TW201540774A - Resin composition - Google Patents

Abstract

The purpose of the present invention is to provide a thermoplastic resin composition having exceptional heat stability as well as excellent mechanical strength and exceptional chemical resistance. The present invention is a resin composition containing 1-10 parts by weight of (C) a core-shell polymer (component C) that comprises a core (component C-1) comprising a cross-linked acrylic-acid-ester-based elastic material configured from an acrylic acid ester having C1-4 alkyl groups and an acrylic acid ester having C5-8 alkyl groups, and a shell (component C-2) having a methacrylic acid ester as the main component, and 8-15 parts by weight of (D) a filler (component D), per 100 parts by weight of a resin component comprising 80-50 parts by weight of (A) a polycarbonate resin (component A) and 20-50 parts by weight of (B) a polyester resin (component B).

Description

Resin composition

The present invention relates to a resin composition and a molded article comprising a polycarbonate resin, a polyester resin, a core-shell polymer having a specific structure, and a filler. More specifically, the present invention relates to a thermoplastic resin which is produced by using a polyester resin produced by a catalyst comprising a specific element and which is excellent in thermal stability, more excellent in mechanical strength, and chemical resistance. Composition.

A resin composition comprising a polycarbonate resin, a polyester resin, a filler, and an impact modifier, because it maintains excellent appearance characteristics, mechanical properties, dimensional stability, and chemical resistance of the polycarbonate resin, It has a rigid resin composition and can be widely used in electrical, electronic, mechanical, OA, vehicle, and medical applications. Further, a molded article comprising a resin composition of a polycarbonate resin, a polyester resin, and a filler (hereinafter also referred to as a PC/PEST/filler alloy) is suitable for a coated member or Since the member used in the uncoated state is particularly useful for vehicle use, OA use, etc., various studies are being conducted.

In recent years, in the field of vehicles and the field of OA, speed reduction of parts and cost reduction are being accelerated. For example, in the use of vehicles, the development of "a resin material as a large-sized part represented by a body panel such as a baffle or a rear door" has become hot. From the above-mentioned excellent characteristics, PC/PEST/filling The material alloy is a preferred resin material. However, and so far Since the heat resistance is not good compared with the material of the steel plate or the like used, the applicable parts and dimensions are limited, and the use thereof is also limited.

In addition, the thinning of parts for the purpose of weight reduction and the trend of reducing the number of parts and modularizing parts in order to reduce costs are accelerating, and in order to easily obtain thinner, more complicated and large-sized molded articles, it is required to improve. Processing characteristics. Further, a method of increasing the forming temperature to improve the fluidity for forming is generally a method of improving the processing characteristics by using an existing apparatus, and therefore, it is required to have better thermal stability. Therefore, in order to achieve lighter parts and lower costs, it is more strongly required that PC/PEST/filler alloys have better resistance to heat and humidity and thermal stability.

Further, in the field where vehicle components, machinery, buildings, and the like require special mechanical strength, it is strongly required to have both rigidity and impact resistance.

In Patent Document 1, in order to improve the heat and humidity resistance of a resin composition containing a polycarbonate resin and a polyester resin, a technique of blending an inorganic compound containing aluminum silicate as a main component has been developed. In addition to the increase in the cost of the resin composition and the number of steps in the production of the resin composition, the addition of the additive also has a problem that the specific purpose is increased, and the original effect, that is, the effect of weight reduction is deteriorated. Also, although thermal stability may be lowered, any finding regarding thermal stability is not shown, and it is technically difficult to say that it is fully discussed.

Patent Document 2 discusses a technique of incorporating a phosphite-based antioxidant into a PC/PEST/filler alloy. According to this technique, the decomposition of the resin during the forming process can be suppressed, but the discussion on the heat and humidity resistance is not performed, and the technical requirements are further improved.

Patent Document 3 discusses a technique of blending an acidic phosphorus-based additive with an inorganic filler having a moisture content of 0.25 wt% or less in a PC/PEST alloy. Although the melt stability is improved by blending a filler having a water content of 0.25 wt% or less, the blended inorganic filler is managed. The amount of water means that the steps in the production of the resin composition increase, resulting in an increase in cost, which cannot be said to be a general-purpose technique. Further, there is no discussion about the heat and humidity resistance of the obtained resin composition, and technical improvement is required.

In Patent Document 4, a technique of controlling the dispersion state to form a pH of 8.0 or more and having no "SiO ₂ unit accounts for 30% by weight or more of the inorganic compound" in the polycarbonate resin is considered. According to this technique, although it was confirmed that the thermal stability during the forming process can be improved, there is no discussion about the heat and humidity resistance. Moreover, in order to obtain this resin composition, there is a possibility that restrictions are imposed in the production method, and as a result, the number of manufacturing steps increases and the cost increases, and it is difficult to say that it is a highly versatile technology.

In order to improve the heat and humidity resistance of the PC/PEST/filler alloy and to improve the thermal stability, the method of blending the additive and the method of controlling the dispersion state of the filler material are difficult to have both moist heat resistance and heat stability, and It has become the main cause of rising costs, so it requires more advanced technology.

Under such circumstances, as a method for satisfying the above requirements for the PC/PEST/filler alloy, it has been proposed to use an alloy material of PET (polyethylene terephthalate) produced by a specific polymerization catalyst (refer to the patent). Literature 5-7). Patent Document 5 proposes to improve the color tone, melt stability, appearance, and moldability of PET produced by a general ruthenium compound or a titanium compound by using a ruthenium catalyst as a polymerization catalyst. However, this technology does not fully satisfy the high thermal stability required in today's vehicles and OA applications, and cannot be used as knowledge related to heat and humidity resistance.

Patent Document 6 proposes to improve color tone, thermal stability, and melt stability by including "a polyester resin produced by using a titanium-containing catalyst compound of 1 to 30 ppm." By reducing the amount of catalyst, although it can improve thermal stability and melt stability, it has heat as the amount of polyester resin increases. The tendency to reduce stability requires more improvement. Again, no knowledge of heat and humidity resistance is suggested.

Patent Document 7 discloses that a polyester resin having a good color tone (b value), a small amount of impurities, and excellent thermal stability during melting can be obtained by using a titanium-containing catalyst compound having a specific structure to produce a polyester resin. However, there is no mention of the effect on the "resin composition containing a resin other than the polyester resin", nor does it suggest any knowledge related to the heat and humidity resistance.

In Patent Document 8, a filler and an impact modifier are used in combination as a method for satisfying the requirements of mechanical strength of a PC/PEST/filler alloy. Although the strength and rigidity are improved by this technique, the effect of improving the rigidity of the impact modifier is not discussed, and it must be technically improved.

Therefore, a polycarbonate resin composition and a molded article which are excellent in mechanical strength such as good heat and humidity resistance, thermal stability, rigidity, and impact resistance are not provided.

(Patent Document 1) Japanese Patent Laid-Open No. Hei 10-237295

(Patent Document 2) Japanese Patent Laid-Open No. Hei 5-222283

(Patent Document 3) Japanese Patent Laid-Open Publication No. 2002-121366

(Patent Document 4) Japanese Patent Laid-Open Publication No. 2000-313799

(Patent Document 5) Japanese Patent Laid-Open No. 51-102043

(Patent Document 6) Japanese Patent Publication No. 2005-521772

(Patent Document 7) WO 03/008479

(Patent Document 8) Japanese Patent Publication No. 9-286904

The object of the present invention is to provide a polycarbonate resin, a polyester resin, A resin composition excellent in mechanical strength such as an impact modifier and a tensile modulus and a Charpy impact strength. Further, an object of the present invention is to provide a resin composition excellent in moist heat resistance and thermal stability. Moreover, an object of the present invention is to provide a molded article comprising the resin composition, in particular, a vehicle interior member and a vehicle exterior member.

As a result of repeated discussions in detail to achieve the above object, the inventors of the present invention found that, as shown in the first and second figures, a polyester resin and a core-shell polymer having a specific structure are blended in a polycarbonate resin. A resin composition excellent in tensile modulus and sand impact strength can be obtained. Further, the obtained resin composition exhibits excellent moist heat resistance and thermal stability, and the present invention has been completed.

According to the present invention, the above problems can be attained by a resin composition comprising: (A) a polycarbonate resin (component A); (B) a polyester resin (component B); and (C) a core. a shell polymer (component C); and (D) a filler (component D); wherein, relative to (A) polycarbonate resin (component A) 80 to 50 parts by weight and (B) polyester resin (component B) 20 100 parts by weight of the resin composition of the composition, (C) the core-shell polymer (component C) is 1 to 10 parts by weight, and (D) the filler (component D) is 0 to 15 parts by weight; (C) The core-shell polymer (component C) is a core composed of a crosslinked acrylate-based elastomer composed of an acrylate having an alkyl group having 1 to 4 carbon atoms and an acrylate having an alkyl group having 5 to 8 carbon atoms ( C-1 component)" and "shell (C-2 component) containing methacrylate as a main component".

The first figure is a comparison between Example 2 and Comparative Examples 6-8.

The second figure is a comparison between Example 12 and Comparative Examples 9-11.

Hereinafter, the present invention will be described in more detail.

(Component A: polycarbonate resin)

The polycarbonate resin used as the component A of the present invention is obtained by reacting a divalent phenol with a carbonate precursor. Examples of the reaction method include an interfacial polymerization method, a melt transesterification method, a solid transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound.

Representative examples of the divalent phenol used herein include hydroquinone, resorcin, 4,4'-biphenol, 1,1-bis(4-hydroxyphenyl)ethane, 2,2. - bis(4-hydroxyphenyl)propane (commonly known as bisphenol A), 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)- 3,3,5-trimethylcyclohexane, 2,2-bis(4-hydroxyphenyl)pentane, 4,4'-(p-phenylenediisopropane)diphenol, 4,4 '-(m-phenylenediisopropane)diphenol, 1,1-bis(4-hydroxyphenyl)-4-isopropylcyclohexane, bis(4-hydroxyphenyl)oxide, double (4-hydroxyphenyl) sulfide, bis(4-hydroxyphenyl)arylene, bis(4-hydroxyphenyl)anthracene, bis(4-hydroxyphenyl)one, bis(4-hydroxyphenyl)ester , bis(4-hydroxy-3-methylphenyl) sulfide, 9,9-bis(4-hydroxyphenyl)anthracene, 9,9-bis(4-hydroxy-3-methylphenyl)anthracene, etc. . A preferred divalent phenol is bis(4-hydroxyphenyl)alane, and among them, bisphenol A is particularly preferable from the viewpoint of impact resistance.

In the present invention, in addition to a general-purpose polycarbonate, that is, a bisphenol A-based polycarbonate, a special polycarbonate produced from other divalent phenols is also used as the component A.

For example, as part or all of the divalent phenol component, 4,4'-(m-phenylenediisopropane)diphenol (hereinafter abbreviated as BPM) and 1,1-bis(4-hydroxyphenyl) ring are used. Hexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (hereinafter referred to as Bis-TMC), 9,9-bis(4-hydroxyphenyl)fluorene, and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene (hereinafter abbreviated as BCF) polycarbonate (separate polymer or copolymer) suitable for dimensional change and morphological stability due to water absorption The requirements are particularly stringent. The divalent phenol other than the BPA is preferably used in an amount of 5 mol% or more, particularly 10 mol% or more, of the entire divalent phenol component constituting the polycarbonate.

In particular, in the case where high rigidity and more excellent hydrolysis resistance are required, the component B constituting the polycarbonate resin composition is particularly preferably a copolymerized polycarbonate of the following (1) to (3).

(1) The BPM of the divalent phenol component constituting the polycarbonate is 20 to 80 mol% (more preferably 40 to 75 mol%, more preferably 45 to 65 mol%), and The BCF is a copolymerized polycarbonate of 20 to 80 mol% (more preferably 25 to 60 mol%, more preferably 35 to 55 mol%).

(2) Among the 100% by mole of the divalent phenol component constituting the polycarbonate, the BPA is 10 to 95 mol% (more preferably 50 to 90 mol%, more preferably 60 to 85 mol%), and The BCF is a copolymerized polycarbonate of 5 to 90 mol% (more preferably 10 to 50 mol%, more preferably 15 to 40 mol%).

(3) Among the 100% by mole of the divalent phenol component constituting the polycarbonate, the BPM is 20 to 80 mol% (preferably 40 to 75 mol%, more preferably 45 to 65 mol%), and Bis - TMC is a copolymerized polycarbonate of 20 to 80 mole % (more preferably 25 to 60 mole %, more preferably 35 to 55 mole %).

These special polycarbonates may be used singly or in combination of two or more kinds as appropriate. Further, these compounds are also used in combination with a general bisphenol A type polycarbonate.

The preparation methods and characteristics of these special polycarbonates are, for example, detailed in the day. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei.

Further, among the above various polycarbonates, the copolymerization composition and the like are adjusted so that the water absorption ratio and the Tg (glass transition temperature) are within the following ranges, and the hydrolysis resistance of the polymer itself is good, and the warpage after molding is low. It is also particularly excellent in nature and is particularly suitable in fields requiring morphological stability.

