the thermoplastic resin composition can be employ | adopted arbitrarily. For example, injection molding method, ultra-high speed injection molding method, injection compression molding method, two-color molding method, hollow molding method such as gas assist, molding method using heat insulating mold, rapid heating mold were used. Molding method, foam molding (including supercritical fluid) method, insert molding method, IMC (in-mold coating molding) molding method, extrusion molding method, sheet molding method, thermoforming method, rotational molding method, laminate molding method, press molding Law. A molding method using a hot runner method can also be used.

  The thermoplastic resin molded article of the present invention formed by molding the thermoplastic resin composition of the present invention can be obtained by blending the fluoropolymer with the melt characteristics of the thermoplastic resin and the sliding properties without impairing the original excellent properties of the thermoplastic resin. It has improved surface properties such as mobility, scratch resistance, water repellency, oil repellency, stain resistance, fingerprint resistance, and flame resistance, and can be used in a wide range of fields as a practical molded body. Is possible.

  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.

[Examples 1-18, Comparative Examples 1-3]
<Manufacture of resin pellets>
Each component described in Tables 2a and 2b to be described later is blended at a ratio (mass ratio) described in Tables 3 and 4 and mixed for 20 minutes with a tumbler, and then manufactured by Nippon Steel Works (TEX30HSST) equipped with 1 vent. And kneaded under the conditions of a screw speed of 200 rpm, a discharge rate of 15 kg / hour, and a barrel temperature of 290 ° C. Thereafter, the molten resin extruded in a strand shape was quenched in a water bath and pelletized using a pelletizer to obtain a pellet of a polycarbonate resin composition.

<Preparation of test piece>
After the pellets obtained by the above-described production method were dried at 120 ° C. for 5 hours, a cylinder temperature of 280 ° C., a mold temperature of 80 ° C., and a molding cycle of 55 were used using a M150AII-SJ type injection molding machine manufactured by Meiki Seisakusho. Injection molding was performed under the conditions of seconds, and a flat test piece (90 mm × 50 mm × 1 mm thickness) was molded.
Similarly, after drying the pellets obtained by the above-described production method at 120 ° C. for 5 hours, using a J50-EP type injection molding machine manufactured by Nippon Steel, a cylinder temperature of 290 ° C. and a mold temperature of 80 ° C. Then, injection molding was performed under the condition of a molding cycle of 30 seconds, and a test piece for UL test having a length of 125 mm, a width of 13 mm, and a thickness of 1.2 mm was molded.

<Near-infrared transmittance evaluation>
Using the above-mentioned flat test piece (thickness 1 mm) as a test piece, the light transmittance (nearly near infrared region) of 800 nm to 1500 nm using a spectral light transmittance measuring device “UV-3100” manufactured by Shimadzu Corporation. Infrared transmittance) was measured. The results are shown in Tables 3 and 4.

<Flame retardance evaluation>
The above-mentioned UL test specimen is conditioned for 48 hours in a temperature-controlled room at 23 ° C. and 50% humidity, and the UL94 test (equipment of plastic materials for equipment parts) is established by the US Underwriters Laboratories (UL). The flame retardancy was evaluated according to a combustion test.
UL94V is a method for evaluating flame retardancy from the after-flame time and drip properties after indirect flame of a burner for 10 seconds on a test piece of a predetermined size held vertically, V-0, V- In order to have flame retardancy of 1 and V-2, it is necessary to satisfy the criteria shown in Table 1 below.

Here, the after-flame time is the length of time for which the flammable combustion of the test piece is continued after the ignition source is moved away. The cotton ignition by the drip is determined by whether or not the labeling cotton, which is about 300 mm below the lower end of the test piece, is ignited by a drip from the test piece. Further, when any one of the five samples did not satisfy the above criteria, it was evaluated as NR (not rated) because V-2 was not satisfied.
The results are shown in Tables 3 and 4.

  From the above results, it can be seen that the near-infrared transmittance and flame retardancy can be improved by blending a polycarbosilane compound as the fluoropolymer dispersant.

