WO2015163479A1 - Composition de résine - Google Patents

Composition de résine Download PDF

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Publication number
WO2015163479A1
WO2015163479A1 PCT/JP2015/062628 JP2015062628W WO2015163479A1 WO 2015163479 A1 WO2015163479 A1 WO 2015163479A1 JP 2015062628 W JP2015062628 W JP 2015062628W WO 2015163479 A1 WO2015163479 A1 WO 2015163479A1
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component
resin
weight
resin composition
acid
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PCT/JP2015/062628
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English (en)
Japanese (ja)
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瞬 指宿
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帝人株式会社
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/03—Injection moulding apparatus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/87—Non-metals or inter-compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates

Definitions

  • the present invention relates to a resin composition and a molded product containing 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 composition comprising a polyester resin produced using a catalyst comprising a specific element, having excellent thermal stability, and excellent mechanical strength and chemical resistance.
  • Resin compositions containing polycarbonate resin, polyester resin, fillers and impact modifiers improve chemical resistance while maintaining the excellent appearance, mechanical and dimensional stability of polycarbonate resin, and add rigidity. Therefore, it is widely used in electrical / electronic, mechanical, OA, vehicle, and medical applications.
  • a molded product formed from a resin composition containing a polycarbonate resin, a polyester resin, and a filler (hereinafter sometimes referred to as PC / PEST / filler alloy) is used as a painted member or unpainted.
  • PC / PEST / filler alloy hereinafter sometimes referred to as PC / PEST / filler alloy
  • Patent Document 1 discusses a technique of blending an inorganic compound containing aluminum silicate as a main component in order to improve the heat and moisture resistance of a resin composition containing a polycarbonate resin and a polyester resin.
  • Patent Document 3 discusses a technique in which an acidic phosphorus-based additive and an inorganic filler whose water content is controlled to 0.25% by weight or less are mixed with PC / PEST alloy. Mixing a filler with a water content of 0.25% by weight or less improves the melt stability.
  • the management of the water content of the inorganic filler to be added means an increase in the number of steps for producing the resin composition. It is difficult to say that it is a general-purpose technology that leads to cost increase.
  • examination about the heat-and-moisture resistance of the obtained resin composition is not carried out, and the further improvement is required technically.
  • Patent Document 4 discusses a technique for controlling the dispersion state so that an inorganic compound having a pH of 8.0 or higher and an SiO 2 unit of 30% by weight or higher does not exist in the polycarbonate resin as much as possible. Although such technology has been confirmed to improve the thermal stability during the molding process, no examination has been made on the heat and moisture resistance. Moreover, in order to obtain such a resin composition, there is a high possibility that the manufacturing method will be restricted. As a result, the number of manufacturing steps is increased and the cost is increased, which is not a highly versatile technique. The method of adding additional additives to improve the heat and moisture resistance and thermal stability of PC / PEST / filler alloy and the method of controlling the dispersion state of the filler make it difficult to achieve both heat and moisture stability.
  • Patent Documents 5-7 an alloy material using PET produced with a specific polymerization catalyst has been proposed as a means for PC / PEST / filler alloy to satisfy the above requirements (see Patent Documents 5-7).
  • Patent Document 5 it is proposed to use a germanium catalyst to improve the color tone, melt stability, appearance, and moldability of PET produced with a general antimony compound or titanium compound as a polymerization catalyst. Yes.
  • Patent Document 6 proposes to improve color tone, thermal stability, and melt stability by including a polyester resin produced by using 1 to 30 ppm of a titanium-containing catalyst compound.
  • Patent Document 7 by producing a polyester resin using a titanium-containing catalyst compound having a specific structure, the polyester resin has a good color tone (b value), little foreign matter, and excellent thermal stability during melting. It is described that a polyester resin is obtained. However, the effect on the resin composition containing a resin other than the polyester resin is not mentioned, and no knowledge about wet heat resistance is taught.
  • Patent Document 8 discusses the use of a filler and an impact modifier in combination as a means for PC / PEST / filler alloy to satisfy the requirements of mechanical strength.
  • An object of the present invention is to provide a resin composition containing a polycarbonate resin, a polyester resin, and an impact modifier, and having excellent mechanical strength such as tensile modulus and Charpy impact strength. Another object of the present invention is to provide a resin composition having excellent heat and humidity resistance and thermal stability. Another object of the present invention is to provide a molded article made of the resin composition, particularly a vehicle interior member and a vehicle exterior member. As a result of intensive studies to achieve the above object, the present inventors have obtained a tensile elastic modulus by blending a polyester resin and a core-shell polymer having a specific structure into a polycarbonate resin, as shown in FIGS. It was also found that a resin composition having excellent Charpy impact strength can be obtained.
  • the obtained resin composition was found to be excellent in heat and moisture resistance and heat stability, and the present invention was completed.
  • the above-mentioned problem is based on 100 parts by weight of a resin composition comprising (A) 80 to 50 parts by weight of a polycarbonate resin (component A) and (B) 20 to 50 parts by weight of a polyester resin (component B).
  • a core (C-1 component) comprising a cross-linked acrylate ester elastic body composed of an acrylate ester having 1 to 4 carbon atoms in the alkyl group and an acrylate ester having 5 to 8 carbon atoms in the alkyl group And 1 to 10 parts by weight of a core-shell polymer (component C) consisting of a shell (component C-2) containing methacrylic acid ester as the main component and 0 to 15 parts by weight of a filler (component D) (D) Is achieved.
  • the polycarbonate resin used as the component A of the present invention is obtained by reacting a dihydric phenol and a carbonate precursor.
  • the reaction method include an interfacial polymerization method, a melt transesterification method, a solid phase transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound.
  • Representative examples of the dihydric phenol used here include hydroquinone, resorcinol, 4,4′-biphenol, 1,1-bis (4-hydroxyphenyl) ethane, and 2,2-bis (4-hydroxyphenyl).
  • a preferred dihydric phenol is bis (4-hydroxyphenyl) alkane, and bisphenol A is particularly preferred from the viewpoint of impact resistance, and is widely used.
  • a general-purpose polycarbonate which is a bisphenol A-based polycarbonate
  • a special polycarbonate manufactured using other dihydric phenols can be used as the A component.
  • BPM 4,4 ′-(m-phenylenediisopropylidene) diphenol
  • Bis-TMC 1,1-bis (4-hydroxy Phenyl) cyclohexane
  • Bis-TMC 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane
  • BCF 9,9-bis (4-hydroxyphenyl)
  • BCF polycarbonate (homopolymer or copolymer) using fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene
  • dihydric phenols other than BPA are preferably used in an amount of 5 mol% or more, particularly 10 mol% or more of the entire dihydric phenol component constituting the polycarbonate.
  • the component B constituting the polycarbonate resin composition is the following copolymeric polycarbonate (1) to (3). It is.
  • BPM is 20 to 80 mol% (more preferably 40 to 75 mol%, more preferably 45 to 65 mol%) in 100 mol% of the dihydric phenol component constituting the polycarbonate, and BCF Is a copolymer polycarbonate having a content of 20 to 80 mol% (more preferably 25 to 60 mol%, still more preferably 35 to 55 mol%).
  • BPA is 10 to 95 mol% (more preferably 50 to 90 mol%, more preferably 60 to 85 mol%) in 100 mol% of the dihydric phenol component constituting the polycarbonate, and BCF Is a copolycarbonate having a content of 5 to 90 mol% (more preferably 10 to 50 mol%, more preferably 15 to 40 mol%).
  • BPM is 20 to 80 mol% (more preferably 40 to 75 mol%, more preferably 45 to 65 mol%) in 100 mol% of the dihydric phenol component constituting the polycarbonate, and Bis -Copolymer polycarbonate having a TMC of 20 to 80 mol% (more preferably 25 to 60 mol%, more preferably 35 to 55 mol%).
  • These special polycarbonates may be used alone or in combination of two or more. Moreover, these can also be mixed and used for the bisphenol A type polycarbonate generally used. The production methods and characteristics of these special polycarbonates are described in detail in, for example, JP-A-6-172508, JP-A-8-27370, JP-A-2001-55435, and JP-A-2002-117580.