(i) a water absorption of 0.05 to 0.15%, preferably 0.06 to 0.13%, and a Tg of 120 to 180 ° C polycarbonate; or (ii) a Tg of 160 to 250 ° C, preferably 170 to 230 ° C, and The water absorption rate is 0.10 to 0.30%, preferably 0.13 to 0.30%, and more preferably 0.14 to 0.27% of polycarbonate.

Here, the water absorption rate of the polycarbonate was measured by using a disk-shaped test piece having a diameter of 45 mm and a thickness of 3.0 mm, and immersing in water at 23 ° C for 24 hours in accordance with ISO 62-1980, and then measuring the water content. Further, Tg (glass transition temperature) is a value obtained by measuring the differential scanning calorimeter (DSC) according to JIS K7121.

As the carbonate precursor, a carbonyl halide, a carbonic acid diester or a halogenated methyl ester can be used, and specific examples thereof include a phosgene, a diphenyl carbonate or a dihalomethyl ester of a divalent phenol. Wait.

When an aromatic polycarbonate resin is produced from the divalent phenol and a carbonate precursor by an interfacial polymerization method, a catalyst, a blocking agent, an antioxidant for preventing oxidation of divalent phenol, and the like may be used depending on the demand. Further, an aromatic polycarbonate resin, a branched polycarbonate resin containing a trifunctional or higher polyfunctional aromatic compound, and an aromatic or aliphatic (including alicyclic) difunctional carboxylic acid are copolymerized. Polyester carbonate resin, copolymerization of difunctional alcohols (including alicyclic) A copolymerized polycarbonate resin and a polyester carbonate resin copolymerized with the bifunctional carboxylic acid and the bifunctional alcohol. Further, it may be a mixture of "a mixture of two or more kinds of aromatic polycarbonate resins".

The branched polycarbonate resin imparts drip resistance and the like to the resin composition of the present invention. Examples of the trifunctional or higher polyfunctional aromatic compound used in the branched polycarbonate resin include 1,3,5-benzenetriol (phloroglucin) and 1-dissorcinol-3,5-di Phloroglucide or 4,6-dimethyl-2,4,6-gin(4-hydroxyphenyl)heptene-2,2,4,6-trimethyl-2,4,6-para (4-hydroxyphenyl)heptane, 1,3,5-gin (4-hydroxyphenyl)benzene, 1,1,1-paranium (4-hydroxyphenyl)ethane, 1,1,1-parameter (3,5-Dimethyl-4-hydroxyphenyl)ethane, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol, 4-{4-[1, a phenol such as 1-bis(4-hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol; tetrakis(4-hydroxyphenyl)methane, bis(2,4-dihydroxybenzene) Ketone, 1,4-bis(4,4-dihydroxytriphenylmethyl)benzene, or trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, and the like Wherein, it is preferably 1,1,1-paraxyl (4-hydroxyphenyl)ethane, 1,1,1-paran (3,5-dimethyl-4-hydroxyphenyl)ethane, particularly preferably 1,1,1-non-(4-hydroxyphenyl)ethane.

In a total of 100 mol% of the constituent unit derived from the divalent phenol and the constituent unit derived from the polyfunctional aromatic compound, the constituent unit derived from the polyfunctional aromatic compound in the branched polycarbonate is 0.01 to 1 The molar % is preferably 0.05 to 0.9 mol%, particularly preferably 0.05 to 0.8 mol%.

Further, particularly in the case of the melt transesterification method, in the case where a branched structural unit is generated as a side reaction, the amount of the branched structural unit is 0.001 to 1 in a total of 100 mol% of the constituent units derived from divalent phenol. The molar % is preferably 0.005 to 0.9 mol%, particularly preferably 0.01 to 0.8 mol%. Further, the ratio of this branched structure can be calculated by ¹ H-NMR measurement.

The aliphatic difunctional carboxylic acid is preferably an α,ω-dicarboxylic acid. Examples of the aliphatic difunctional carboxylic acid include azelaic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, eicosanedioic acid, and the like. A linear saturated aliphatic dicarboxylic acid and an alicyclic dicarboxylic acid such as cyclohexanedicarboxylic acid. The difunctional alcohol is preferably an alicyclic diol, and examples thereof include cyclohexane dimethanol, cyclohexane diol, and tricyclodecane dimethanol.

Further, a polycarbonate-polyorganosiloxane copolymer copolymerizing a polyorganosiloxane unit can be used.

The polycarbonate resin can be produced by an interfacial polymerization method, a melt transesterification method, a solid transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound. These reaction forms are known in various literatures, patent publications, and the like.

The viscosity average molecular weight of the polycarbonate resin is preferably from 10,000 to 50,000, more preferably from 14,000 to 30,000, more preferably from 14,000 to 26,000. In a polycarbonate resin having a viscosity average molecular weight of less than 10,000, good mechanical properties cannot be obtained. On the other hand, the resin composition obtained from the polycarbonate resin having a viscosity average molecular weight of more than 50,000 has poor fluidity at the time of injection molding, which results in poor versatility.

Further, the polycarbonate resin may be obtained by mixing a viscosity average molecular weight outside the range. In particular, a polycarbonate resin having a viscosity average molecular weight exceeding the range (50,000) improves the entropy elasticity of the resin. As a result, in the gas-assisted molding and the foam molding used for forming the structural member of the reinforcing resin material, good moldability was found. This improvement in formability is better than that of the branched polycarbonate. As a preferred aspect, the A-1 component is a polycarbonate resin (component A-1-1) having a viscosity average molecular weight of 70,000 to 300,000, and a polycarbonate resin having a viscosity average molecular weight of 10,000 to 30,000 (A-1-2). It can also be used as a component) A polycarbonate resin having a viscosity average molecular weight of 16,000 to 35,000 (hereinafter referred to as "a polycarbonate resin containing a high molecular weight component").

In the polycarbonate resin containing a high molecular weight component, the molecular weight of the component A-1-1 is preferably from 70,000 to 200,000, more preferably from 80,000 to 200,000, more preferably from 100,000 to 200,000, particularly preferably from 100,000 to 160,000. Further, the molecular weight of the component A-1-2 is preferably 10,000 to 25,000, more preferably 11,000 to 24,000, more preferably 12,000 to 24,000, particularly preferably 12,000 to 23,000.

In the polycarbonate resin containing a high molecular weight component, the A-1-1 component and the A-1-2 component may be mixed in various ratios to adjust to a predetermined molecular weight range. Preferably, the high molecular weight component contains 100% by weight of the polycarbonate resin, and the A-1-1 component is 2 to 40% by weight; more preferably 3 to 30% by weight of the A-1-1 component. More preferably, it is 4 to 20% by weight of the component A-1-1, and particularly preferably 5 to 20% by weight of the component A-1-1.

In addition, as a method of preparing a polycarbonate resin containing a high molecular weight component, for example, (1) a method of separately polymerizing the A-1-1 component and the A-1-2 component, and mixing the components, (2) A method of producing a polycarbonate resin exhibiting a peak of a plurality of polymers in a molecular weight distribution diagram obtained by a GPC method, represented by a method shown in Japanese Laid-Open Patent Publication No. Hei 5-306336 a method for producing the polycarbonate resin to satisfy the conditions of the component A-1 of the present invention, and (3) a polycarbonate resin obtained by the production method (the method for producing (2)) and a separately produced A a method of mixing the -1-1 component and/or the A-1-2 component.

The viscosity average molecular weight referred to in the present invention is calculated by the following method: First, "0.7 g of a polycarbonate resin is dissolved in 100 ml of methylene chloride at 20 ° C" using an Oswald viscometer. For the solution, obtain the specific viscosity (η _sp ) calculated by the following formula; specific viscosity (η _sp )=(tt ₀ )/t ₀

[t ₀ is the number of seconds of the methylene chloride drop, t is the number of seconds of the sample solution]

From the obtained specific viscosity (η _sp ), the viscosity average molecular weight M was calculated by the following formula.

η _sp /c=[η]+0.45×[η] ² c (where [η] is the ultimate viscosity)

[η]=1.23×10 ^-4 M ^0.83

c=0.7

Moreover, the viscosity average molecular weight of the polycarbonate resin in the resin composition of the present invention is calculated by the following method. That is, the composition is mixed with a methylene chloride having a weight of 20 to 30 times to dissolve the soluble component in the composition. This soluble component was obtained by filtration through Celite. Thereafter, the solvent in the resulting solution was removed. The solid after removal of the solvent is sufficiently dried to obtain a solid component dissolved in the methylene chloride. 0.7 g of this solid was dissolved in a solution of 100 ml of methylene chloride, and then the specific viscosity at 20 ° C was determined in the same manner as above, and the viscosity average molecular weight M was calculated from the specific viscosity in the same manner as above.

(Component B: polyester resin)

The polyester resin used as the component B of the present invention is a polymer or a copolymer obtained by subjecting an aromatic dicarboxylic acid or a reactive derivative thereof to a condensation reaction of a diol or an ester derivative thereof as a main component.

The aromatic dicarboxylic acid referred to herein is preferably selected from the group consisting of "terephthalic acid, isophthalic acid, phthalic acid, 1,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-biphenyl ether dicarboxylic acid, 4,4'-biphenylmethane dicarboxylic acid, 4,4'-biphenylsulfonyl dicarboxylate Acid, 4,4'-biphenylisopropane dicarboxylic acid, 1,2-bis(phenoxy)ethane-4,4'-dicarboxylic acid, 2,5-nonanedicarboxylic acid, 2, An aromatic dicarboxylic acid such as 6-anthracene dicarboxylic acid, 4,4'-p-tri (ter) phenyldicarboxylic acid or 2,5-pyridinedicarboxylic acid, or diphenylmethanedicarboxylic acid, Diphenyl ether dicarboxylic acid and β-hydroxyethoxybenzoic acid For use, it is particularly preferred to use terephthalic acid or 2,6-naphthalene dicarboxylic acid. The aromatic dicarboxylic acid may be used in combination of two or more kinds. Further, as long as a small amount is used, the dicarboxylic acid may be one or more of an aliphatic dicarboxylic acid such as adipic acid, sebacic acid, sebacic acid or dodecanedioic acid, or cyclohexanedicarboxylic acid. An alicyclic dicarboxylic acid or the like is used in combination.

Further, examples of the diol as a component of the polyester resin include ethylene glycol, propylene glycol, butylene glycol, hexene glycol, neopentyl glycol, and pentane methylene. Aliphatic diols such as ethylene glycol, hexamethylene glycol, decaethylene glycol, 2-methyl-1,3-propanediol, diethylene glycol, triethylene glycol, etc. An alicyclic diol such as 1,4-cyclohexanedimethanol, an aromatic ring-containing diol such as 2,2-bis(β-hydroxyethoxyphenyl)propane, or the like, and the like . Further, as long as it is a small amount, one or more long-chain diols having a molecular weight of 400 to 6,000, that is, polyethylene glycol, poly-1,3-propylene glycol, and polytetramethylene glycol may be used. Equal copolymerization.

Further, the polyester resin can be branched by introducing a small amount of a branching agent. The type of the branching agent is not limited, and examples thereof include symmetric benzenetricarboxylic acid, trimellitic acid, trimethylolethane, trimethylolpropane, and pentaerythritol.

As a specific polyester resin, in addition to polyethylene terephthalate (PET), polytrimethylene terephthalate, polybutylene terephthalate (PBT), polybutylene terephthalate, Polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), polyethylene-1,2-bis(phenoxy)ethane-4,4'-dicarboxylate, etc. Other examples include copolymerized polyester resins such as polyethylene isophthalate/polyethylene terephthalate, polybutylene terephthalate/polybutylene isophthalate. Among these resins, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polybutylene naphthalate are preferably used. And mixtures of such compounds.

Further, the terminal group structure of the polyester resin is not particularly limited, and may be a case where the ratio of the hydroxyl group to the carboxyl group in the terminal group is substantially the same. Further, the terminal groups are also blocked by reacting a compound reactive with the terminal group.

The polyester is preferably produced by polymerizing a dicarbonic acid component and the diol component in the presence of a specific titanium-based catalyst in the presence of a specific titanium-based catalyst, and discharging water or a lower alcohol as a by-product out of the system. Resin.

The titanium-based catalyst described above includes a reaction product of the following titanium compound component (A) and phosphorus compound component (B).

The titanium compound component (A) is selected from the titanium compound (1) represented by the following formula (I) and the aromatic polyvalent carboxylic acid represented by the titanium compound (1) and the following formula (II) or At least one titanium compound component of the group consisting of the titanium compound (2) obtained by the acid anhydride reaction.

[wherein, in the formula (I), R ¹ , R ² , R ³ and R ⁴ each independently represent an alkyl group having 2 to 10 carbon atoms, k represents an integer of 1 to 3, and k is 2 or 3 In the case, two or three R ² and R ³ may be the same or different from each other.