[Examples 19 and 20, Comparative Examples 4 and 5]
<Manufacture of resin pellets>
The components described in Tables 2a and 2b described above were blended at the ratios (mass ratios) described in Tables 5 and 6, mixed for 20 minutes with a tumbler, and then manufactured by Nippon Steel Works (TEX30HSST) equipped with 1 vent. And kneaded under the conditions of a screw speed of 200 rpm, a discharge rate of 15 kg / hour, and a barrel temperature of 290 ° C. Thereafter, the molten resin extruded in a strand shape was quenched in a water bath and pelletized using a pelletizer to obtain a pellet of a polycarbonate resin composition.

<Fluidity evaluation>
・ MVR (Melt Volume Rate)
The pellets obtained by the above production method were dried at 120 ° C. for 4 hours or more, and then measured under the conditions of a measurement temperature of 300 ° C. and a measurement load of 1.2 kgf (11.8 N) in accordance with ISO 1133. This is shown in FIG.

-Q value After drying the pellet obtained by the above-mentioned manufacturing method at 120 degreeC for 4 hours or more, using a high load type flow tester by the method of JIS K7210 appendix C, conditions of 280 degreeC and a load of 160 kgf The flow rate Q value (unit: x10 ⁻² cm ³ / sec) per unit time of the composition was measured below to evaluate the fluidity. An orifice having a diameter of 1 mm and a length of 10 mm was used. It shows that it is excellent in fluidity | liquidity, so that Q value is high. The results are shown in Table 6.

<Preparation of test piece>
After drying the pellets obtained by the above-mentioned production method at 120 ° C. for 5 hours, using a J50-EP type injection molding machine manufactured by Nippon Steel, the cylinder temperature is 280 ° C. when no fibrous reinforcing material is included. When the mold temperature is 80 ° C. and the molding cycle is 30 seconds, and the fibrous reinforcing material is included, the cylinder temperature is 300 ° C., the mold temperature is 110 ° C., and the molding cycle is 30 seconds. Then, a test piece for UL test having a thickness of 1.58 mm or 1.2 mm was formed.
Moreover, after drying the pellet obtained by the above-mentioned manufacturing method at 120 ° C. for 5 hours, using an M150AII-SJ type injection molding machine manufactured by Meiki Seisakusho, cylinder temperature 280 ° C., mold temperature 80 ° C., molding Injection molding was performed under the condition of a cycle of 55 seconds, and a flat test piece (three-stage thickness of 90 mm × 50 mm × 1-2-3 mm) was molded.
Similarly, after drying the pellets obtained by the above-described production method at 120 ° C. for 5 hours, the fibrous reinforcing material was added using a CYCAP M-2 manufactured by Sumitomo Heavy Industries, Ltd. and a clamping force 75T. If not included, the cylinder temperature is 280 ° C, the mold temperature is 80 ° C, and the molding cycle is 45 seconds. If the fibrous reinforcement is included, the cylinder temperature is 300 ° C, the mold temperature is 110 ° C, and the molding cycle is 45 seconds. Molding was performed to form an ISO multipurpose test piece (4 mm) and an ISO multipurpose test piece (3 mm).

<Flame retardance evaluation>
Using the above-described UL test specimen, the UL test was performed in the same manner as in Example 1, and the evaluation was performed in the same manner.
The results are shown in Tables 5 and 6.

<Reflectance evaluation>
The above-mentioned flat test piece (1-2-3 mm thick three-stage thickness) was used as a test piece, and the reflectance was measured using a 3 mm thick portion. The measurement was performed using a spectrocolorimeter CM3600d manufactured by Konica Minolta Co., Ltd., in a D65 / 10-degree field of view and SCI normal measurement mode, and evaluated by the reflectance value at a wavelength of 440 nm. The results are shown in Table 6.

<Heat resistance evaluation>
Using an ISO multipurpose test piece (4 mm), the deflection temperature under load was measured under the condition of a load of 1.80 MPa in accordance with ISO75-1 and ISO75-2. The results are shown in Tables 5 and 6. In Tables 5 and 6, it is expressed as “DTUL”.

<Bending characteristic evaluation>
Using an ISO multipurpose test piece (4 mm), bending stress and bending elastic modulus were measured at 23 ° C. in accordance with ISO178. The results are shown in Tables 5 and 6.

<Impact resistance evaluation>
Using an ISO multipurpose test piece (3 mm), Charpy impact strength (unit: kJ / m ² ) with a notch was measured at 23 ° C. in accordance with ISO 179. The results are shown in Tables 5 and 6.

From Table 5, it can be seen that the bending characteristics are improved by blending the fibrous reinforcing material.
From Table 6, it can be seen that the reflectance can be increased by blending titanium oxide.