  • the water absorption of the polycarbonate is a value obtained by measuring the moisture content after being immersed in water at 23 ° C. for 24 hours in accordance with ISO 62-1980 using a disc-shaped test piece having a diameter of 45 mm and a thickness of 3.0 mm. is there.
  • Tg glass transition temperature
  • DSC differential scanning calorimeter
  • the carbonate precursor carbonyl halide, carbonic acid diester, haloformate or the like is used, and specific examples include phosgene, diphenyl carbonate, dihaloformate of dihydric phenol, and the like.
  • the aromatic polycarbonate resin is a branched polycarbonate resin copolymerized with a trifunctional or higher polyfunctional aromatic compound, or a polyester carbonate resin copolymerized with an aromatic or aliphatic (including alicyclic) difunctional carboxylic acid. And a copolymer polycarbonate resin copolymerized with a bifunctional alcohol (including alicyclic), and a polyester carbonate resin copolymerized with the bifunctional carboxylic acid and the bifunctional alcohol together.
  • Branched polycarbonate resin can impart anti-drip performance and the like to the resin composition of the present invention.
  • the trifunctional or higher polyfunctional aromatic compound used in the branched polycarbonate resin include phloroglucin, phloroglucid, or 4,6-dimethyl-2,4,6-tris (4-hydroxydiphenyl) heptene-2, 2 , 4,6-trimethyl-2,4,6-tris (4-hydroxyphenyl) heptane, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) Ethane, 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, 4- ⁇ 4- [ Trisphenol such as 1,1-bis (4-hydroxyphenyl) ethyl] benz
  • the structural unit derived from the polyfunctional aromatic compound in the branched polycarbonate is 0.1% in a total of 100 mol% of the structural unit derived from the dihydric phenol and the structural unit derived from the polyfunctional aromatic compound.
  • the amount is from 01 to 1 mol%, preferably from 0.05 to 0.9 mol%, particularly preferably from 0.05 to 0.8 mol%.
  • a branched structural unit may be generated as a side reaction.
  • the amount of the branched structural unit is also 0.1% in a total of 100 mol% with a structural unit derived from a dihydric phenol.
  • a content of 001 to 1 mol%, preferably 0.005 to 0.9 mol%, particularly preferably 0.01 to 0.8 mol% is preferred. Regarding the ratio of such branched structures 1 It is possible to calculate by H-NMR measurement.
  • the aliphatic bifunctional carboxylic acid is preferably ⁇ , ⁇ -dicarboxylic acid.
  • aliphatic difunctional carboxylic acid examples include sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, icosanedioic acid and other straight-chain saturated aliphatic dicarboxylic acids, and cyclohexanedicarboxylic acid.
  • Preferred are alicyclic dicarboxylic acids such as As the bifunctional alcohol, an alicyclic diol is more preferable, and examples thereof include cyclohexanedimethanol, cyclohexanediol, and tricyclodecane dimethanol.
  • the polycarbonate resin can be produced by an interfacial polymerization method, a melt transesterification method, a solid phase transesterification method of a carbonate prepolymer, a ring-opening polymerization method of a cyclic carbonate compound, or the like. These reaction formats are well known in various documents and patent publications.
  • the viscosity average molecular weight of the polycarbonate resin is preferably 10,000 to 50,000, more preferably 14,000 to 30,000, and further preferably 14,000 to 26,000.
  • a resin composition obtained from a polycarbonate resin having a viscosity average molecular weight exceeding 50,000 is inferior in versatility in that it is inferior in fluidity during injection molding.
  • the polycarbonate resin may be obtained by mixing those having a viscosity average molecular weight outside the above range.
  • a polycarbonate resin having a viscosity average molecular weight exceeding the range (50,000) improves the entropy elasticity of the resin. As a result, good moldability is exhibited in gas assist molding and foam molding which may be used when molding a reinforced resin material into a structural member.
  • a polycarbonate resin having a viscosity average molecular weight of 70,000 to 300,000 (component A-1-1) and a polycarbonate resin having a viscosity average molecular weight of 10,000 to 30,000 (A Polycarbonate resin having a viscosity average molecular weight of 16,000 to 35,000 (hereinafter sometimes referred to as “high molecular weight component-containing polycarbonate resin”).
  • the molecular weight of the A-1-1 component is preferably 70,000 to 200,000, more preferably 80,000 to 200,000, still more preferably 100,000 to 200,000, Particularly preferred is 100,000 to 160,000.
  • the molecular weight of the A-1-2 component is preferably 10,000 to 25,000, more preferably 11,000 to 24,000, still more preferably 12,000 to 24,000, and particularly preferably 12,000 to 23. , 000.
  • the high molecular weight component-containing polycarbonate resin can be obtained by mixing the A-1-1 component and the A-1-2 component at various ratios and adjusting so as to satisfy a predetermined molecular weight range.
  • the A-1-1 component is 2 to 40% by weight, more preferably the A-1-1 component is 3 to 30% by weight,
  • the A-1-1 component is preferably 4 to 20% by weight, and particularly preferably the A-1-1 component is 5 to 20% by weight.
  • a method for preparing a polycarbonate resin containing a high molecular weight component (1) a method in which the A-1-1 component and the A-1-2 component are polymerized independently and mixed, (2) In the same system, a polycarbonate resin showing a plurality of polymer peaks in a molecular weight distribution chart by GPC method represented by the method shown in JP-A-306336 is used. And (3) a polycarbonate resin obtained by such a production method (production method (2)), a separately produced A-1-1 component and / or A-1- Examples include a method of mixing two components.
  • the viscosity average molecular weight referred to in the present invention is first determined by the specific viscosity ( ⁇ SP ) At 20 ° C.
  • the viscosity average molecular weight of the polycarbonate resin in the resin composition of the present invention is calculated as follows. That is, the composition is mixed with 20 to 30 times its weight of methylene chloride to dissolve soluble components in the composition. Such soluble matter is collected by Celite filtration. Thereafter, the solvent in the obtained solution is removed. The solid after removal of the solvent is sufficiently dried to obtain a solid component that dissolves in methylene chloride. A specific viscosity at 20 ° C.
  • the polyester resin used as the component B of the present invention is a polymer or copolymer obtained by a condensation reaction mainly comprising an aromatic dicarboxylic acid or a reactive derivative thereof and a diol or an ester derivative thereof.
  • aromatic dicarboxylic acid terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, 4,4′-biphenyl ether Dicarboxylic acid, 4,4′-biphenylmethane dicarboxylic acid, 4,4′-biphenylsulfone dicarboxylic acid, 4,4′-biphenylisopropylidenedicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4′-dicarboxylic acid Acid, 2,5-anthracene dicarboxylic acid, 2,6-anthracene dicarboxylic acid, 4,4′-p-terphenylene dicarboxylic acid, aromatic dicarboxylic acid such as 2,5-pyridinedicarboxylic acid, diphenylmethane dicarboxylic acid, di
  • Aromatic dicarboxylic acids may be used as a mixture of two or more. In addition, if the amount is small, it is also possible to use a mixture of one or more aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid and dodecanediic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, etc. together with the dicarboxylic acid. .
  • diol that is a component of the polyester resin examples include ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, pentamethylene glycol, hexamethylene glycol, decamethylene glycol, and 2-methyl-1,3-propanediol.
  • Aliphatic diols such as diethylene glycol and triethylene glycol, alicyclic diols such as 1,4-cyclohexanedimethanol, diols containing aromatic rings such as 2,2-bis ( ⁇ -hydroxyethoxyphenyl) propane, and the like A mixture thereof may be mentioned.
  • one or more long chain diols having a molecular weight of 400 to 6,000 that is, polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol, etc. may be copolymerized.
  • the polyester resin can be branched by introducing a small amount of a branching agent.
  • branching agent A trimesic acid, a trimellitic acid, a trimethylol ethane, a trimethylol propane, a pentaerythritol, etc. are mentioned.