[wherein, in the formula (II), m represents an integer of 2 to 4].

The phosphorus compound component (B) is a phosphorus compound component composed of at least one of the phosphorus compounds (3) represented by the following formula (III).

[In the formula (III), R ⁵ represents an unsubstituted or substituted aryl group having 6 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms].

The polyester resin produced by using the above specific titanium-based catalyst is superior in thermal stability and moist heat resistance as compared with the case of using lanthanum, cerium and other titanium-based catalysts. In the case of using the above specific titanium-based catalyst, the amount of the additive such as the hue stabilizer and the heat stabilizer added at the time of production is small, and the quality is stable, so that it can be used. It can reduce the decomposition of additives in a hot environment or in a hot and humid environment, and can be a material excellent in thermal stability and moist heat resistance.

In the reaction product of the titanium compound component (A) and the phosphorus compound component (B), the titanium compound conversion amount (mTi) of the titanium compound component (A) and the phosphorus atom conversion amount of the phosphorus compound component (B) (mP) The reaction molar ratio (mTi/mP) is preferably in the range of 1/3 to 1/1, and preferably in the range of 1/2 to 1/1.

The titanium atom conversion amount of the titanium compound component (A) is "the molar amount of each titanium compound contained in the titanium compound component (A)" and "the number of titanium atoms contained in one molecule of the titanium compound" The total value of the product; the amount of the phosphorus atom in terms of the phosphorus atom content of the phosphorus compound component (B) is "the molar amount of each phosphorus compound contained in the phosphorus compound component (B)" and "the phosphorus compound 1 molecule The total value of the product of the number of phosphorus atoms. In the phosphorus compound represented by the formula (III), since one phosphorus atom is contained per molecule, the phosphorus atom of the phosphorus compound is equivalent to the molar amount of the phosphorus compound.

When the reaction molar ratio (mTi/mP) is more than 1/1, that is, if the amount of the titanium compound component (A) is too large, the color tone of the polyester resin obtained by the obtained catalyst is deteriorated (b value) Too high) and its heat resistance is not good. When the reaction molar ratio (mTi/mP) is less than 1/3, that is, the amount of the titanium compound component (A) is too small, the catalyst activity of the resulting catalyst with respect to the polyester becomes insufficient.

The titanium compound (1) represented by the above formula (I) used in the titanium compound component (A) includes titanium tetrabutoxide, titanium tetraisopropoxide, titanium tetrapropoxide, and tetraethyl b. An alkyl titanate such as a tetraalkoxy titanium such as a oxytitanium or a decyl trititanate or a hexaalkyldititanate, and among these types, it is preferably used in the present invention. As the tetraalkoxy titanium having good reactivity of the phosphorus compound component used, titanium tetrabutoxide is particularly preferably used.

The titanium compound (2) used in the titanium compound component (A) is obtained by reacting the titanium compound (1) with an aromatic polyvalent carboxylic acid represented by the formula (II) or an anhydride thereof. The aromatic polyvalent carboxylic acid of the formula (II) and an anhydride thereof are preferably selected from the group consisting of phthalic acid, trimellitic acid, Hemimellitic acid, pyromellitic acid, and the like. Group. It is particularly preferable to use a trimellitic anhydride having a high reactivity with the titanium compound (1) and having a high affinity with the polyester of the obtained polycondensation catalyst.

The aromatic polyvalent carboxylic acid or its anhydride is mixed in a solvent, and a part or all of it is dissolved in a solvent, and the titanium compound (1) is dropped into the mixed solution, and heated at a temperature of 0 ° C to 200 ° C for 30 minutes. In the above, it is preferred to carry out the reaction of the titanium compound (1) with the aromatic polyvalent carboxylic acid of the formula (II) or an anhydride thereof by heating at a temperature of 30 to 150 ° C for 40 to 90 minutes. The reaction pressure at this time is not particularly limited, and normal pressure is sufficient. Further, the catalyst may be selected from those in which a part or all of the compound of the formula (II) or an acid anhydride thereof is appropriately selected, but is preferably selected from the group consisting of ethanol, ethylene glycol, and trimethylene. Glycol, tetramethylene glycol, benzene, xylene, and the like.

The reaction molar ratio of the titanium compound (1) to the compound represented by the formula (II) or an anhydride thereof is not limited. However, when the ratio of the titanium compound (1) is too high, "the color tone of the obtained polyester resin is deteriorated, and the softening point is lowered". On the other hand, when the ratio of the titanium compound (1) is too low, it is difficult to aggregate. The case of a condensation reaction. Therefore, the molar ratio of the reaction of the titanium compound (1) with the compound of the formula (II) or its anhydride is preferably controlled in the range of 2/1 to 2/5. The reaction product obtained by the reaction may be directly supplied to the reaction with the phosphorus compound (3), or may be recrystallized by using a solvent composed of acetone, methanol, and/or ethyl acetate to be purified. This is reacted with the phosphorus compound (3).

In the phosphorus compound (3) of the formula (III) used in the phosphorus compound component (B), an aryl group having 6 to 20 carbon atoms represented by R ⁵ or an alkane having 1 to 20 carbon atoms The group may be unsubstituted or may be substituted with one or more substituents. The substituent includes, for example, a carboxyl group, an alkyl group, a hydroxyl group, an amine group and the like.

The phosphorus compound (3) of the formula (III) includes, for example, monomethyl phosphate, monoethyl phosphate, monotrimethyl phosphate, mono-n-butyl phosphate, monohexyl phosphate, Monoheptyl phosphate, monooctyl phosphate, monodecyl phosphate, monodecyl phosphate, dodecyl phosphate, lauryl phosphate, monooleyl phosphate, single Tetradecyl phosphate, monophenyl phosphate, monobenzyl phosphate, mono(4-lauryl)phenyl phosphate, mono(4-methylphenyl)phosphate, mono(4-ethylphenyl) Phosphate, mono(4-propylphenyl)phosphate, mono(4-laurylphenyl)phosphate, monotriphosphate, monophosphoryl phosphate, monobiphenyl phosphate, mononaphthyl phosphate a monoalkyl phosphate such as an ester or a monodecyl phosphate, or a monoaryl phosphate, and these compounds may be used singly or as a mixture of two or more kinds, for example, as a monoalkyl phosphate and a monoaryl group. A mixture of phosphatidyl phosphates is used. In the case where the above phosphorus compound is used as a mixture of two or more kinds, the proportion of the monoalkyl phosphate is preferably 50% or more, more preferably 90% or more, and particularly preferably 100%.

The catalyst is prepared from the titanium compound component (A) and the phosphorus compound component (B) by, for example, mixing the phosphorus compound component (B) composed of at least one phosphorus compound (3) of the formula (III) with a solvent, one or all of the phosphorus compound component (B) is dissolved in a solvent, and the titanium compound component (A) is dropped into the mixed solution, and generally, it is preferably 50 ° C to 200 ° C, preferably 70 ° C The temperature of ~150 ° C; preferably 1 minute to 4 hours, preferably 30 minutes to 2 hours to heat the reaction system. In the reaction, the reaction pressure is not particularly limited, and may be any one under pressure (0.1 to 0.5 MPa), at normal pressure or under reduced pressure (0.001 to 0.1 MPa), but it is usually carried out under normal pressure.

Further, the solvent for the phosphorus compound component (B) of the formula (III) used in the above-mentioned catalyst preparation reaction is not particularly limited as long as it can dissolve at least a part of the phosphorus compound component (B), but is preferably selected from the group consisting of For example, a solvent composed of at least one of ethanol, ethylene glycol, trimethylene glycol, tetramethylene glycol, benzene, and xylene. It is particularly preferable to use a compound which is the same as the ethylene glycol component constituting the finally desired polyester as a solvent.

The reaction product of the titanium compound component (A) and the phosphorus compound component (B) is separated from the reaction system by means of centrifugal precipitation treatment or filtration, and can be used as a catalyst for producing a polyester resin without being purified. Alternatively, the separated reaction product may be recrystallized by a recrystallization agent such as acetone, methanol, and/or water to be purified, and the obtained purified product may be used as a catalyst. Further, the reaction product may not be separated from the reaction system, but the reaction mixture containing the reaction product may be used as a catalyst-containing mixture as it is.

As the titanium-based catalyst, it is preferable that the titanium compound (1) composed of at least one titanium compound (1) of the formula (I) (where k is 1), that is, titanium tetraalkoxide, and the formula The reaction product of the phosphorus compound component (B) composed of at least one phosphorus compound of (III) is used as a catalyst.

Further, it is preferred to use a compound represented by the following formula (IV) as a titanium contact Media.

[In the above formula, R ⁶ and R ⁷ each independently represent an alkyl group having 2 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms]

A catalyst comprising a titanium/phosphorus compound represented by the formula (IV) has high catalytic activity, and the polyester resin produced therefrom has a good color tone (low b value) and practically has a sufficiently low content of acetaldehyde. A residual trimetallic body of a residual metal and an ester of an aromatic dicarboxylic acid and an alkylene glycol, and which has practically sufficient polymer properties.

The titanium-based catalyst preferably contains 50% by weight or more of the titanium/phosphorus compound of the above formula (IV), and more preferably contains 70% by weight or more.

The amount of the titanium-based catalyst used is a molar amount of titanium atoms, and the total amount of the millimolar amount of the aromatic dicarboxylic acid component contained in the polymerization starting material is preferably from 2 to 40 millimoles. Preferably, it is 5 to 35 millimol%, more preferably 10 to 30 millimol%. If it is less than 2 mmol%, the effect of promoting the polymerization of the polymerization starting material by the catalyst becomes insufficient, resulting in insufficient polyester production efficiency, and a polyester resin having a desired degree of polymerization may not be obtained. On the other hand, when it exceeds 40 mmol%, the color tone (b value) of the obtained polyester resin is insufficient to have a yellowish appearance, so that the practicality is lowered.

The method for producing an alkylene glycol ester of an aromatic dicarboxylic acid and/or an oligomer thereof is not limited, but generally, an "aromatic dicarboxylic acid or an ester-forming derivative thereof" and "stretching" are used. An alkyl glycol or an ester-forming derivative thereof is produced by a heating reaction. For example, use as polyparaphenylene The ethylene glycol ester of terephthalic acid and/or its oligomer of the raw material of ethylene diformate is produced by directly esterifying terephthalic acid with ethylene glycol, or The lower alkyl ester of terephthalic acid is subjected to a transesterification reaction with ethylene glycol or an addition reaction of ethylene oxide with terephthalic acid. Further, in the alkylene glycol ester of the aromatic dicarboxylic acid and/or its oligomer, other dicarboxylic acid esters copolymerized therewith may be added as an additional component, and the amount thereof is not impaired in practice. The amount within the range of the effect of the method of the present invention is preferably 10 mol% or less, and is preferably in the range of 5 mol% or less (specifically, based on the total amount of the acid component).

The copolymerizable additional component, preferably as an acid component, may be selected from aliphatic and alicyclic dicarboxylic acids such as sebacic acid, sebacic acid, and 1,4-cyclohexanedicarboxylic acid. And a hydroxycarboxylic acid, for example, one or more of β-hydroxyethoxybenzoic acid and p-oxybenzoic acid; and the ethylene glycol component may be selected, for example, from ethylene glycol having 2 or more carbon atoms. , 1,4-cyclohexanedimethanol, neopentyl glycol, bisphenol A, bisphenol S aliphatic, alicyclic, aromatic diol compound, and polyoxyalkylene glycol 1 More than one ester or an anhydride thereof. The above-mentioned additional component esters may be used singly or in combination of two or more kinds. Among them, the amount of the copolymerization is preferably within the above range.

Further, in the case where terephthalic acid and/or dimethyl terephthalate is used as a starting material, 70% by weight or more can be used based on the weight of the total acid component constituting the polyester. The terephthalic acid is recovered by recovering dimethyl terephthalate obtained by depolymerization of polyalkylene terephthalate or by hydrolyzing it. In this case, the target polyalkylene terephthalate is preferably polyethylene terephthalate. From the viewpoint of efficient resource utilization, it is particularly preferable to use recycled PET bottles and recycled fibers. For the product and the recovered polyester film product, it is preferable to use the polymer chips or the like generated in the production steps of the products as a raw material source for polyester production. Here, the poly(terephthalic acid) will be recovered. The method of depolymerizing the base ester to obtain dimethyl terephthalate is not particularly limited, and any method known in the art can be employed. For example, after depolymerization of the recovered polyalkylene terephthalate using ethylene glycol, the depolymerization product is supplied to a transesterification reaction with a lower alcohol such as methanol, and the reaction mixture is refined to be recovered. a lower alkyl ester of terephthalic acid, which is then supplied to a transesterification reaction with an alkylene glycol, and the resulting phthalic acid/alkylene glycol ester is polycondensed. A polyester resin was obtained. Further, the method for recovering terephthalic acid from the recovered dimethyl terephthalate is not particularly limited, and any conventional method can be used. For example, after recovering the dimethyl terephthalate by a recrystallization method and/or a distillation method from the reaction mixture obtained by the transesterification reaction, the mixture is heated with water under high temperature and high pressure to be hydrolyzed and recovered. Terephthalic acid. Among the impurities contained in the terephthalic acid obtained by this method, the content of 4-carboxybenzaldehyde, p-toluic acid, benzoic acid, and dimethyl hydroxyterephthalate is preferably 1 ppm or less in total. Further, the content of monomethyl terephthalate is preferably in the range of 1 to 5000 ppm. The terephthalic acid recovered by the above method is directly subjected to an esterification reaction with an alkylene glycol, and the obtained ester is subjected to polycondensation, whereby a polyester resin can be produced.