  The present invention can be used in a wide range of industrial fields. For example, electrical and electronic equipment and parts thereof, OA equipment, information terminal equipment, mechanical parts, home appliances, vehicle parts, building members, various containers, and leisure goods. -Miscellaneous goods, lighting equipment, and various automotive sensor devices such as near infrared laser welding members, face orientation detection devices, rain sensors, and face authentication devices in the fields of automobiles, electrical equipment / electronics, and other precision equipment, It is suitable for use in the fields of various security devices such as fingerprint authentication devices and vein authentication devices, sensor device members typified by various information / communication devices such as remote controllers and infrared communication devices.

Claims (16)

  A thermoplastic resin composition comprising a thermoplastic resin, a fluoropolymer, and a fluoropolymer dispersant, wherein the fluoropolymer dispersant comprises a polycarbosilane compound. The polycarbosilane compound has a main chain structure composed of at least one structural unit of structural units represented by the following formulas (1) to (3) and a hydrocarbon residue. Item 2. The thermoplastic resin composition according to Item 1.

(In formulas (1) to (3), R ¹ , R ² , and R ³ each independently represent a monovalent hydrocarbon group, a hydrogen atom, or a silyl group, and a, b, and c are each independently , 0 or 1. The plurality of R ¹ , R ² and R ³ contained in the main chain structure may be the same or different.   The thermoplastic resin composition according to claim 2, wherein the hydrocarbon residue is a divalent hydrocarbon group. The thermoplastic resin composition according to claim 3, wherein the polycarbosilane compound is a polycarbosilane compound having a repeating unit represented by the following formula (4) and having a number average molecular weight of 100 to 20000. .

(In the formula (4), R ¹ , R ² , a and b are as defined in the formula (1), A ¹ represents a divalent hydrocarbon group having 1 to 12 carbon atoms, p, q Each independently represents an integer of 1 to 8. R ¹ , R ² and A ¹ may be the same or different in all repeating units. The thermoplastic resin composition according to claim 4, wherein the polycarbosilane compound is a polycarbosilane compound having a repeating unit represented by the following formula (5) and having a number average molecular weight of 100 to 20000. .

(In the formula ^{(5), R 1, R} 2 have the same meanings as in the formula (4), ^{A 2} is ^.R 1, ^{R 2} and ^{A 2} which represents an alkylene group having 1 to 12 carbon atoms, each and every In the repeating unit, they may be the same or different.) 6. The thermoplastic resin composition according to claim 5, wherein the polycarbosilane compound is a polycarbosilane compound having a repeating unit represented by the following formula (6) and having a number average molecular weight of 100 to 20000. .

  The fluoropolymer is contained in an amount of 0.001 to 3 parts by mass and a fluoropolymer dispersant in an amount of 0.005 to 10 parts by mass with respect to 100 parts by mass of the thermoplastic resin. The thermoplastic resin composition described in 1.   The thermoplastic resin composition according to any one of claims 1 to 7, wherein the fluoropolymer is a fluoroolefin polymer having a fibril-forming ability.   Furthermore, a flame retardant is contained, The thermoplastic resin composition of any one of the Claims 1 thru | or 8 characterized by the above-mentioned.   The thermoplastic resin composition according to claim 9, wherein 0.001 to 30 parts by mass of the flame retardant is contained with respect to 100 parts by mass of the thermoplastic resin.   The thermoplastic resin composition according to claim 9 or 10, wherein the flame retardant is a metal salt compound.   The thermoplastic resin composition according to claim 11, wherein the metal salt compound is an alkali metal salt of an organic sulfonic acid.   The heat according to claim 12, wherein the alkali metal salt of the organic sulfonic acid is at least one selected from an alkali metal salt of a fluorinated aliphatic sulfonic acid and an alkali metal salt of an aromatic sulfonic acid. Plastic resin composition.   The thermoplastic resin composition according to claim 13, wherein the alkali metal salt of the fluorinated aliphatic sulfonic acid is an alkali metal salt of perfluoroalkanesulfonic acid.   The thermoplastic resin composition according to any one of claims 1 to 14, wherein the thermoplastic resin is a polycarbonate resin.   A thermoplastic resin molded article obtained by molding the thermoplastic resin composition according to any one of claims 1 to 15.