  • polyester resins include polyethylene terephthalate (PET), polypropylene terephthalate, polybutylene terephthalate (PBT), polyhexylene terephthalate, polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), polyethylene-1,2-
  • PET polyethylene terephthalate
  • PBT polypropylene terephthalate
  • PEN polyethylene naphthalate
  • PBN polybutylene naphthalate
  • a copolymer polyester resin such as polyethylene isophthalate / terephthalate, polybutylene terephthalate / isophthalate, and the like can be given.
  • polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate and a mixture thereof having a good balance of mechanical properties and the like can be preferably used.
  • the terminal group structure of the polyester resin is not particularly limited, and the ratio of the hydroxyl group and the carboxyl group in the terminal group may be large, in addition to the case where the ratio is large.
  • those terminal groups may be sealed by reacting a compound having reactivity with such terminal groups.
  • Such a polyester resin is produced by polymerizing a dicarboxylic acid component and the diol component while heating in the presence of a specific titanium-based catalyst and discharging by-product water or lower alcohol out of the system according to a conventional method. It is preferable.
  • the above titanium-based catalyst includes a reaction product of the following titanium compound component (A) and phosphorus compound component (B).
  • the titanium compound component (A) includes a titanium compound (1) represented by the following general formula (I), an aromatic polyvalent carboxylic acid represented by the titanium compound (1) and the following general formula (II), or anhydrous It is at least one titanium compound component selected from the group consisting of a titanium compound (2) obtained by reacting with a product.
  • R 1 , R 2 , R 3 And R 4 Each independently represents an alkyl group having 2 to 10 carbon atoms, k represents an integer of 1 to 3, and when k is 2 or 3, 2 or 3 R 2 And R 3 May be the same as or different from each other.
  • 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 general 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-mentioned specific titanium-based catalyst is superior in thermal stability and wet heat resistance compared to the case of using germanium, antimony and other titanium-based catalysts.
  • the quality is stable even if the amount of additives such as hue stabilizer and heat stabilizer during production is less than when other catalysts are used. Since decomposition of the additive in a thermal environment or a moist heat environment is reduced, it is presumed that the thermal stability and the heat and humidity resistance are excellent.
  • the titanium compound equivalent molar amount (mTi) of the titanium compound component (A) and the phosphorus atom equivalent molar amount of the phosphorus compound component (B) is preferably in the range of 1/3 to 1/1, and more preferably in the range of 1/2 to 1/1.
  • the molar amount in terms of titanium atom of the titanium compound component (A) is the product of 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 phosphorus atom equivalent molar amount of the phosphorus compound component (B) is the molar amount of each phosphorus compound contained in the phosphorus compound component (B) and the phosphorus atoms contained in one molecule of the phosphorus compound. It is the total value of the product with the number. However, since the phosphorus compound represented by the formula (III) contains one phosphorus atom per molecule, the phosphorus atom equivalent molar amount of the phosphorus compound is equal to the molar amount of the phosphorus compound.
  • reaction molar ratio (mTi / mP) is greater than 1/1, that is, when the amount of the titanium compound component (A) is excessive, the color tone of the polyester resin obtained using the resulting catalyst (b value is too high). ) And its heat resistance may be reduced. Further, when the reaction molar ratio (mTi / mP) is less than 1/3, that is, when the amount of the titanium compound component (A) becomes too small, the catalytic activity of the resulting catalyst for the polyester formation reaction may be insufficient. is there.
  • Examples of the titanium compound (1) represented by the general formula (I) used for the titanium compound component (A) include titanium tetrabutoxide, titanium tetraisopropoxide, titanium tetrapropoxide, and titanium tetraethoxide.
  • Examples include tetraalkoxides, and alkyl titanates such as octaalkyltrititanates and hexaalkyldititanates, and among these, titanium having good reactivity with the phosphorus compound component used in the present invention. It is preferable to use tetraalkoxides, and it is particularly preferable to use titanium tetrabutoxide.
  • the titanium compound (2) used for the titanium compound component (A) is obtained by reacting the titanium compound (1) with the aromatic polyvalent carboxylic acid represented by the general formula (II) or an anhydride thereof.
  • the aromatic polyvalent carboxylic acid of the general formula (II) and its anhydride are preferably selected from the group consisting of phthalic acid, trimellitic acid, hemimellitic acid, pyromellitic acid and their anhydrides. In particular, it is more preferable to use trimellitic anhydride having good reactivity with the titanium compound (1) and high affinity with the polyester of the resulting polycondensation catalyst.
  • the reaction between the titanium compound (1) and the aromatic polyvalent carboxylic acid of the general formula (II) or its anhydride is carried out by mixing the aromatic polyvalent carboxylic acid or its anhydride in a solvent and partially or entirely Is dissolved in a solvent, and the titanium compound (1) is dropped into this mixed solution and heated at a temperature of 0 ° C. to 200 ° C. for 30 minutes or more, preferably at a temperature of 30 to 150 ° C. for 40 to 90 minutes. Is called.
  • the reaction pressure at this time is not particularly limited, and normal pressure is sufficient.
  • the catalyst can be appropriately selected from those capable of dissolving a required amount of the compound of the formula (II) or part or all of its anhydride, preferably ethanol, ethylene glycol, trimethylene It is selected from glycol, tetramethylene glycol, benzene, xylene and the like.
  • anhydride preferably ethanol, ethylene glycol, trimethylene It is selected from glycol, tetramethylene glycol, benzene, xylene and the like.
  • the reaction molar ratio between the titanium compound (1) and the compound represented by the formula (II) or its anhydride There is no limitation on the reaction molar ratio between the titanium compound (1) and the compound represented by the formula (II) or its anhydride. However, if the proportion of the titanium compound (1) is too high, the color tone of the resulting polyester resin may be deteriorated or the softening point may be lowered. On the contrary, if the proportion of the titanium compound (1) is too low, it is heavy. The condensation reaction may be difficult
  • the reaction molar ratio between the titanium compound (1) and the compound of the formula (II) or its anhydride is preferably controlled within the range of 2/1 to 2/5.
  • the reaction product obtained by this reaction may be directly subjected to the reaction with the above-mentioned phosphorus compound (3) or recrystallized using a solvent comprising acetone, methyl alcohol and / or ethyl acetate. Then, this may be reacted with the phosphorus compound (3).
  • R 5 The aryl group having 6 to 20 carbon atoms or the alkyl group having 1 to 20 carbon atoms represented by the formula may be unsubstituted or substituted by one or more substituents May be. Examples of the substituent include a carboxyl group, an alkyl group, a hydroxyl group, and an amino group.
  • the phosphorus compound (3) of the general formula (III) includes, for example, monomethyl phosphate, monoethyl phosphate, monotrimethyl phosphate, mono-n-butyl phosphate, monohexyl phosphate, monoheptyl phosphate, monooctyl phosphate, monononyl phosphate, Monodecyl phosphate, monododecyl phosphate, monolauryl phosphate, monooleyl phosphate, monotetradecyl phosphate, monophenyl phosphate, monobenzyl phosphate, mono (4-dodecyl) phenyl phosphate, mono (4-methylphenyl) phosphate, mono (4 -Ethylphenyl) phosphate, mono (4-propylphenyl) phosphate, mono (4-dodecylphenyl) phosphate, monotolylphosphate Monoalkyl phosphates and monoaryl phosphates such as phosphat
  • a phosphorus compound component (B) comprising at least one phosphorus compound (3) of the formula (III) and a solvent are prepared.
  • the normal reaction system is preferably 50 ° C to 200 ° C, more preferably Is carried out by heating at a temperature of 70 ° C. to 150 ° C., preferably for 1 minute to 4 hours, more preferably for 30 minutes to 2 hours.
  • the reaction pressure is not particularly limited, and may be any of under pressure (0.1 to 0.5 MPa), normal pressure, or reduced pressure (0.001 to 0.1 MPa). Usually performed under normal pressure.
  • the solvent for the phosphorus compound component (B) of the formula (III) used in the catalyst preparation reaction is not particularly limited as long as at least a part of the phosphorus compound component (B) can be dissolved.