In the polyester resin used in the present invention, the timing of adding a catalyst to the polymerization starting material is as long as the polycondensation reaction of the aromatic dicarboxylic acid alkylene glycol ester and/or its oligomer is started. Any previous stage is OK, and there are no restrictions on how to add it. For example, an aromatic dicarboxylic acid alkylene glycol ester may be prepared, a catalyst solution or a slurry may be added to the reaction system to start a polycondensation reaction, or the aromatic dicarboxylic acid alkylene group may be prepared. In the case of ethylene glycol ester, a solution or slurry of the catalyst is added to the reaction system together with or after the starting material.

The production reaction conditions of the polyester resin used in the present invention are also not particularly limited. In general, the polycondensation reaction should be carried out at a temperature of 230 to 320 ° C, under normal pressure, or under reduced pressure. (0.1 Pa ~ 0.1 MPa), or these conditions are combined to carry out polycondensation for 15 to 300 minutes.

In the polyester resin used in the present invention, a reaction stabilizer such as trimethyl phosphate may be added to the reaction system at any stage in the production of the polyester according to the demand, and further, depending on the demand, the reaction may be carried out. The system is blended with one or more of an antioxidant, a UV absorber, a flame retardant, a fluorescent whitening agent, a matting agent, a toner, an antifoaming agent, and other additives. In particular, the polyester resin preferably contains at least one antioxidant having a hindered phenol compound, but the content thereof is preferably 1% by weight or less based on the weight of the polyester resin. When the content is more than 1% by weight, "the quality of the obtained product may be deteriorated due to thermal deterioration of the antioxidant itself" may occur.

The hindered phenol compound for an antioxidant used in the polyester resin used in the present invention may be selected from pentaerythritol-indole [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] ,3,9-bis{2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propanyloxy]-1,1-dimethylethyl}-2 And 4,8,10-tetraoxaspiro (5,5) undecane or the like is preferably used in combination with the hindered phenol-based antioxidant and a thioether-based secondary antioxidant. The method of adding the hindered phenol-based antioxidant to the polyester resin is not particularly limited, but is preferably a transesterification reaction or an addition at any stage after the completion of the esterification reaction or before the completion of the polymerization reaction.

Further, in order to finely adjust the color tone of the obtained polyester resin, azo, triphenylmethane, quinoline, lanthanide, phthalocyanine may be added to the reaction system in the production stage of the polyester resin. A toner composed of one or more kinds of an organic blue pigment or an inorganic blue pigment. Further, in the production method of the present invention, it is of course not necessary to use "an inorganic cyan pigment containing cobalt or the like which lowers the heat stability of the polyester resin" as a toner. Therefore, the polyester resin used in the present invention does not actually contain cobalt.

The polyester resin used in the present invention preferably contains 0.001 ppm to 100 ppm of a titanium element derived from the above catalyst. The content is preferably from 0.001 ppm to 50 ppm, more preferably from 1 ppm to 50 ppm. If the titanium element contained is more than 100 ppm, the thermal stability and the moist heat resistance may be deteriorated; if less than 0.001 ppm, the residual amount of the catalyst of the polyester resin used is greatly reduced, representing a polyester resin. Manufacturing becomes difficult, and good mechanical strength, thermal stability, and moist heat stability may not be obtained.

The polyester resin has a viscosity of 0.4 to 1.2. The preferred viscosity range is from 0.45 to 0.95, more preferably from 0.50 to 0.9. When the viscosity of the polyester resin is less than 0.4, sufficient impact characteristics and chemical resistance may not be obtained. When the viscosity is more than 1.0, the fluidity at the time of injection molding is lowered, and flow marks or coloring may occur. Poor appearance of this appearance.

Polyester resin, polyethylene terephthalate resin (PET) and polybutylene terephthalate resin (PBT), the blending ratio (weight ratio) (PET/PBT) should be 1/7~7 /8. The blending ratio is preferably 1/7 to 1/2, more preferably 1/7 to 1/4. When the blend ratio is greater than 7/8, the chemical corrosion resistance is lowered, and when it is less than 1/7, the fluidity may be lowered.

The content of the component B is 20 to 50 parts by weight, preferably 20 to 45 parts by weight, and more preferably 25 to 40 parts by weight, per 100 parts by weight of the resin component. When the content is less than 20 parts by weight, the effect of improving chemical resistance cannot be exhibited, and if it exceeds 50 parts by weight, the heat and humidity resistance is lowered or the impact strength is lowered.

(C component: core-shell polymer)

The core-shell polymer used in the present invention is composed of a crosslinked acrylate-based elastomer composed of an acrylate having an alkyl group having 1 to 4 carbon atoms and an alkyl group having 5 to 8 carbon atoms. Nuclear (C-1 component) and "shell with methacrylate as a main component (C-2 component)" A core-shell polymer. When the core-shell polymer other than the above-described composition is used as the component C, sufficient impact characteristics and rigidity cannot be obtained, and the chemical resistance is lowered depending on the compound.

The constitutive monomer of the component C-1, that is, the acrylate having an alkyl group having 1 to 4 carbon atoms, may, for example, be methacrylate, ethacrylate, propyl acrylate or butyl acrylate. Further, examples of the acrylate having an alkyl group having 5 to 8 carbon atoms include hexyl acrylate, heptyl acrylate, and 2-ethylhexyl acrylate. The most preferred combination is a crosslinked acrylic alkyl elastomer composed of butyl acrylate and 2-ethylhexyl acrylate. Moreover, components other than the alkyl acrylate may be contained in the range which does not inhibit the effect of this invention.

The component C-2 is derived from a (meth) acrylate (for example, methyl methacrylate or the like). A vinyl aromatic compound, a monomer mixture of a vinyl cyanide compound and a (meth) acrylate, etc., may be copolymerized with other vinyl monomers copolymerizable as needed.

In the core-shell polymer used in the component C, the content of the component C-1 is preferably 50 to 99% by weight, preferably 65 to 95% by weight, most preferably 75 to 90% by weight based on 100% by weight of the component C. weight%. When the content of the component C-1 is less than 50% by weight, sufficient impact characteristics may not be obtained. Moreover, if it is more than 99% by weight, it may not be able to obtain sufficient impact characteristics, which is not preferable.

Further, the content of the acrylate having an alkyl group having 5 to 8 carbon atoms in the component C-1 is preferably 10 to 99% by weight, and more preferably 25 to 90% by weight, based on 100% by weight of the C-1 component. More preferably, it is 35 to 80% by weight, and most preferably 40 to 70% by weight. When it is less than 10% by weight, sufficient impact characteristics may not be obtained, and if it is more than 99% by weight, heat resistance may be lowered, which is not preferable.

The content of the core-shell polymer is from 1 to 10 parts by weight, preferably from 2 to 9 parts by weight, more preferably from 3 to 8 parts by weight, per 100 parts by weight of the resin component. If it is less than 1 part by weight, it cannot be fully obtained. If the impact characteristics are more than 10 parts by weight, the rigidity and chemical resistance are low.

(D component: filling material)

As the filler used in the present invention, a conventionally known filler may be used, but a filler to be used is preferably selected from the group consisting of a fibrous glass filler, a plate glass filler, a fibrous carbon filler, and a non-fibrous material. At least one filler material of the group consisting of a carbon filler material and a silicate mineral.

(D-1; fibrous glass filler)

Examples of the fibrous glass filler to be used in the present invention include glass fibers (including metal coated glass fibers) and glass polishing fibers. The glass fiber which becomes the base of this fibrous glass filler is a predetermined fiber shape by extending the molten glass by various methods, and quenching. The quenching and extension of this case are not particularly limited. Further, the cross-sectional shape may be a perfect shape other than a perfect circle such as an elliptical shape, a braided shape, a flat shape, or a trilobal shape. Further, it may be a shape in which a shape other than a perfect circle is mixed in a perfect shape. Flat shape means that the average length of the fiber cross section is 10~50μm, preferably 15~40μm, preferably 20~35μm, and the ratio of long diameter to short diameter (long diameter/short diameter) is 1.5. ~8, preferably 2~6, more preferably 2.5~5 shape.

Further, the fibrous fiber filler having a high aspect ratio such as glass fiber preferably has an average fiber diameter of 1 to 25 μm, preferably 3 to 17 μm. In the case of using a filler having an average fiber diameter in this range, good mechanical strength can be found without impairing the appearance of the molded article. Further, the fiber length of the high aspect ratio fibrous glass filler is preferably from 60 to 500 μm, more preferably from 100 to 400 μm, particularly preferably from 120 to 350 μm, as the number average fiber length in the resin composition. Moreover, the average fiber length of this number is observed by an optical microscope to observe the high-temperature ashing of the molded article and the solvent. The amount of residue of the filler to be processed, such as dissolution and decomposition by the drug, and the value calculated from the image by the image analysis device. Further, when calculating this value, the fiber diameter is a value calculated by a method that does not calculate a length below the target value. The aspect ratio of the high aspect ratio fibrous glass filler material is preferably from 10 to 200, preferably from 15 to 100, more preferably from 20 to 50. The aspect ratio of the filler material is the average fiber diameter divided by the average fiber length.

Generally, glass fibers are short-fibrillated using a pulverizer such as a ball mill to produce a milled glass fiber. For example, the aspect ratio of the fibrous glass filler having a low aspect ratio of the ground glass fiber is preferably 2 to 10, preferably 3 to 8. The fiber length of the low aspect ratio fibrous glass filler is preferably from 5 to 150 μm, preferably from 9 to 80, as the number average fiber length in the resin composition. Further, the average fiber diameter is preferably from 1 to 15 μm, more preferably from 3 to 13 μm.

(D-2; sheet glass filling material)

The sheet-like glass filler which is preferably used in the present invention may, for example, be a metal-coated glass chip, or a glass chip containing a metal oxide-coated glass chip.

The glass cullet which is the base of the plate-shaped glass filler is a plate-shaped glass filler manufactured by the method of a cylinder blow method, a melt-gel method, etc.. The size of the glass cullet raw material can be selected according to the degree of pulverization and classification. The average particle diameter of the glass cullet used for the raw material is preferably from 10 to 1,000 μm, more preferably from 20 to 500 μm, still more preferably from 30 to 300 μm. The above range is intended to have both excellent handleability and formability. In general, the plate-shaped glass filler is cracked by melt-kneading with a resin to reduce the average particle diameter. The number average particle diameter of the plate-like glass filler in the resin composition is preferably from 10 to 200 μm, more preferably from 15 to 100 μm, still more preferably from 20 to 80 μm. In addition, the number average particle diameter is a plate-shaped glass which is observed by an optical microscope for the high-temperature ashing of the molded article, the dissolution by the solvent, and the decomposition by the drug. The residue of the glass filler material and the value calculated from the image by the image analysis device. Further, when calculating this value, the thickness of the fragment is a value calculated by a method that does not calculate a thickness below the target value. Further, the thickness is preferably 0.5 to 10 μm, more preferably 1 to 8 μm, and still more preferably 1.5 to 6 μm. The plate-shaped glass filler having the above-described number average particle diameter and thickness can achieve good mechanical strength, appearance, and moldability.

The glass composition of the fibrous glass filler and the sheet glass filler described above can be applied to various glass compositions typified by A glass, C glass, and E glass, and is not particularly limited. The glass filler may contain components such as TiO ₂ , SO _{3 ,} and P ₂ O ₅ depending on the requirements. Among these compounds, E glass (alkali-free glass) is preferred. Further, from the viewpoint of improving the mechanical strength, the glass filler is preferably subjected to surface treatment by a conventional surface treatment agent such as a decane coupling agent, a titanate coupling agent or an aluminate coupling agent. Further, glass fibers (including coated metal or coated metal oxide) and glass chips (including coated metal or coated metal oxide) are preferably used as an olefin resin, a styrene resin, an acrylic resin, or a polyester resin. A bundling treatment is carried out by using an epoxy resin or an urethane resin. The amount of the sizing agent adhered to the filler material to be bundled is preferably from 0.5 to 8% by weight, preferably from 1 to 4% by weight, based on 100% by weight of the filler.

Furthermore, the fibrous glass filler of the present invention and the sheet glass filler include those coated with different materials. As such a different material, it is preferably exemplified as a metal and a metal oxide. As the metal, silver, copper, nickel, and aluminum can be exemplified. Further, examples of the metal oxide include titanium oxide, cerium oxide, zirconium oxide, iron oxide, aluminum oxide, and cerium oxide. The surface coating method of the different materials is not particularly limited, and examples thereof include various conventional plating methods (for example, electroplating, electroless plating, and hot-dip plating), vacuum vapor deposition, and ion coating. CVD method (for example, thermal CVD, MOCVD, plasma CVD, etc.), PVD method, sputtering method, and the like.

(D-3; fibrous carbon filler)

Examples of the fibrous carbon filler to be used in the present invention include carbon fibers (including metal-coated carbon fibers), ground carbon fibers, vapor-grown carbon fibers, and carbon nanotubes. The carbon nanotubes may have a fiber diameter of 0.003 to 0.1 μm, and any of a single layer, a double layer, and a plurality of layers, preferably a multilayer (so-called MWCNT). Among these compounds, carbon fibers (including metal-coated carbon fibers) are preferred from the viewpoint of excellent mechanical strength and from the viewpoint of imparting good electrical conductivity. Moreover, good electrical conductivity is one of the important characteristics required for resin materials among digital precision equipment (for example, represented by digital cameras) in recent years.

As the carbon fiber, any of a cellulose system, a polyacrylonitrile system, and a pitch system can be used. Further, it is possible to use a carbon fiber obtained by a method of spinning, which does not undergo a non-melting step, and is composed of a polymer and a solvent which combine a methylene bond of an aromatic sulfonic acid or a salt thereof. The raw material composition is prevented or formed, and then the method of carbonizing it is represented. Further, any of a general-purpose type, a medium elastic modulus type, and a high elastic modulus type can also be used. Among these compounds, a polyacrylonitrile-based high modulus type is particularly preferable.

Further, the average fiber diameter of the carbon fibers is not particularly limited, but is usually 3 to 15 μm, preferably 5 to 13 μm. The carbon fiber having an average fiber diameter in this range exhibits good mechanical strength and fatigue characteristics without impairing the appearance of the molded article. Further, the fiber length of the carbon fiber is preferably from 60 to 500 μm, more preferably from 80 to 400 μm, particularly preferably from 100 to 300 μm, as the number average fiber length in the resin composition. In addition, the number average fiber length is a value calculated by a video analysis device by observing the residue of carbon fiber collected by high-temperature ashing of a molded article, dissolution by a solvent, decomposition by a drug, or the like by an optical microscope. Again, it is "The value calculated by the method of not calculating the length of the fiber length when calculating this value". The aspect ratio of the carbon fiber is preferably in the range of 10 to 200, more preferably in the range of 15 to 100, and more preferably in the range of 20 to 50. The aspect ratio of the fibrous carbon filler refers to the value obtained by dividing the average fiber diameter by the average fiber length.

Further, in order to improve the adhesion to the base resin and to improve the mechanical strength, it is preferred to subject the surface of the carbon fiber to oxidation treatment. Although the oxidation treatment method is not particularly limited, it is preferably exemplified by, for example, (1) a method of treating a fibrous carbon filler by an acid or an alkali or a salt thereof, or an oxidizing gas, and (2) having an oxygen-containing gas. a method of firing a fibrous carbon-filled fiber or a fibrous carbon filler at a temperature of 700 ° C or higher and (3) after oxidizing the fibrous carbon filler in the presence of an inert gas of the compound A method of heat treatment in the presence of an inert gas.

The metal coated carbon fiber is a metal layer coated on the surface of the carbon fiber. Examples of the metal include silver, copper, nickel, and aluminum. From the viewpoint of corrosion resistance of the metal layer, nickel is preferable. As a method of metal coating, various methods described in the previous "surface coating with different materials in a glass filling material" can be employed. Among them, the plating method should be used. Moreover, in the case of coating the carbon fiber with the metal, for example, the carbon fiber described above may be used as the carbon fiber to be the substrate. The thickness of the metal coating layer is preferably 0.1 to 1 μm, more preferably 0.15 to 0.5 μm. More preferably 0.2 to 0.35 μm.

The carbon fiber (including the metal-coated carbon fiber) is preferably subjected to a bundling treatment using an olefin resin, a styrene resin, an acrylic resin, a polyester resin, an epoxy resin, and an urethane resin. From the viewpoint of excellent mechanical strength, a fibrous carbon filler treated with an urethane resin or an epoxy resin is particularly suitable for the present invention.

(D-4; non-fibrous carbon filler)

Examples of the non-fibrous carbon filler to be used in the present invention include carbon black, graphite, fullerene, and the like. Among these compounds, carbon black and graphite are preferable from the viewpoint of mechanical strength, moist heat resistance, and thermal stability. As the carbon black, from the viewpoint of conductivity, carbon black having a DBP oil absorption of from 100 ml/100 g to 500 ml/100 g is preferable. This carbon black is, in general, acetylene black and Ketjen black. Specifically, for example, DENKA BLACK manufactured by Denki Kogyo Co., Ltd., VULCANX C-72 manufactured by CABOT Co., Ltd., BP-2000, Ketjen black EC manufactured by LION Co., Ltd., and Ketjen black EC-600JD.

As the graphite, any of natural graphite having a mineral name of graphite or various artificial graphites can be used. As the natural graphite, any of earthy graphite, scaly graphite (also referred to as stellite graphite) and flake graphite (Flake Graphite) can be used. Further, the artificial graphite is obtained by heat-treating the amorphous carbon to artificially align the irregularly arranged fine graphite crystals, and in addition to the artificial graphite used in the general carbon material, it also contains kish graphite. Decompose graphite and thermally decompose graphite. Artificial graphite generally used for carbon materials is usually made of petroleum coke or stone carbon-based pitch coke and is produced by graphitization.

The graphite of the present invention also contains expanded graphite which can be thermally expanded by performing a treatment represented by an acid treatment, or graphite which is subjected to the expansion treatment. The particle diameter of the graphite of the present invention is preferably in the range of 2 to 300 μm. The particle diameter is preferably from 5 to 200 μm, more preferably from 7 to 100 μm, particularly preferably from 7 to 50 μm. By satisfying this range, good mechanical strength and appearance of the molded article can be achieved. On the other hand, when the average particle diameter is less than 2 μm, the effect of improving the rigidity is small. When the average particle diameter exceeds 300 μm, the impact resistance is remarkably lowered, and the so-called graphite relief on the surface of the molded article is obtained. It is a bad situation, so it is not good.

The amount of carbon fixed in the graphite of the present invention is preferably 80% by weight or more, more preferably 90% by weight or more, and still more preferably 98% by weight or more. Further, the volatile component of the graphite of the present invention is preferably 3% by weight or less, more preferably 1.5% by weight or less, and still more preferably 1% by weight or less.

The average particle diameter of the graphite in the present invention means the particle diameter before the resin composition, and the particle diameter is determined by the laser diffraction or scattering method.

Further, as long as the properties of the composition of the present invention are not impaired, in order to increase the affinity with the thermoplastic resin, the surface of the graphite may be subjected to a surface treatment such as epoxy treatment, urethane treatment, decane coupling treatment, and oxidation treatment. Wait.

(D-5; citrate mineral)

The filler used in the present invention may, for example, be a citrate mineral. The component D-5 is preferably a citrate mineral, a decanoate, a dicaprate, a cyclic citrate or a chain citrate composed of at least a metal oxide component and a SiO ₂ component. The citrate mineral may be in a crystalline state. Further, the crystallization may be any metamorphosis of each citrate mineral, and the shape of the crystal may be various shapes such as a fiber or a plate.

The citrate mineral may be a composite oxide, an oxoate (constituted by an ionic lattice), or a compound of a solid solution, and further, the composite oxide may be a single oxidation of two or more kinds. a combination of two or more kinds of a single oxide and an oxyacid salt; further, a solid solution of two or more kinds of metal oxides in a solid solution, and two or more kinds of oxyacid salts Any of the solid solutions. Further, it may be a hydrate. The form of the crystal water in the hydrate may be introduced as a Si-OH, introduced as a hydroquinone ion, ionically introduced as a hydroxide ion (OH ^- ) with respect to a metal cation, and entered as a H ₂ O molecule. Any form of the constructor.

As the citrate mineral, a synthetic product corresponding to a natural product can be used. As The artificial compound may be any of various conventionally known methods, for example, a silicate mineral obtained by various synthesis methods such as a solid reaction, a hydrothermal reaction, and an ultrahigh pressure reaction.

Specific examples of the citrate mineral in each metal oxide component include the following examples. The indication in the parentheses here is the name of the mineral or the like having the citrate mineral as a main component, and means that the compound in the parentheses can be used as an exemplified metal salt.

Examples of the component containing K ₂ O include K ₂ O‧SiO ₂ , K ₂ O‧4SiO ₂ ‧H ₂ O, K ₂ O‧Al ₂ O ₃ ‧2SiO ₂ (hexagonal kaxander; Kalsilite) K ₂ O‧Al ₂ O ₃ ‧4SiO ₂ (leucite) and K ₂ O‧Al ₂ O ₃ ‧6SiO ₂ (ortretic feldspar).

Examples of the component containing Na ₂ O include Na ₂ O‧SiO ₂ and its hydrate, Na ₂ O‧2SiO ₂ , 2Na ₂ O‧SiO ₂ , Na ₂ O‧4SiO ₂ , Na ₂ O‧3SiO ₂ ‧3H ₂ O, Na ₂ O‧Al ₂ O ₃ ‧2SiO ₂ , Na ₂ O‧Al ₂ O ₃ ‧4SiO ₂ (emerite pyroxene), 2Na ₂ O‧3CaO‧5SiO ₂ , 3Na ₂ O‧2CaO‧5SiO ₂ and Na ₂ O‧Al ₂ O ₃ ‧6SiO ₂ (sodium feldspar).

Examples of the component containing Li ₂ O include Li ₂ O‧SiO ₂ , 2Li ₂ O‧SiO ₂ , Li ₂ O‧SiO ₂ ‧H ₂ O, 3Li ₂ O‧2SiO ₂ , Li ₂ O‧Al ₂ O ₃ ‧4 SiO ₂ (leaf feldspar), Li ₂ O‧Al ₂ O ₃ ‧2 SiO ₂ (eucryptite), and Li ₂ O‧Al ₂ O ₃ ‧4 SiO ₂ (iron spodumene).

Examples of the component containing BaO include BaO‧SiO ₂ , 2BaO‧SiO ₂ , BaO‧Al ₂ O ₃ ‧2SiO ₂ (anthracene), and BaO‧TiO ₂ ‧3SiO ₂ (bentonite).

As a component containing CaO in its composition, 3CaO‧SiO ₂ (alite of cement clinker mineral), 2CaO‧SiO ₂ (belite of cement clinker mineral), 2CaO ‧MgO‧2SiO ₂ (magnesium feldspar), 2CaO‧Al ₂ O ₃ ‧SiO ₂ (calcium feldspar), solid solution of feldspar and feldspar (yellow feldspar), CaO‧SiO ₂ (silver ash) (including either α-form or β-form)), CaO‧MgO‧2SiO ₂ (dopphosite), CaO‧MgO‧SiO ₂ (grayite olivine), 3CaO‧MgO‧2SiO ₂ (magnesium strontium calcium) Shim), CaO‧Al ₂ O ₃ ‧2SiO ₂ (alkaline), SCaO‧6SiO ₂ ‧5H ₂ O (saltite, other 5CaO‧6SiO ₂ ‧9H ₂ O, etc.) Tobermorite group) hydrates, 2CaO ‧ SiO ₂ ‧ H ₂ O (metamenite) hydrated limestone series hydrates, 6CaO‧6SiO ₂ ‧ H ₂ O (hard calcite) Hydrate, white calcium zeolite series hydrate such as 2CaO‧SiO ₂ ‧2H ₂ O (white calcium zeolite), CaO‧Al ₂ O ₃ ‧2SiO ₂ ‧H ₂ O (hard column), CaO‧FeO‧2SiO ₂ ( Tourmaline), 3CaO‧2SiO ₂ (brown zircon), 3CaO‧Al ₂ O ₃ ‧3SiO ₂ (calcium garnet), 3CaO‧ Fe ₂ O ₃ ‧3SiO ₂ (calcium iron garnet), 6CaO‧4Al ₂ O ₃ ‧FeO‧SiO ₂ (multicolor mineral, pleochroite) and clinozoisite, red pebbles, brown stone, Vesuvius Stone, axe, scawtite and pyroxene.

Further, as the citrate mineral containing CaO as a component thereof, for example, Portland cement is mentioned. The type of Portland cement is not particularly limited, but any of ordinary, early strength, super early strength, medium heat, sulfate resistance, white, and the like can be used. Further, various mixed cements such as blast furnace cement, cerium oxide cement, fly ash cement, etc. may also be used as the component B. Further, examples of the citrate mineral containing CaO in other components include blast fumace slag and ferrite iron.

Examples of the ZnO contained in the composition include ZnO‧SiO ₂ , 2ZnO‧SiO ₂ (troostite), and 4ZnO‧2SiO ₂ ‧H ₂ O (heteropolar ore).