  • ethanol ethylene
  • a solvent consisting of at least one selected from glycol, trimethylene glycol, tetramethylene glycol, benzene, xylene and the like is preferably used.
  • reaction product containing reaction mixture it may be used as a production catalyst, or the separated reaction product is purified by recrystallization from a recrystallization agent such as acetone, methyl alcohol and / or water, and the purified product obtained thereby. May be used as a catalyst. Moreover, you may use the reaction product containing reaction mixture as a catalyst containing mixture as it is, without isolate
  • a recrystallization agent such as acetone, methyl alcohol and / or water
  • a titanium compound component (A) comprising at least one titanium compound (1) of the above formula (I) (where k represents 1), that is, titanium tetraalkoxide, and the above formula (III) It is preferable that the reaction product with the phosphorus compound component (B) comprising at least one phosphorus compound is used as a catalyst. Furthermore, a compound represented by the following general formula (IV) is preferably used as the titanium-based catalyst. [R in the above formula 6 And R 7 Each independently represents an alkyl group having 2 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms.
  • the catalyst containing the titanium / phosphorus compound represented by the formula (IV) has high catalytic activity, and the polyester resin produced using the catalyst has a good color tone (low b value) and is practically sufficient. In addition, it has a low content of acetaldehyde, a residual metal and a cyclic trimer of an ester of an aromatic dicarboxylic acid and an alkylene glycol, and has practically sufficient polymer performance.
  • the titanium / phosphorus compound of the general formula (IV) is preferably contained in an amount of 50% by weight or more, and more preferably 70% by weight or more.
  • the amount of the titanium-based catalyst used is preferably an amount such that the mmol amount in terms of titanium atom is 2 to 40 mm% with respect to the total mmol amount of the aromatic dicarboxylic acid component contained in the polymerization starting material. It is more preferably ⁇ 35 mm%, and even more preferably 10-30 mm%. If it is less than 2 mm%, the catalyst's promotion effect on the polycondensation reaction of the polymerization starting material becomes insufficient, the polyester production efficiency becomes insufficient, and a polyester resin having a desired degree of polymerization cannot be obtained. There is.
  • the color tone (b value) of the resulting polyester resin becomes insufficient and becomes yellowish, and its practicality may be lowered.
  • the aromatic dicarboxylic acid or its ester-forming derivative and the alkylene glycol or its ester-forming derivative are heated. Produced by reacting.
  • an ethylene glycol ester of terephthalic acid and / or a low polymer thereof used as a raw material for polyethylene terephthalate may be obtained by directly esterifying terephthalic acid and ethylene glycol, or by converting a lower alkyl ester of terephthalic acid and ethylene glycol It is produced by a method of transesterification or an addition reaction of terephthalic acid with ethylene oxide.
  • the above-described aromatic dicarboxylic acid alkylene glycol ester and / or a low polymer thereof may contain other dicarboxylic acid ester copolymerizable therewith as an additional component, so that the effect of the method of the present invention is not substantially impaired.
  • the copolymerizable additional component is preferably an acid component such as aliphatic and alicyclic dicarboxylic acids such as adipic acid, sebacic acid, 1,4-cyclohexanedicarboxylic acid, and hydroxycarboxylic acids such as One or more of ⁇ -hydroxyethoxybenzoic acid, p-oxybenzoic acid, and the like and a glycol component, for example, alkylene glycol having 2 or more carbon atoms, 1,4-cyclohexanedimethanol, neopentyl glycol, bisphenol A , An ester with one or more of aliphatic, cycloaliphatic, aromatic diol compounds such as bisphenol S and polyoxyalkylene glycol, or anhydrides thereof.
  • an acid component such as aliphatic and alicyclic dicarboxylic acids such as adipic acid, sebacic acid, 1,4-cyclohexanedicarboxylic acid, and hydroxycarboxylic
  • the postscript component ester may be used alone or in combination of two or more thereof.
  • the copolymerization amount is preferably within the above range.
  • terephthalic acid and / or dimethyl terephthalate is used as a starting material
  • recovered dimethyl terephthalate obtained by depolymerizing polyalkylene terephthalate or recovered terephthalic acid obtained by hydrolyzing this is used as polyester.
  • the target polyalkylene terephthalate is polyethylene terephthalate.
  • the method for depolymerizing the recovered polyalkylene terephthalate to obtain dimethyl terephthalate is not particularly limited, and any conventionally known method can be employed.
  • the depolymerized product is subjected to a transesterification reaction with a lower alcohol such as methanol, and the reaction mixture is purified to recover the lower alkyl ester of terephthalic acid.
  • the polyester resin can be obtained by subjecting this to an ester exchange reaction with alkylene glycol and polycondensing the resulting phthalic acid / alkylene glycol ester.
  • the method for recovering terephthalic acid from the recovered dimethyl terephthalate is not particularly limited, and any conventional method may be used.
  • dimethyl terephthalate can be recovered from the reaction mixture obtained by the transesterification reaction by recrystallization and / or distillation, and then hydrolyzed with water at high temperature and high pressure to recover terephthalic acid.
  • the total content of 4-carboxybenzaldehyde, p-toluic acid, benzoic acid and dimethyl hydroxyterephthalate is preferably 1 ppm or less.
  • the content of monomethyl terephthalate is preferably in the range of 1 to 5000 ppm.
  • a polyester resin can be produced by directly esterifying the terephthalic acid recovered by the above-described method with an alkylene glycol and polycondensing the resulting ester.
  • the timing of adding the catalyst to the polymerization starting material is any stage before the start of the polycondensation reaction of the aromatic dicarboxylic acid alkylene glycol ester and / or its low polymer.
  • an aromatic dicarboxylic acid alkylene glycol ester may be prepared and a polycondensation reaction may be initiated by adding a catalyst solution or slurry to the reaction system, or the aromatic dicarboxylic acid alkylene glycol ester may be A catalyst solution or slurry may be added to the reaction system together with the starting material during preparation or after its preparation.
  • the production reaction conditions for the polyester resin used in the present invention are not particularly limited.
  • the polycondensation reaction is preferably performed at a temperature of 230 to 320 ° C. under normal pressure or reduced pressure (0.1 Pa to 0.1 MPa) or a combination of these conditions for 15 to 300 minutes.
  • a reaction stabilizer such as trimethyl phosphate may be added to the reaction system at any stage in the production of the polyester.
  • an agent, a flame retardant, a fluorescent brightening agent, a matting agent, a color adjusting agent, an antifoaming agent, and other additives may be blended.
  • the polyester resin preferably contains an antioxidant containing at least one hindered phenol compound, but the content thereof is 1% by weight or less based on the weight of the polyester resin. preferable. When the content exceeds 1% by weight, there may be a disadvantage that the quality of the obtained product is deteriorated due to thermal deterioration of the antioxidant itself.
  • the hindered phenol compound for antioxidant used in the polyester resin used in the present invention is pentaerythritol-tetra extract [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 3.9.
  • organic blue pigments such as azo, triphenylmethane, quinoline, anthraquinone, phthalocyanine and the like are included in the reaction system.
  • a color adjusting agent composed of one or more blue pigments can be added.
  • the polyester resin used in the present invention is substantially free of cobalt.
  • the polyester resin used in the present invention preferably contains 0.001 ppm to 100 ppm of the titanium element derived from the catalyst.
  • the content is more preferably 0.001 ppm to 50 ppm, and further preferably 1 ppm to 50 ppm. If the content of titanium element is more than 100 ppm, thermal stability and heat-and-moisture resistance may be deteriorated. If the content is less than 0.001 ppm, the remaining amount of catalyst of the polyester resin used is significantly lower, making it difficult to produce the polyester resin. In some cases, good mechanical strength, thermal stability and wet heat stability may not be obtained.
  • the intrinsic viscosity of the polyester resin is preferably 0.4 to 1.2. A more preferable range of the intrinsic viscosity is 0.45 to 0.95, and further preferably 0.50 to 0.9.
  • the polyester resin is a polyethylene terephthalate resin (PET) and a polybutylene terephthalate resin (PBT), and the blending ratio (weight ratio) (PET / PBT) is preferably 1/7 to 7/8.