Examples of the component containing MnO include MnO‧SiO ₂ , 2MnO‧SiO ₂ , CaO‧4MnO‧5SiO ₂ (rhuite), and iron manganese sodium kozulite.

As the component containing FeO, for example, FeO‧SiO ₂ (ferrite), 2FeO‧SiO ₂ (fayalite), 3FeO‧Al ₂ O ₃ ‧3SiO ₂ (valley), and 2CaO‧5FeO‧ 8SiO ₂ ‧H ₂ O (actinolite) and the like.

Examples of the component including CoO in the composition include CoO‧SiO ₂ and 2CoO‧SiO ₂ .

As the component containing MgO, for example, MgO‧SiO ₂ (block talc, enstatite), 2MgO‧SiO ₂ (magnesium silicate), 3MgO‧Al ₂ O ₃ ‧3SiO ₂ (magnesium aluminum) Garnet, 2MgO‧2Al ₂ O ₃ ‧5SiO ₂ (cordierite), 2MgO‧3SiO ₂ ‧5H ₂ O, 3MgO‧4SiO ₂ ‧H ₂ O (talc), 5MgO‧8SiO ₂ ‧9H ₂ O Pu Shi), 4MgO‧6SiO ₂ ‧7H ₂ O (sepiolite), 3MgO‧2SiO ₂ ‧2H ₂ O (yellow olivine), 5MgO‧2CaO‧8SiO ₂ ‧H ₂ O (Tremolite), 5MgO‧Al ₂ O ₃ ‧3SiO ₂ ‧4H ₂ O (chlorite), K ₂ O‧6MgO‧Al ₂ O ₃ ‧6SiO ₂ ‧2H ₂ O (phlogopite), Na ₂ O‧3MgO‧3Al ₂ O ₃ ‧8SiO ₂ ‧H ₂ O (blue amphibole) and magnesium tourmaline, amphibole, brown amphibole, vermiculite, bentonite, etc.

As Fe ₂ O ₃ as a component, Fe ₂ O ₃ ‧ SiO ₂ etc. are mentioned, for example.

As a person component comprising ZrO ₂ includes, for example: ZrO ₂ ‧SiO ₂ (zircon) AZS refractory and the like.

As the component containing Al ₂ O ₃ , for example, Al ₂ O ₃ ‧ SiO ₂ (chondrite, andalusite, kyanite), 2Al ₂ O ₃ ‧ SiO ₂ , Al ₂ O ₃ ‧ ₃ SiO ₂ , 3Al ₂ O ₃ ‧2SiO ₂ (mullite), Al ₂ O ₃ ‧2SiO ₂ ‧2H ₂ O (kaolinite), Al ₂ O ₃ ‧4 SiO ₂ ‧H ₂ O (pyrophyllite), Al ₂ O ₃ ‧4 SiO ₂ ‧H ₂ O (saponite), K ₂ O‧3Na ₂ O‧4Al ₂ O ₃ ‧8SiO ₂ (Nitrite), K ₂ O‧3Al ₂ O ₃ ‧6SiO ₂ ‧2H ₂ O (White Cloud Mother, sericite), K ₂ O‧6MgO‧Al ₂ O ₃ ‧6SiO ₂ ‧2H ₂ O (phlogopite) and various zeolites, fluorophlogopite and biotite.

Among the above-mentioned citrate minerals, talc, quartz, and ash are particularly preferable from the viewpoints of good balance between rigidity and impact resistance, excellent heat and humidity resistance, thermal stability, and appearance, and easy availability.

(D-5-i) talc

The talc in the present invention is chemically composed of aqueous magnesium ruthenate, and is generally represented by the chemical formula 4SiO ₂ ‧3MgO‧2H ₂ O, which is usually a scaly particle having a layered structure, and is also in composition. It is composed of 56 to 65% by weight of SiO ₂ , 28 to 35% by weight of MgO, and about 5% by weight of H ₂ O. It contains 0.03 to 1.2% by weight of Fe ₂ O ₃ , 0.05 to 1.5% by weight of Al ₂ O ₃ , 0.05 to 1.2% by weight of CaO, 0.2% by weight or less of K ₂ O, 0.2% by weight or less of Na ₂ O, and the like. As a small amount of other ingredients. As a preferred talc composition, it is preferably SiO ₂ : 62 to 63.5% by weight; MgO: 31 to 32.5 % by weight; Fe ₂ O ₃ : 0.03 to 0.15% by weight; Al ₂ O ₃ : 0.05 to 0.25% by weight and CaO: 0.05~0.25% by weight. Further, the ignition loss is preferably 2 to 5.5% by weight. In the preferred composition, a resin composition having good thermal stability and a hue can be obtained, and a good molded article can be produced by raising the molding processing temperature. Thereby, the composition of the present invention can be further highly fluidized, and can correspond to a thin molded article of a large or complicated shape.

The particle diameter of the talc is preferably in the range of 0.1 to 50 μm (preferably 0.1 to 10 μm, more preferably 0.2 to 5 μm, particularly preferably 0.2 to 3.5 μm) by the precipitation method. Therefore, preferred talc of the present invention has the above preferred composition and has an average particle diameter of 0.2 to 5 μm of talc. Further, it is particularly preferable to use talc having a bulk density of 0.5 (g/cm ³ ) or more as a raw material. As the talc which satisfies this condition, "Upn HS-T0.8" manufactured by Lin Huacheng Co., Ltd. can be exemplified. The average particle diameter of talc refers to D50 (median diameter of particle diameter distribution) measured by X-ray penetrating method which is one of liquid phase precipitation methods. Specific examples of the apparatus for performing the measurement include Sedigraph 5100 manufactured by Micromeritics Co., Ltd., and the like.

Further, the method for preparing the talc from the original stone is not particularly limited, and an axial flow mil method, a ring mil method, a roller mil method, a ball mil method, a jet mil method may be used. And the container rotary compression shear type mil method and the like. Further, the talc after the pulverization is preferably subjected to classification treatment by various classifiers to make the particle diameter distribution uniform. The classifier is not particularly limited, and examples thereof include an impact inertial classifier (variable impact machine), a Coanda effect utilization type inertia classifier (Elbow-Jet, etc.), and a centrifugal classifier (multi-stage cyclone, microplex, Dispersion separator, Accu-cut, turbo classifier, terboplex, microseparator, super separator, etc.).

Further, from the viewpoint of the handleability and the like, the talc is preferably in an agglomerated state, and as a method of producing the talc, there is a method of performing exhaust gas compression, a method of compressing using a sizing agent, and the like. From the viewpoint of being simple and avoidable the incorporation of the sizing agent resin component into the resin composition of the present invention, a method by degassing compression is particularly preferable.

(D-5-ii) Quartz

Quartz can be used with an average particle size of 5 to 250 μm. The average particle diameter (D50 (median diameter of the particle diameter distribution)) measured by the laser diffraction and scattering method is preferably 5 to 50 μm. If the average particle diameter of quartz is less than 5 μm, it is difficult to obtain an effect of improving rigidity. On the other hand, a resin composition containing quartz having an average particle diameter of more than 250 μm tends to be saturated with mechanical properties, and on the other hand, appearance and flame retardancy are deteriorated. Further, the average particle diameter of quartz is measured by a laser diffraction, a scattering method or a vibration type screening method. By laser diffraction and scattering, it is preferable to carry out 95% by weight or more of quartz by 325 mesh by a vibrating screening method. For quartz having a particle diameter of more than this, a vibrating screening method is generally used. In the vibrating screening method of the present invention, first, a quartz powder 100 g used is sieved for 10 minutes by using a vibrating sieve and a JIS standard sieve which is superimposed in the order of opening. The weight of the powder remaining on each sieve was measured to determine the particle size distribution.

As the thickness of quartz, a thickness of 0.01 to 1 μm actually measured by observation with an electron microscope can be used. The preferred thickness is 0.03 to 0.3 μm. Can use an aspect ratio of 5~200, preferably For 10~100. Further, it is preferable to use muscovite quartz as the quartz to be used, and its Mohs hardness is about 3. Muscovite quartz can achieve high rigidity and high strength compared to other quartz such as phlogopite, and can solve the problem of the present invention at a higher level. Therefore, preferred quartz of the present invention is a muscovite having an average particle diameter of 5 to 250 μm, preferably 5 to 50 μm. As the preferred quartz, for example, "A-21" manufactured by Yamaguchi Mica Industrial Co., Ltd. can be exemplified. Further, the pulverization method of quartz can be produced by any of the dry pulverization method and the wet pulverization method. The dry pulverization method is low in cost and relatively common, but on the other hand, the wet pulverization method can effectively pulverize quartz thinner and finer (improving the effect of increasing the rigidity of the resin composition). In the present invention, quartz which is a wet pulverization method is preferred.

(D-5-iii) ash stone

The fiber diameter of the ash stone is preferably 0.1 to 10 μm, more preferably 0.1 to 5 μm, and more preferably 0.1 to 3 μm. Further, the aspect ratio (average fiber length / average fiber diameter) is preferably 3 or more. The upper limit of the aspect ratio is, for example, 30 or less. Here, the fiber diameter was observed by an electron microscope to observe the reinforced filler, and individual fiber diameters were determined, and the number average fiber diameter was calculated from the measured value. The use of an electron microscope is difficult to accurately measure the size of a target in an optical microscope. The fiber diameter is obtained by randomly extracting a filler for measuring the fiber diameter from an image observed by an electron microscope, measuring the fiber diameter in the vicinity of the center portion, and calculating the number average fiber diameter from the obtained measured value. . The observation was performed at an observation magnification of about 1000 times and the number of measurement samples was 500 or more (600 or less is preferable). On the other hand, in the measurement of the average fiber length, the filler was observed with an optical microscope, and individual lengths were determined, and the number average fiber length was calculated from the measured value. The observation of the optical microscope was started from the preparation of a sample of "dispersed into a state in which the fillers did not excessively overlap each other". The observation system was carried out under the condition of 20 times of the objective lens, and the observed image was taken as a video material by a CCD camera with a pixel of about 250,000. The image analysis device was used to analyze the obtained image data, and the length of the pure fiber was calculated using a program for obtaining the maximum distance between two points of the image data. Under these conditions, the size of each pixel is equivalent to a length of 1.25 μm, and the number of measurements is 500 or more (600 or less is more suitable for operation). In the ash stone of the present invention, since the resin composition sufficiently reacts with the whiteness originally possessed, it is preferable to strongly remove the iron component mixed in the raw material ore by a magnetic separator, and to mix in the wear of the machine when the raw material ore is pulverized. Iron composition. The iron content in the ash stone by the magnetic separator is preferably 0.5% by weight or less in the case of conversion to Fe ₂ O ₃ . Therefore, the preferred ash stone of the present invention has a fiber diameter of 0.1 to 10 μm, preferably 0.1 to 5 μm, more preferably 0.1 to 3 μm. The average particle diameter is 5 to 250 μm, preferably 5 to 50 μm, and the iron content is 0.5% by weight or less in the case of conversion to Fe ₂ O ₃ . As such a preferable ash stone, for example, SHYSEI MATEC Co., Ltd. (SH-1250), (SH-1800), Kansai MATEC Co., Ltd. (KGP-H40), and NYCO Co., Ltd. "NYGLOS4" can be mentioned.

The bismuth salt mineral in the present invention may be preferably a decane coupling agent (including an alkyl alkoxy decane, a polyorganohydrohydrohalo oxane, etc.), a higher fatty acid ester, or an oxygen compound, although it is preferably not subjected to surface treatment. For example, various surface treatment agents such as phosphorous acid, phosphoric acid, carboxylic acid, and carboxylic acid anhydride, and paraffin are surface-treated. Further, granules such as various resins, higher fatty acid esters, and paraffin wax may be granulated to form granules. Among the silicate minerals in the present invention, talc or ash stone is particularly preferred. This talc or apatite has good rigidity and impact resistance, and in the case of blending with a polycarbonate resin and a polyester resin, deterioration of hue and deterioration of appearance (for example, generation of silver bars) are less.

In the resin composition of the present invention, the content of the component D is 0 to 15 parts by weight, preferably 8 to 15 parts by weight, more preferably 9 to 14 parts by weight, more preferably 10 parts, per 100 parts by weight of the resin component. 12 parts by weight. If the upper limit is exceeded, the impact strength is low. If the lower limit is not exceeded, the rigidity improvement effect is not Foot, it is not good.

(other additives)

The resin composition of the present invention may contain various additives (flame retardant, fluorine-containing anti-drip agent, stabilizer, ultraviolet absorber, etc.) blended in a general polycarbonate resin in addition to the components A to D described above. A release agent, a coloring material, a compound having endothermic properties, an antistatic agent, an acidity adjuster, etc.) (for details of various additives, refer to WO2011/087141, etc.).

The phosphorus-based stabilizer which is preferably used in the present invention may, for example, be phosphorous acid, phosphoric acid, phosphinic acid, phosphonic acid, such esters, and tertiary phosphine. Among these compounds, phosphorous acid, phosphoric acid, phosphinic acid, phosphonic acid, triorganophosphate compound, and acid phosphate compound are particularly preferable. Further, the organic group in the acid phosphate compound includes one of a substituent, a disubstituted group, and the like. Any of the following exemplified compounds corresponding to the compound may be contained in the same manner.

As the triorganophosphate compound, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tridecyl phosphate, dodecyl phosphate, trilaurin can be exemplified. Luryl phosphate, tristearate phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthogonal biphenyl Phosphate, tributoxyethyl phosphate, and the like. Among these compounds, a trialkyl phosphate is preferred. The carbon number of the trialkyl phosphate is preferably from 1 to 22, preferably from 1 to 4. A particularly preferred trialkyl phosphate is trimethyl phosphate.

The acid phosphate compound may, for example, be a methyl acid phosphate, an ethyl acid phosphate, a butyl acid phosphate, a butoxyethyl acid phosphate, an octyl acid phosphate or a mercapto group. Acid phosphate, lauric acid phosphate, stearic acid phosphate, oil thio acid Phosphate ester, benzyl acid phosphate, phenyl acid phosphate, nonylphenyl acid phosphate, cyclohexyl phosphate, phenoxy vinyl phosphate, alkoxy polyethylene glycol Acid phosphate, bisphenol A acid phosphate, and the like. Among these compounds, long-chain dialkyl acid phosphate having a carbon number of 10 or more is preferable because it can effectively improve thermal stability, and the acid phosphate has high self-stability.

Examples of the phosphite compound include triphenyl phosphite, decylphenyl phosphite, trimethyl phosphite, trioctyl phosphite, and trioctyl decylphosphite. Ester, dimercaptomonophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl Phosphate ester, monooctyl diphenyl phosphite, ginseng (diethylphenyl) phosphite, bis(iso-propylphenyl) phosphite, ginseng (di-n-butylphenyl) Phosphite, ginseng (2,4-di-tert-butylphenyl) phosphite, ginseng (2,6-di-t-butylphenyl) phosphite, distearyl decyl pentaerythritol II Phosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite , bis(2,6-di-t-butyl-4-ethylphenyl)pentaerythritol diphosphite, bis{2,4-bis(1-methyl-1-phenylethyl)phenyl} Pentaerythritol diphosphite, phenyl bisphenol A pentaerythritol diphosphite, bis(nonylphenyl) pentaerythritol diphosphite, Dicyclohexyl pentaerythritol diphosphite, and the like.

Further, as another phosphite compound, a ring structure can be used by reacting with a divalent phenol. For example, 2,2'-methylenebis(4,6-di-t-butylphenyl)(2,4-di-t-butylphenyl)phosphite, 2,2' can be exemplified. -methylenebis(4,6-di-t-butylphenyl)(2-tert-butyl-4-methylphenyl)phosphite, 2,2-methylenebis(4,6 - Di-t-butylphenyl) octyl phosphite, and the like.

Examples of the phosphonite compound include ruthenium (2,4-di-t-butylphenyl)-4,4'-linked phenyldiphosphinate, and ruthenium (2,4-di- Tributylphenyl)-4,3'-linked phenyldiphosphinate, bismuth(2,4-di-t-butylphenyl)-3,3'-linked phenyldiphosphine Acid ester, bismuth (2,6-di-t-butylphenyl)-4,4'-linked phenyl diphosphinate, hydrazine (2,6-di-t-butylphenyl)- 4,3'-linked phenyl diphosphinate, bismuth (2,6-di-t-butylphenyl)-3,3'-linked phenyl diphosphinate, bis (2, 4-di-t-butylphenyl)-4-phenyl-phenylphosphinate, bis(2,4-di-tert-butylphenyl)-3-phenyl-phenylphosphinic acid Ester, bis(2,6-di-n-butylphenyl)-3-phenyl-phenylphosphinate, bis(2,6-di-t-butylphenyl)-4-phenyl - phenylphosphinate, bis(2,6-di-t-butylphenyl)-3-phenyl-phenylphosphinate, and the like. Among them, it is preferably bis(di-tert-butylphenyl)-linked phenyl diphosphinate, bis(di-tert-butylphenyl)-phenyl-phenylphosphinate, preferably Is bis(2,4-di-t-butylphenyl)-linked phenyl diphosphinate, bis(2,4-di-t-butylphenyl)-phenyl-phenylphosphine Acid ester. This phosphonite compound is preferably used in combination with a phosphite compound having "an aryl group substituted with two or more of the above alkyl groups".

The phosphonate compound may, for example, be dimethyl phenylphosphonate, diethyl phenylphosphonate or dipropyl phenylphosphonate.

As the tertiary phosphine, triethylphosphine, tripropylphosphine, tributylphosphine, trioctylphosphine, tripentylphosphine, dimethylphenylphosphine, dibutylphenylphosphine, diphenyl can be cited. Methylphosphine, diphenyloctylphosphine, triphenylphosphine, tri-p-tolylphosphine, trinaphthylphosphine, diphenylbenzylphosphine, and the like. A particularly preferred third stage phosphine is triphenylphosphine.

Preferred phosphorus-based stabilizers are a triorganophosphate compound, an acid phosphate compound, and a phosphite compound represented by the following formula (XIII). It is particularly preferred to incorporate a triorganophosphate compound.

In the formula (XIII), R and R' represent an alkyl group having 6 to 30 carbon atoms or an aryl group or an alkylaryl group having 6 to 30 carbon atoms, which may be the same or different.

As described above, as the phosphonite compound, hydrazine (2,4-di-tert-butylphenyl)-co-phenylphenyl diphosphinate is preferred; stability with the phosphonite as a main component As the agent, commercially available Sandostab P-EPQ (trademark, manufactured by Clariant Co., Ltd.) and Irgafos P-EPQ (trademark, manufactured by CIBA SPECIALTY CHEMICALS) can be used.

Further, among the above formula (XIII), preferred phosphite compounds are distequine pentaerythritol diphosphite, bis(2,4-di-t-butylphenyl)pentane pentaerythritol diphosphite. , bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite and bis{2,4-bis(1-methyl-1-phenylethyl)phenyl} Pentaerythritol diphosphite.

In the resin composition of the present invention, a thermoplastic resin other than the A component and the B component may be blended with an elastomer, another flow modifier, an antibacterial agent, a dispersant such as a fluid paraffin, a photocatalyst antifouling agent, and a photosensitive discoloration. Agents, etc.

Examples of the other resin include a polyamide resin, a polyimide resin, a polyether phthalimide resin, a polyurethane resin, a silicone resin, a polyphenylene ether resin, and a poly Polyolefin resin such as phenyl sulfide resin, polysulfonated resin, polyethylene, polypropylene, etc.; polystyrene resin, acrylonitrile/styrene copolymer (AS resin), polymethyl acrylate resin, phenol resin, ring A resin such as an oxygen resin, a cyclic polyolefin resin, a polylactic acid resin, a polycaprolactone resin, and a thermoplastic fluororesin (for example, represented by a polyvinylidene fluoride resin). Examples of the elastomer include an acrylic elastomer, a polyester elastomer, and a polyamide-based elastomer.

The content of the thermoplastic resin and the elastomer described above is preferably 30 parts by weight or less, and more preferably 20 parts by weight or less, based on 100 parts by weight of the resin component.

(Method for Producing Resin Composition)

The preparation of the resin composition of the present invention can be carried out by any method. For example, a method in which the component A, the component B, the component C, the component D, and other optional components are mixed in advance, and then melt-kneaded and pelletized is performed.

Examples of the means for preliminary mixing include a nauta mixer, a V-type mixer, a Henschel mixer, a mechanochemical polishing apparatus, and an extrusion mixer. In the preliminary mixing, granulation can be carried out by a granulator, a briquetting machine or the like according to the demand. As another method, for example, when a powder form is used as the component A, a part of the powder is mixed with the blended additive to prepare a master batch of the powder-diluted additive, and used. The method of this masterbatch. After the preliminary mixing, the melt kneading machine typified by a vented biaxial extruder is melt-kneaded, and granulated by means of a granulator or the like. As the melt kneading machine, a Banbury mixer, a kneading drum, a thermostatic stirring vessel, and the like may be additionally exemplified, and a vented twin-shaft extruder is preferable.

Further, a method of separately supplying each component to a melt kneader represented by a biaxial extruder may be used. Further, for example, a method of separately supplying a part of the components to the melt kneading machine separately from the remaining components. In particular, in the case of blending an inorganic filler, the inorganic filler is preferably supplied from a supply port on the way of the extruder, and in a molten resin, using a supply device such as a side feeder. The method and granulation for preliminary mixing are also the same as described above. Further, in the case where the blended component has a liquid material, it may be supplied to a melt kneader using a so-called liquid injection device or a liquid addition device.

As the extruder, it is preferable to use an apparatus having an exhaust port that "exhaustes the moisture in the raw material or the volatile gas generated from the melt-kneading resin." A vacuum pump is preferably provided for efficiently discharging the generated moisture and volatile gas from the exhaust port to the outside of the extruder. Further, a screen for removing foreign matter or the like mixed in the extruded raw material may be placed in a region in front of the die portion of the extruder to remove the foreign matter from the resin composition. Examples of the screen include a gold mesh, a screen changer, a sintered metal plate (such as a disk filter), and the like.

Examples of the melt kneading machine include a Banbury mixer, a kneading drum, a uniaxial extruder, and a multi-axis extruder of three or more axes.

Further, it is preferable that the component A and the component B contain less moisture before the melt-kneading. Therefore, it is preferable to dry or knead either or both of the A component or the B component by a method such as various hot air drying, electromagnetic wave drying, or vacuum drying. In the melt kneading, the suction degree of the exhaust port is 1 to 60 kPa, preferably in the range of 2 to 30 kPa.

The resin which is extruded as described above may be directly cut to pelletize it, or after the strands are formed, the strand may be cut by a pelletizer to be pelletized. In the case of granulation, in the case where it is necessary to reduce the influence of external dust, it is preferable to clean the environment around the extruder. Further, in the production of the pellets, various methods proposed in the polycarbonate resin for optical discs can be used, and the shape distribution of the particles can be appropriately narrowed, the miss cuts can be reduced, and the transportation or transportation can be reduced. The tiny powder and the reduction of bubbles (vacuum bubbles) that occur inside the strands and particles. With such prescriptions, the high cycle of formation can be achieved and the proportion of undesirable occurrences such as silver can be reduced. Further, the shape of the particles may be a general shape such as a cylinder, a corner column, or a spherical shape, but is preferably a columnar shape. The diameter of the cylinder should be 1~5mm, preferably 1.5~4mm, more preferably 2~3.3mm. On the other hand, the length of the cylinder is preferably 1 to 30 mm, more preferably 2 to 5 mm, and more preferably 2.5 to 3.5 mm.

(molded article formed using the resin composition of the present invention)

By molding the pellets produced as described above, a molded article formed using the resin composition of the present invention can be obtained. Preferably, it is obtained by injection molding and extrusion molding. In the injection molding, not only general molding methods but also injection compression molding, injection pressure molding, gas-assisted injection molding, foam molding (including a method of injecting a supercritical fluid), insert molding, and in-mold coating molding are also possible. Insulation mold forming, rapid heating and cooling mold forming, two-color molding, multi-color molding, sandwich molding, and ultra-high-speed injection molding. Further, any of the cold runner method and the hot runner method can be selected for molding.

Further, in the extrusion molding, various shaped extruded articles, sheets, films, and the like can be obtained. In the formation of a sheet or a film, an inflation method, a calender method, a casting method, or the like can also be used. Further, a heat shrinkable tube can also be formed by applying a specific stretching operation. Further, the resin composition of the present invention can be used as a molded article by spin molding or blow molding.

The inventors of the present invention have now considered that the preferred embodiment of the present invention is formed by combining the preferred ranges of the above-described respective elements, for example, representative examples thereof described in the following examples. Of course, the invention is not limited to the forms.

Example

Hereinafter, the present invention will be more specifically described by way of examples, but the invention is not limited thereto. Further, the parts in the examples are parts by weight, and % is % by weight unless otherwise specified. Further, the evaluation and the production of the resin pellets were carried out by the following methods.

(I) Evaluation of resin composition

(i) Titanium content analysis: Measurement was carried out using an Agilent 7500 cs, an ICP mass spectrometer manufactured by Agilent Technologie. In addition, the sample is added with sulfuric acid in the weighed sample and borrowed After the resin was ashed by microwave decomposition, nitric acid was further added and subjected to microwave decomposition, and the obtained residual metal was made to a constant volume with ultrapure water, and the amount of Ti element was measured from the residue.

(ii) Rigidity: After drying the obtained pellets at 120 ° C for 5 hours, the injection molding machine (SG-150U manufactured by Sumitomo Heavy Industries, Ltd.) was used at a cylinder temperature of 280 ° C and a mold temperature of 70 ° C. The formed piece was molded, and the tensile modulus was measured in accordance with ISO 527-1 and 2.