  • the blending ratio is more preferably 1/7 to 1/2, and even more preferably 1/7 to 1/4. When the blending ratio is larger than 7/8, the chemical resistance is lowered, and when it is smaller than 1/7, the fluidity may be lowered.
  • the content of component B is 20 to 50 parts by weight, preferably 20 to 45 parts by weight, more preferably 25 to 40 parts by weight, per 100 parts by weight of the resin component. If the content is less than 20 parts by weight, the chemical resistance improving effect is not observed, and if it exceeds 50 parts by weight, the heat and humidity resistance is lowered and the impact strength is lowered.
  • C component: core-shell polymer The core-shell polymer used in the present invention is a crosslinked acrylate ester elastic body composed of an acrylate ester having 1 to 4 carbon atoms in the alkyl group and an acrylate ester having 5 to 8 carbon atoms in the alkyl group.
  • a core-shell polymer comprising a core (component C-1) and a shell (component C-2) containing methacrylic acid ester as a main component.
  • a core-shell polymer other than those described above is used as the C component, sufficient impact characteristics and rigidity cannot be obtained, and chemical resistance is lowered depending on the compound.
  • the acrylic acid ester having 1 to 4 carbon atoms in the alkyl group which is a constituent monomer of the C-1 component, include methyl acrylate, ethyl acrylate, propyl acrylate, and butyl acrylate.
  • Examples of the acrylate ester having 5 to 8 carbon atoms in the alkyl group include hexyl acrylate, heptyl acrylate, and 2-ethylhexyl acrylate.
  • the most preferred combination is a crosslinked alkyl acrylate elastic body composed of butyl acrylate and 2-ethylhexyl acrylate.
  • the C-2 component is derived from a (meth) acrylic acid ester (for example, methyl methacrylate).
  • the content of the C-1 component is preferably 50 to 99% by weight, more preferably 65 to 95% by weight, and more preferably 75 to 90% of 100% by weight of the C component. Most preferred is wt%. If the content of the C-1 component is less than 50% by weight, sufficient impact characteristics may not be obtained. On the other hand, if it exceeds 99% by weight, sufficient impact characteristics may not be obtained, which is not preferable.
  • the content of the acrylate ester having 5 to 8 carbon atoms in the alkyl group in the C-1 component is preferably 10 to 99% by weight, and 25 to 90% by weight in 100% by weight of the C-1 component. More preferred is 35 to 80% by weight, and most preferred is 40 to 70% by weight. If the amount is less than 10% by weight, sufficient impact characteristics may not be obtained. If the amount is more than 99% by weight, the heat resistance may decrease, which is not preferable.
  • the content of the core-shell polymer is 1 to 10 parts by weight, preferably 2 to 9 parts by weight, and more preferably 3 to 8 parts by weight with respect to 100 parts by weight of the resin component.
  • filler Conventionally known fillers can be used as the filler used in the present invention, and preferred fillers include fibrous glass filler, plate-like glass filler, fibrous carbon filler, and non-fibrous carbon. It is at least one filler selected from the group consisting of fillers and silicate minerals.
  • D-1 fibrous glass filler
  • fibrous glass filler examples include glass fibers (including metal-coated glass fibers) and glass milled fibers.
  • the glass fiber which becomes the base of the fibrous glass filler is obtained by rapidly cooling molten glass while drawing it by various methods to obtain a predetermined fiber shape.
  • the rapid cooling and stretching are not particularly limited.
  • the cross-sectional shape may be other than a perfect circle such as an ellipse, a cane, a flat shape, and a three-leaf shape in addition to a perfect circle. Further, it may be a mixture of a perfect circle and a shape other than a perfect circle.
  • the flat shape means that the average value of the major axis of the fiber cross section is 10 to 50 ⁇ m, preferably 15 to 40 ⁇ m, more preferably 20 to 35 ⁇ m, and the average value of the ratio of major axis to minor axis (major axis / minor axis) is 1.5.
  • the shape is 8 to 8, preferably 2 to 6 and more preferably 2.5 to 5.
  • the average fiber diameter of the fibrous glass filler having a high aspect ratio such as glass fiber is preferably 1 to 25 ⁇ m, and more preferably 3 to 17 ⁇ m. When a filler having an average fiber diameter in this range is used, good mechanical strength can be expressed without impairing the appearance of the molded product.
  • the fiber length of the high aspect ratio fibrous glass filler is preferably 60 to 500 ⁇ m, more preferably 100 to 400 ⁇ m, and particularly preferably 120 to 350 ⁇ m as the number average fiber length in the resin composition.
  • the number-average fiber length is a value calculated by an image analyzer from an image obtained by observing the residue of the filler collected by processing such as high-temperature ashing of a molded product, dissolution with a solvent, and decomposition with a chemical, using an optical microscope. It is. Further, when calculating such a value, the fiber diameter is used as a guide and the length is less than that.
  • the aspect ratio of the high aspect ratio fibrous glass filler is preferably 10 to 200, more preferably 15 to 100, and still more preferably 20 to 50.
  • the aspect ratio of the filler is a value obtained by dividing the average fiber length by the average fiber diameter.
  • Glass milled fiber is usually produced by shortening glass fiber using a pulverizer such as a ball mill.
  • the aspect ratio of the fibrous glass filler having a low aspect ratio such as glass milled fiber is preferably 2 to 10, more preferably 3 to 8.
  • the fiber length of the low aspect ratio fibrous glass filler is preferably 5 to 150 ⁇ m, more preferably 9 to 80 ⁇ m as the number average fiber length in the resin composition.
  • the average fiber diameter is preferably 1 to 15 ⁇ m, more preferably 3 to 13 ⁇ m.
  • the plate-like glass filler suitably used in the present invention include glass flakes including metal-coated glass flakes and metal oxide-coated glass flakes.
  • the glass flake used as the base of the plate-like glass filler is a plate-like glass filler produced by a method such as a cylindrical blow method or a sol-gel method.
  • Various kinds of glass flake raw materials can be selected depending on the degree of pulverization and classification.
  • the average particle size of the glass flakes used as the raw material is preferably 10 to 1000 ⁇ m, more preferably 20 to 500 ⁇ m, and still more preferably 30 to 300 ⁇ m. This is because the above range is excellent in both handleability and moldability.
  • a plate-like glass filler is cracked by melt-kneading with a resin, and its average particle size is reduced.
  • the number average particle size of the plate-like glass filler in the resin composition is preferably 10 to 200 ⁇ m, more preferably 15 to 100 ⁇ m, and still more preferably 20 to 80 ⁇ m.
  • the number average particle size is calculated by an image analyzer from an image obtained by observing the residue of the sheet glass filler collected by high temperature ashing of the molded product, dissolution with a solvent, decomposition with chemicals, etc. with an optical microscope. Is the value to be Further, when calculating such a value, the flake thickness is used as a guide and the length of the flake is not counted.
  • the thickness is preferably 0.5 to 10 ⁇ m, more preferably 1 to 8 ⁇ m, and further preferably 1.5 to 6 ⁇ m.
  • the plate-shaped glass filler having the above-mentioned number average particle diameter and thickness achieves good mechanical strength, appearance, and moldability.
  • Various glass compositions represented by A glass, C glass, E glass and the like are applied to the glass composition of the above-described fibrous glass filler and plate glass filler, and is not particularly limited.
  • Such glass fillers are optionally made of TiO 2 , SO 3 , And P 2 O 5 And the like.
  • E glass non-alkali glass
  • the glass filler is preferably subjected to a surface treatment with a known surface treatment agent such as a silane coupling agent, a titanate coupling agent, or an aluminate coupling agent from the viewpoint of improving mechanical strength.
  • a known surface treatment agent such as a silane coupling agent, a titanate coupling agent, or an aluminate coupling agent from the viewpoint of improving mechanical strength.
  • Glass fibers (including those coated with metal or metal oxide) and glass flakes (including those coated with metal or metal oxide) are olefin resins, styrene resins, acrylic resins, Those that have been converged with a polyester resin, an epoxy resin, a urethane resin, or the like are preferably used.