(iii) Sand impact strength: After drying the obtained various pellets at 120 ° C for 5 hours, an injection molding machine (SG-150U manufactured by Sumitomo Heavy Industries, Ltd.), a cylinder temperature of 280 ° C, and a mold temperature of 70 ° C Next, the formed piece was molded, and the measurement of the impact strength of the satin with the notch was carried out in accordance with ISO179.

(iv) Moisture-resistance: After the obtained resin pellets were dried at 120 ° C for about 5 hours, and the water content in the pellets was 200 ppm or less, an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd.: SG260M-HP) was used. A test piece having a length of 70 mm, a width of 50 mm, and a thickness of 2 mm was continuously injection molded under the conditions of a cylinder temperature of 280 ° C, a mold temperature of 70 ° C, a molding cycle of 50 seconds, and an injection speed of 15 mm / sec. The test piece was placed in an environment of a temperature of 23 ° C and a relative humidity of 50% for 24 hours to serve as a test piece before the wet heat treatment, and the test piece before the wet heat treatment was placed at a temperature of 80 ° C and a relative humidity of 95%. The sample was placed in a constant temperature and humidity tester for 500 hours, and then subjected to a wet heat treatment, and then placed in an environment of a temperature of 23 ° C and a relative humidity of 50% for 24 hours as a test piece after the wet heat treatment.

In the case of avoiding the incorporation of foreign matter, the test pieces before the wet heat treatment and the wet heat treatment are respectively pulverized and dried at 120 ° C for about 5 hours so that the water content is 200 ppm or less, and the temperature is 280 ° C for each pulverized sample. The melt flow rate (MVR; Melt volume rate) was measured in accordance with the method of ISO 1133 under the condition of a load of 2.16 kgf. The measurement is made by Toyo Seiki The semi-automatic melt indexer 2A type is manufactured by the company. The heat and humidity resistance was calculated by the following formula to calculate the rate of change (ΔMVR) before and after the wet heat treatment. The larger the ΔMVR, the more severe the deterioration of the resin representing the molded article, and the worse the moist heat resistance, and the ΔMVR is preferably 200 or less, and more preferably 170 or less.

△MVR (moisture resistance) = 100 × (MVR of test piece after wet heat treatment) / (MVR of test piece before wet heat treatment)

(v) Thermal stability: After the obtained resin pellets were dried at 120 ° C for about 5 hours to have a water content of 200 ppm or less in the pellets, an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd.: SG260M-HP) was used. A test piece having a length of 70 mm, a width of 50 mm, and a thickness of 2.0 mm was continuously injection-molded under conditions of a cylinder temperature of 280 ° C, a mold temperature of 70 ° C, a molding cycle of 50 seconds, and an injection speed of 15 mm / sec to obtain a test piece of a continuous molded product ( The test piece of the continuous molded product has substantially the same quality as the test piece before the wet heat treatment). After the test piece of the continuous molded product was obtained, the molding machine was stopped for 10 minutes to allow the molten resin to remain in the cylinder of the molding machine. After the molding machine was stopped for 10 minutes, the molding was started again, and after the molding, the second molded article was used as a test piece for the retained molded article.

When the impurities are mixed, the continuous molded product and the retained molded product are pulverized, and dried at 120 ° C for about 5 hours to have a water content of 200 ppm or less. Then, for each pulverized sample, the temperature is 280 ° C and the load is 2.16 kgf. The melt flow rate (MVR; Melt volume rate) was measured in accordance with the method of ISO 1133. The measurement was carried out by a semi-automatic melt indexer 2A type manufactured by Toyo Seiki Co., Ltd. The thermal stability was calculated by the following formula to calculate the MVR change rate (ΔMVR (thermal stability)) before and after the retention. The larger the ΔMVR (thermal stability), the more severe the deterioration of the resin at the time of retention, and the worse the thermal stability, and the ΔMVR is preferably 150 or less, and more preferably 130 or less.

ΔMVR (thermal stability) = 100 × (MVR of the test piece of the retained molded product) / (MVR of the test piece of the continuous molded product)

(vi) Chemical resistance: For the test piece prepared in the (iii) sand impact test, a bending strain of 6 MPa was applied, and it was immersed in a commercially available environment at a temperature of 23 ° C and a relative humidity of 50%. After 30 minutes of gasoline, the appearance was visually observed and evaluated. In addition, the evaluation is carried out by the following benchmarks.

O: No abnormality was found.

×: Appearance change such as crack or whitening was observed in the molded article

Examples 1 to 12 and Comparative Examples 1 to 11

The polycarbonate resin, the polyester resin, the filler, and various additives are mixed in a mixer in the blending amounts described in Tables 1 to 3, and then melt-kneaded using a vented twin-axis extruder to obtain the present invention. Particles composed of the resin composition. In addition to the filler, various additives are prepared in advance as a mixture with the polycarbonate resin powder for a concentration of 10 to 100 times the blending amount, and then mixed as a whole by a mixer. The vented twin-shaft extruder was manufactured by Nippon Steel Co., Ltd.: TEX30α-31.5BW-2V (completely engaged, co-rotating, and two screw shafts). It is the type of the kneading area in front of the exhaust port. The discharge conditions were a discharge amount of 20 kg/h, a screw shaft rotation number of 130 rpm, and an exhaust vacuum degree of 3 kPa, and the extrusion temperature was 270 ° C from the first supply port to the mold portion.

The components indicated by the symbols in Tables 1 to 3 are as follows.

(component A)

A-1: Linear aromatic polycarbonate resin powder having a viscosity average molecular weight of 22,400

(B component)

(B-1 component)

PBT-1: Polybutylene terephthalate resin with an IV value of 0.87 (Bao Li Plastic Co., Ltd. DURANEX 500FP (trade name))

(B-2 ingredient)

PET-1: polyethylene terephthalate resin prepared by the following manufacturing method (having a viscosity of 0.53, a titanium content of 23 ppm)

(Production method)

While stirring a solution of monolauryl phosphate in ethylene glycol heated to 100 ° C, a mixture of ethylene glycol and acetic acid containing titanium tetrabutoxide is slowly added to make a titanium compound and a phosphorus compound. The reaction is completed to produce a catalyst. After the ester oligomer is produced from ethylene glycol and terephthalic acid, it is placed in a polycondensation reaction tank together with a catalyst to carry out a polycondensation reaction. By monitoring the loading of the agitating blades in the reaction system, the extent to which the polycondensation proceeds is confirmed to terminate the reaction when the desired degree of polymerization is reached. Thereafter, the reaction mixture in the system was continuously extruded from the discharge portion, and cooled and solidified and cut to adjust the granular particles of polyethylene terephthalate having a particle diameter of about 3 mm.

(C component)

C-1: EXL2390: Acrylic core-shell polymer (manufactured by Rohm and Haas Co., Ltd.: Paraloid EXL-2390 (trade name), core is a butyl acrylate component of about 50% by weight and 2-ethylhexyl acrylate component About 40% by weight of shell-shell polymer having a shell of about 10% by weight of methyl methacrylate)

C-2 (comparative): EXL2388: Acrylic core-shell polymer (manufactured by Rohm and Haas Co., Ltd.: Paraloid EXL-2388 (trade name), nucleus is a butyl acrylate component of about 90 % by weight of core-shell polymer with a shell of about 10% by weight of methyl methacrylate)

C-3 (comparative): EXL-2620: styrene rubbery polymer (manufactured by Rohm and Haas Co., Ltd.: Paraloid EXL-2620 (trade name), core is polybutadiene 70% by weight, shell is styrene And 30% by weight of methyl methacrylate core-shell polymer)

C-4 (comparative): S2001: a composite rubber 90 having a structure in which methyl methacrylate and a structure in which a "polyorganoanthracene rubber component and a polyalkyl (meth) acrylate rubber component are intertwined to form an inseparable state" Composite rubber-based graft copolymer formed by weight-% graft polymerization (METABLEN S-2001 (trade name) manufactured by Mitsubishi Rayon Co., Ltd.)

(D component)

D-1: Asbestos with an average particle diameter of 4 μm (made by Kansai MATEC Co., Ltd.: KGP-H40)

D-2: Asbestos with an average particle diameter of 5 μm (manufactured by KINSEI MATEC Co., Ltd.: SH-1250)

D-3: Compressed micronized talc (manufactured by Linhuacheng Co., Ltd.: Upn HS-T0.8)

D-4: Wet-pulverized quartz having an average particle diameter of 22 μm (manufactured by Yamaguchi Quartz Co., Ltd.: A-21)

(other ingredients)

AO-1: bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite (made by ADEKA: ADEKA STAB PEP-24G)

AO-2: Trimethyl phosphate (manufactured by Daiba Chemical Industry Co., Ltd.: TMP)

Effect of the invention

From the first graph comparing "Example 2 using C-1 as component C" and "Comparative examples 6 to 8 using C-2, C-3, and C-4 as component C", it is clear that the examples are as follows. In 2, both the tensile modulus and the sand impact strength are excellent.

Similarly, the second graph comparing "Example 12 using C-1 as a C component" and "Comparative examples 9 to 11 using C-2, C-3, and C-4 as a C component" can be clearly known. In Example 12, both the tensile modulus and the sand impact strength were excellent.

Thus, the resin composition of the present invention is excellent in both the tensile modulus and the sand impact strength. Further, the resin composition of the present invention is excellent in thermal stability and has good chemical corrosion resistance.

Industrial utilization possibility

The resin composition of the present invention can be widely used in various fields such as buildings, building materials, agricultural materials, marine materials, vehicles, electrical and electronic equipment, machinery, and the like.

Claims (12)

A resin composition comprising: (A) a polycarbonate resin (component A); (B) a polyester resin (component B); (C) a core-shell polymer (component C); and (D) a filler (D) (Component): (C) 100 parts by weight of (A) polycarbonate resin (component A) and 100 parts by weight of (B) 20 to 50 parts by weight of the polyester resin (component B), (C) The core-shell polymer (component C) is 1 to 10 parts by weight, and the (D) filler (component D) is 0 to 15 parts by weight. Further, (C) the core-shell polymer (component C) is composed of alkyl carbon. a core (C-1 component) composed of a crosslinked acrylate elastomer composed of an acrylate of 1 to 4 and an acrylate having an alkyl group of 5 to 8 and a "shell having a methacrylate as a main component" ( Composition of component C-2). The resin composition of claim 1, wherein the component B is polyethylene terephthalate resin (PET) and polybutylene terephthalate resin (PBT), and the blend ratio (weight ratio) ) (PET/PBT) is 1/7~7/8. The resin composition of the first aspect of the invention, wherein the polyester resin (component B) is a polyester resin polymerized using a compound containing the following reaction product as a catalyst: selected from the following formula (I) The titanium compound (1) shown, and the titanium compound (2) obtained by reacting the titanium compound (1) with an aromatic polyvalent carboxylic acid represented by the following formula (II) or an anhydride thereof The phosphorus compound component composed of at least one of the titanium compound component and at least one of the phosphorus compound (3) represented by the following formula (III) is a titanium atom equivalent molar amount (mTi) of the titanium compound component. a reaction product obtained by performing a reaction in a range of 1/3 to 1/1 of a molar molar ratio (mP/mP) of a phosphorus atom equivalent to a molar atom (mP) of the phosphorus compound component; and the polyester resin satisfies (i) and (ii); (i) having a viscosity of 0.4 to 1.2; (ii) a titanium element derived from a catalyst of 0.001 ppm to 100 ppm; Wherein, in the formula (I), R ¹ , R ² , R ³ and R ⁴ each independently represent an alkyl group having 2 to 10 carbon atoms, k represents an integer of 1 to 3, and k is 2 or 3 In the case of two or three R ² and R ³ systems, respectively, the same or different; Wherein, in the formula (II), m represents an integer of 2 to 4; Wherein, in the formula (III), R ⁵ is an unsubstituted or substituted aryl group having 6 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms. The resin composition of claim 1, wherein the polyester resin (component B) has a titanium element content of 0.001 to 50 ppm. The resin composition of the first aspect of the invention, wherein the polyester resin (component B) is a polyester resin obtained by polymerizing a compound represented by the following formula (IV) as a catalyst; In the above formula, R ⁶ and R ⁷ each independently represent an alkyl group having 2 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms. The resin composition of claim 1, wherein the polyester resin (component B) is polyethylene terephthalate. The resin composition of claim 1, wherein the polyester resin (component B) is polybutylene terephthalate. The resin composition of claim 1, wherein the component C-1 is a core formed of a crosslinked acrylate-based elastomer composed of butyl acrylate and 2-ethylhexyl acrylate. The resin composition of claim 1, wherein the component D is a filler selected from the group consisting of glass, talc, quartz, ash, zeolite, carbon fiber, and graphite. The resin composition of claim 9, wherein the component D is an inorganic filler selected from the group consisting of talc, quartz, and ash. A molded article obtained by subjecting a resin composition according to any one of claims 1 to 10 to injection molding. The injection molded article according to claim 11, wherein the injection molded article is an inner and outer member for a vehicle.