  • the amount of sizing agent adhering to the sizing agent is preferably 0.5 to 8% by weight, more preferably 1 to 4% by weight in 100% by weight of the filler.
  • the fibrous glass filler and the plate-like glass filler of the present invention include those in which different materials are surface-coated.
  • Preferred examples of such dissimilar materials include metals and metal oxides.
  • the metal include silver, copper, nickel, and aluminum.
  • the metal oxide include titanium oxide, cerium oxide, zirconium oxide, iron oxide, aluminum oxide, and silicon oxide.
  • plating methods for example, electrolytic plating, electroless plating, hot dipping, etc.
  • vacuum deposition methods for example, electrolytic plating, electroless plating, hot dipping, etc.
  • ion plating methods for example, thermal CVD, MOCVD, plasma CVD, etc.
  • PVD method sputtering method, etc.
  • fibrous carbon filler examples include carbon fibers (including metal-coated carbon fibers), carbon milled fibers, vapor grown carbon fibers, and carbon nanotubes.
  • the carbon nanotube may be any one of a fiber diameter of 0.003 to 0.1 ⁇ m, a single layer, a double layer, and a multilayer, and a multilayer (so-called MWCNT) is preferable.
  • carbon fibers (including metal-coated carbon fibers) are preferable in that they are excellent in mechanical strength and can impart good electrical conductivity. Good electrical conductivity has become one of important characteristics required for resin materials in recent digital precision equipment (represented by, for example, a digital still camera).
  • any of cellulose, polyacrylonitrile, pitch and the like can be used.
  • it is obtained by a method in which a raw material composition comprising a polymer and a solvent due to a methylene bond of aromatic sulfonic acids or their salts is prevented or molded, and then subjected to spinning without passing through an infusibilization step typified by carbonization. It is also possible to use those that have been used.
  • any of general-purpose type, medium elastic modulus type, and high elastic modulus type can be used. Among these, polyacrylonitrile-based high elastic modulus type is particularly preferable.
  • the average fiber diameter of the carbon fiber is not particularly limited, but is usually 3 to 15 ⁇ m, preferably 5 to 13 ⁇ m.
  • a carbon fiber having an average fiber diameter in such a range can exhibit good mechanical strength and fatigue characteristics without impairing the appearance of the molded product.
  • the preferred fiber length of the carbon fiber is preferably 60 to 500 ⁇ m, more preferably 80 to 400 ⁇ m, particularly preferably 100 to 300 ⁇ m as the number average fiber length in the resin composition.
  • the number average fiber length is a value calculated by an image analyzer from an optical microscope observation from the carbon fiber residue collected by high temperature ashing of the molded product, dissolution with a solvent, and decomposition with a chemical. is there. Further, when calculating such a value, a value having a length equal to or shorter than the fiber length is a value obtained by a method not counting.
  • 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 still more preferably in the range of 20 to 50.
  • the aspect ratio of the fibrous carbon filler is a value obtained by dividing the average fiber length by the average fiber diameter. Furthermore, it is preferable that the surface of the carbon fiber is oxidized for the purpose of improving the adhesion with the matrix resin and improving the mechanical strength.
  • the oxidation treatment method is not particularly limited, for example, (1) a method in which a fibrous carbon filler is treated with an acid or alkali or a salt thereof, or an oxidizing gas, (2) a fiber that can be converted into a fibrous carbon filler, or A method of firing the fibrous carbon filler at a temperature of 700 ° C. or higher in the presence of an inert gas containing an oxygen-containing compound; and (3) after the fibrous carbon filler is oxidized and then in the presence of the inert gas.
  • the method of heat-treating with is suitably exemplified.
  • Metal coated carbon fiber is a carbon fiber surface coated with a metal layer.
  • the metal examples include silver, copper, nickel, and aluminum, and nickel is preferable from the viewpoint of the corrosion resistance of the metal layer.
  • various methods described above for the surface coating with different materials in the glass filler can be employed. Of these, the plating method is preferably used.
  • the thickness of the metal coating layer is preferably 0.1 to 1 ⁇ m, more preferably 0.15 to 0.5 ⁇ m. More preferably, it is 0.2 to 0.35 ⁇ m.
  • Such carbon fibers are preferably those that are converged with an olefin resin, a styrene resin, an acrylic resin, a polyester resin, an epoxy resin, a urethane resin, or the like.
  • a fibrous carbon filler treated with a urethane resin or an epoxy resin is suitable in the present invention because of its excellent mechanical strength.
  • D-4; non-fibrous carbon filler examples include carbon black, graphite, fullerene and the like. Among these, carbon black and graphite are preferable from the viewpoint of mechanical strength, heat and humidity resistance, and thermal stability.
  • carbon black having a DBP oil absorption of 100 ml / 100 g to 500 ml / 100 g is preferable from the viewpoint of conductivity.
  • Such carbon black is generally acetylene black or ketjen black. Specific examples include Denka Black manufactured by Denki Kagaku Kogyo Co., Ltd., Vulcan XC-72 and BP-2000 manufactured by Cabot Corporation, Ketjen Black EC and Ketjen Black EC-600JD manufactured by Lion Corporation.
  • graphite either natural graphite, which is made of graphite under the mineral name, or various artificial graphites can be used.
  • any of earth-like graphite, scale-like graphite (Vein Graphite also called massive graphite), and scale-like graphite (Flake Graphite) can be used.
  • Artificial graphite is obtained by heat-treating amorphous carbon and artificially aligning irregularly arranged fine graphite crystals.
  • Kish graphite, cracked graphite, And pyrolytic graphite Kish graphite, cracked graphite, And pyrolytic graphite.
  • Artificial graphite used for general carbon materials is usually produced by graphitization treatment using petroleum coke or coal-based pitch coke as a main raw material.
  • the graphite of the present invention may contain expanded graphite that can be thermally expanded by treatment represented by acid treatment, or graphite that has been expanded.
  • the particle size of the graphite of the present invention is preferably in the range of 2 to 300 ⁇ m.
  • the particle size is more preferably 5 to 200 ⁇ m, further preferably 7 to 100 ⁇ m, and particularly preferably 7 to 50 ⁇ m.
  • good mechanical strength and molded product appearance are achieved.
  • the average particle size is less than 2 ⁇ m, the effect of improving the rigidity may be reduced, and if the average particle size exceeds 300 ⁇ m, the impact resistance is significantly reduced, and so-called graphite floats on the surface of the molded product. This is not preferable.
  • the amount of fixed carbon 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.
  • the volatile content 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 graphite refers to the particle diameter before becoming a resin composition, and the particle diameter is determined by a laser diffraction / scattering method.
  • the surface of graphite is subjected to surface treatment such as epoxy treatment, urethane treatment, silane coupling treatment, and oxidation treatment in order to increase the affinity with the thermoplastic resin as long as the characteristics of the composition of the present invention are not impaired. It may be given.
  • D-5 silicate mineral
  • D-5 component is at least a metal oxide component and SiO 2
  • SiO 2 It is a silicate mineral composed of components, and orthosilicate, disilicate, cyclic silicate, chain silicate, and the like are suitable.
  • Silicate minerals take a crystalline state, and the crystals may be in any transformation that each silicate mineral can take, and the shape of the crystals may take various forms such as fibers and plates.
  • Silicate minerals may be complex oxides, oxyacid salts (consisting of ionic lattices), or solid solution compounds, and complex oxides are combinations of two or more single oxides, and single oxides and oxygen acids. Any of two or more combinations with a salt may be used, and also in a solid solution, any of a solid solution of two or more metal oxides and a solid solution of two or more oxyacid salts may be used. Hydrates may also be used. The form of water of crystallization in the hydrate is that which enters as hydrogen silicate ion as Si—OH, and hydroxide ion (OH ⁇ ) As ionic ions, and H in the gaps in the structure 2 Any form of O molecules may be used.
  • silicate mineral an artificial synthetic product corresponding to a natural product can be used.
  • artificial compound silicate minerals obtained from various conventionally known methods, for example, various synthetic methods using solid reaction, hydrothermal reaction, ultrahigh pressure reaction and the like can be used.
  • Specific examples of silicate minerals in each metal oxide component include the following.
  • the description in parentheses is the name of a mineral or the like mainly composed of such a silicate mineral, and means that the compound in parentheses can be used as the exemplified metal salt.
  • K 2 As a component containing O in its component, K 2 O ⁇ SiO 2 , K 2 O ⁇ 4SiO 2 ⁇ H 2 O, K 2 O ⁇ Al 2 O 3 ⁇ 2SiO 2 (Calcylite), K 2 O ⁇ Al 2 O 3 ⁇ 4SiO 2 (White ryu), and K 2 O ⁇ Al 2 O 3 ⁇ 6SiO 2 (Positive feldspar).
  • BaO as a component of BaO / SiO 2 2BaO ⁇ SiO 2 , BaO ⁇ Al 2 O 3 ⁇ 2SiO 2 (Celsian) and BaO ⁇ TiO 2 ⁇ 3SiO 2 (Bent eye).
  • Portland cement can be mentioned as a silicate mineral containing CaO as its component.
  • the type of Portland cement is not particularly limited, and any of normal, early strength, ultra-early strength, moderate heat, sulfate resistance, white, and the like can be used.
  • various mixed cements such as blast furnace cement, silica cement, fly ash cement and the like can be used as the B component.
  • blast furnace slag, a ferrite, etc. can be mentioned as a silicate mineral which contains other CaO in the component.
  • ZnO as its component is ZnO.SiO 2 2ZnO ⁇ SiO 2 (Trostite) and 4ZnO ⁇ 2SiO 2 ⁇ H 2 O (heteropolar ore) and the like.
  • MnO MnO ⁇ SiO 2 2MnO ⁇ SiO 2
  • FeO ⁇ SiO 2 Ferocilite
  • 2FeO ⁇ SiO 2 Iron olivine
  • 3FeO ⁇ Al 2 O 3 ⁇ 3SiO 2 Almandin
  • 2CaO ⁇ 5FeO ⁇ 8SiO 2 ⁇ H 2 O Tetsuakuchinosenite
  • CoO as a component in CoO / SiO 2 And 2CoO ⁇ SiO 2 Etc.
  • Fe 2 O 3 As the component containing Fe 2 O 3 ⁇ SiO 2 Etc.
  • ZrO 2 As a component containing ZrO, 2 ⁇ SiO 2 (Zircon) and AZS refractories.
  • Al 2 O 3 As a component containing 2 O 3 ⁇ SiO 2 (Sillimanite, Andalusite, Kyanite), 2Al 2 O 3 ⁇ SiO 2 , Al 2 O 3 ⁇ 3SiO 2 3Al 2 O 3 ⁇ 2SiO 2 (Mullite), Al 2 O 3 ⁇ 2SiO 2 ⁇ 2H 2 O (Kaolinite), Al 2 O 3 ⁇ 4SiO 2 ⁇ H 2 O (Pyrophyllite), Al 2 O 3 ⁇ 4SiO 2 ⁇ H 2 O (bentonite), K 2 O.3Na 2 O ⁇ 4Al 2 O 3 ⁇ 8SiO 2 (Kasumi stone), K 2 O ⁇ 3Al 2 O 3 ⁇ 6SiO 2
  • Talc Talc in the present invention is hydrous magnesium silicate in terms of chemical composition, and generally has the chemical formula 4SiO 2 ⁇ 3MgO ⁇ 2H 2 It is represented by O and is usually a scaly particle having a layered structure. 2 56 to 65% by weight, MgO 28 to 35% by weight, H 2 O is composed of about 5% by weight.
  • Fe as other minor components 2 O 3 0.03 to 1.2% by weight, Al 2 O 3 0.05 to 1.5% by weight, CaO 0.05 to 1.2% by weight, K 2 O is 0.2 wt% or less, Na 2 O contains 0.2% by weight or less.
  • a more preferable composition of talc is SiO. 2 : 62-63.5 wt%, MgO: 31-32.5 wt%, Fe 2 O 3 : 0.03-0.15 wt%, Al 2 O 3 : 0.05 to 0.25% by weight, and CaO: 0.05 to 0.25% by weight are preferable.
  • the ignition loss is preferably 2 to 5.5% by weight.
  • the composition of the present invention can be further fluidized, and can be used for thin molded products having larger or complex shapes.
  • the average particle size measured by the sedimentation method is 0.1 to 50 ⁇ m (more preferably 0.1 to 10 ⁇ m, still more preferably 0.2 to 5 ⁇ m, particularly preferably 0.2 to 3.5 ⁇ m). ) Is preferable. Therefore, a more preferable talc of the present invention is a talc having the above-mentioned preferable composition and having an average particle diameter of 0.2 to 5 ⁇ m.
  • the bulk density is 0.5 (g / cm 3 ) It is particularly preferable to use the talc as described above as a raw material.
  • talc As an example of talc satisfying such conditions, “Upn HS-T0.8” manufactured by Hayashi Kasei Co., Ltd. is exemplified.
  • the average particle size of talc refers to D50 (median diameter of particle size distribution) measured by an X-ray transmission method which is one of liquid phase precipitation methods.
  • Sedigraph 5100 manufactured by Micromeritics Inc. can be cited.
  • the manufacturing method when talc is crushed from raw stone there is no particular restriction on the manufacturing method when talc is crushed from raw stone, and the axial flow mill method, the annular mill method, the roll mill method, the ball mill method, the jet mill method, the container rotary compression shearing mill method, etc. are used. can do. Further, the talc after pulverization is preferably classified by various classifiers and having a uniform particle size distribution.
  • talc is preferably in an aggregated state in view of its handleability and the like, and as such a production method, there are a method by deaeration compression, a method using a sizing agent, and a method of compression.
  • the degassing compression method is preferable in that the sizing agent resin component which is simple and unnecessary is not mixed into the resin composition of the present invention.
  • Mica having an average particle size of 5 to 250 ⁇ m can be used.
  • mica having an average particle diameter (D50 (median diameter of particle diameter distribution)) measured by a laser diffraction / scattering method of 5 to 50 ⁇ m. If the average particle diameter of mica is less than 5 ⁇ m, it is difficult to obtain the effect of improving rigidity.
  • a resin composition containing mica having an average particle size exceeding 250 ⁇ m is inferior in appearance and flame retardancy while its mechanical properties tend to be saturated.
  • the average particle diameter of mica is measured by a laser diffraction / scattering method or a vibration sieving method.
  • the laser diffraction / scattering method it is preferable that the 325 mesh pass is performed on 95% by weight or more of mica by the vibration sieving method.
  • the vibration sieving method is generally used.
  • the vibration sieving method of the present invention first, sieving is carried out for 10 minutes using a JIS standard standard sieve in which 100 g of mica powder to be used is stacked in the order of openings using a vibration sieve device. This is a method of obtaining the particle size distribution by measuring the weight of the powder remaining on each sieve.
  • the thickness of mica one having a thickness measured by observation with an electron microscope of 0.01 to 1 ⁇ m can be used.
  • the thickness is preferably 0.03 to 0.3 ⁇ m.
  • An aspect ratio of 5 to 200, preferably 10 to 100 can be used.
  • the mica used is preferably mascobite mica, and its Mohs hardness is about 3. Muscovite mica can achieve higher rigidity and strength than other mica such as phlogopite, and solves the problems of the present invention at a better level.
  • a more preferred mica of the present invention is a mascobite having an average particle diameter of 5 to 250 ⁇ m, more preferably 5 to 50 ⁇ m.
  • a suitable mica for example, “A-21” manufactured by Yamaguchi Mica Industry Co., Ltd.
  • the mica may be pulverized by either dry pulverization or wet pulverization.
  • the dry pulverization method is more inexpensive and more general, but the wet pulverization method is effective for pulverizing mica more thinly and finely (the rigidity improvement effect of the resin composition becomes higher).
  • the wet pulverized mica is more preferable.
  • (D-5-iii) Wollastonite The fiber diameter of wollastonite is preferably 0.1 to 10 ⁇ m, more preferably 0.1 to 5 ⁇ m, still more preferably 0.1 to 3 ⁇ m.
  • the aspect ratio (average fiber length / average fiber diameter) is preferably 3 or more. The upper limit of the aspect ratio is 30 or less.
  • the fiber diameter is obtained by observing the reinforcing filler with an electron microscope, obtaining individual fiber diameters, and calculating the number average fiber diameter from the measured values.
  • the electron microscope is used because it is difficult for an optical microscope to accurately measure the size of a target level.
  • the filler for which the fiber diameter is to be measured is randomly extracted, the fiber diameter is measured near the center, and the number average fiber is obtained from the obtained measured value. Calculate the diameter.
  • the observation magnification is about 1000 times, and the number of measurement is 500 or more (600 or less is suitable for work).
  • the measurement of average fiber length observes a filler with an optical microscope, calculates
  • Observation with an optical microscope begins with the preparation of a dispersed sample so that the fillers do not overlap each other. Observation is performed under the condition of 20 times the objective lens, and the observed image is taken as image data into a CCD camera having about 250,000 pixels. The obtained image data is calculated by using a program for obtaining the maximum distance between two points of the image data using an image analysis device. Under such conditions, the size per pixel corresponds to a length of 1.25 ⁇ m, and the number of measurement is 500 or more (600 or less is suitable for work).
  • the wollastonite of the present invention is a magnetic separator that reflects the iron content mixed in the raw material ore and the iron content mixed due to equipment wear when pulverizing the raw material ore in order to sufficiently reflect the inherent whiteness in the resin composition. It is preferable to remove as much as possible.
  • the iron content in wollastonite is Fe. 2 O 3 It is preferably 0.5% by weight or less in terms of Therefore, the more preferable wollastonite of the present invention has a fiber diameter of 0.1 to 10 ⁇ m, more preferably 0.1 to 5 ⁇ m, and further preferably 0.1 to 3 ⁇ m.
  • the average particle size is 5 to 250 ⁇ m, more preferably 5 to 50 ⁇ m, and the iron content is Fe 2 O 3 Wollastonite in an amount of 0.5% by weight or less.
  • suitable wollastonite include “SH-1250” and “SH-1800” manufactured by Kinsei Matech Corporation, “KGP-H40” manufactured by Kansai Matec Corporation, “NYGLOS4” manufactured by NYCO Corporation, and the like.
  • the silicate mineral in the present invention is preferably not surface-treated, but a silane coupling agent (including alkylalkoxysilane and polyorganohydrogensiloxane), higher fatty acid ester, acid compound (for example, phosphorous acid, Surface treatment may be carried out with various surface treatment agents such as phosphoric acid, carboxylic acid, and carboxylic acid anhydride) and wax. Furthermore, it may be granulated with a sizing agent such as various resins, higher fatty acid esters, and waxes.
  • talc and wollastonite are particularly suitable.
  • 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 with respect to 100 parts by weight of the resin component. More preferably, it is 10 to 12 parts by weight. If the upper limit is exceeded, the impact strength will decrease, and if it is less than the lower limit, the effect of improving the rigidity will be insufficient, such being undesirable.
  • the resin composition of the present invention includes various additives (flame retardants, fluorine-containing anti-dripping agents, stabilizers, ultraviolet absorbers, release agents, Dyes and pigments, compounds having heat ray absorbing performance, antistatic agents, acidity adjusting agents, and the like) (for details of various additives, refer to WO2011 / 088741).
  • additives flame retardants, fluorine-containing anti-dripping agents, stabilizers, ultraviolet absorbers, release agents, Dyes and pigments, compounds having heat ray absorbing performance, antistatic agents, acidity adjusting agents, and the like
  • phosphorus stabilizer preferably used in the present invention include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, esters thereof, and tertiary phosphine.
  • phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, triorganophosphate compounds, and acid phosphate compounds are particularly preferable.
  • the organic group in the acid phosphate compound includes any of mono-substituted, di-substituted, and mixtures thereof. Any of the following exemplified compounds corresponding to the compound is similarly included.
  • Triorganophosphate compounds include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tridecyl phosphate, tridodecyl phosphate, trilauryl phosphate, tristearyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, diphenyl Examples include cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, and the like. Among these, trialkyl phosphate is preferable.
  • the carbon number of the trialkyl phosphate is preferably 1 to 22, more preferably 1 to 4.
  • a particularly preferred trialkyl phosphate is trimethyl phosphate.
  • the acid phosphate compound include methyl acid phosphate, ethyl acid phosphate, butyl acid phosphate, butoxyethyl acid phosphate, octyl acid phosphate, decyl acid phosphate, lauryl acid phosphate, stearyl acid phosphate, oleyl acid phosphate, behenyl acid phosphate, behenyl acid phosphate Nonylphenyl acid phosphate, cyclohexyl acid phosphate, phenoxyethyl acid phosphate, alkoxy polyethylene glycol acid phosphate, bisphenol A acid phosphate, and the like.
  • long-chain dialkyl acid phosphates having 10 or more carbon atoms are effective for improving thermal stability, and the acid phosphate itself is preferable because of high stability.
  • the phosphite compound include triphenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl Monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, tris (diethylphenyl) phosphite, tris (di-iso-propylphenyl
  • Still other phosphite compounds that react with dihydric phenols and have a cyclic structure can be used.
  • 2,2′-methylenebis (4,6-di-tert-butylphenyl) (2,4-di-tert-butylphenyl) phosphite 2,2′-methylenebis (4,6-di-tert- Examples include butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, and the like.
  • Examples of the phosphonite compound include tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3′-biphenylenedi.
  • Such a phosphonite compound is preferable because it can be used in combination with a phosphite compound having an aryl group in which two or more alkyl groups are substituted.
  • Examples of the phosphonate compound include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate.
  • Tertiary phosphine includes triethylphosphine, tripropylphosphine, tributylphosphine, trioctylphosphine, triamylphosphine, dimethylphenylphosphine, dibutylphenylphosphine, diphenylmethylphosphine, diphenyloctylphosphine, triphenylphosphine, tri-p-tolyl.
  • Examples include phosphine, trinaphthylphosphine, diphenylbenzylphosphine, and the like.
  • a particularly preferred tertiary phosphine is triphenylphosphine.
  • Suitable phosphorus stabilizers are triorganophosphate compounds, acid phosphate compounds, and phosphite compounds represented by the following formula (XIII). It is particularly preferable to add a triorganophosphate compound.
  • R and R ′ each represents an alkyl group having 6 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an alkylaryl group, and may be the same or different from each other.
  • tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite is preferred as the phosphonite compound
  • the stabilizer containing phosphonite as a main component is Sandostab P-EPQ (trademark, manufactured by Clariant).
  • Irgafos P-EPQ trademark, CIBA SPECIALTY manufactured by CHEMICALS
  • more preferred phosphite compounds are distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di). -Tert-butyl-4-methylphenyl) pentaerythritol diphosphite, and bis ⁇ 2,4-bis (1-methyl-1-phenylethyl) phenyl ⁇ pentaerythritol diphosphite.
  • the resin composition of the present invention contains thermoplastic resins other than the A component and B component, elastomers, other flow modifiers, antibacterial agents, dispersants such as liquid paraffin, photocatalytic antifouling agents, photochromic agents and the like. can do.
  • examples of such other resins include polyamide resins, polyimide resins, polyetherimide resins, polyurethane resins, silicone resins, polyphenylene ether resins, polyphenylene sulfide resins, polysulfone resins, polyolefin resins such as polyethylene and polypropylene, polystyrene resins, acrylonitrile / styrene.
  • Resins such as copolymer (AS resin), polymethacrylate resin, phenol resin, epoxy resin, cyclic polyolefin resin, polylactic acid resin, polycaprolactone resin, and thermoplastic fluororesin (for example, represented by polyvinylidene fluoride resin) Can be mentioned.
  • the elastomer include acrylic elastomers, polyester elastomers, polyamide elastomers, and the like.
  • the content of the other thermoplastic resin or elastomer is preferably 30 parts by weight or less, more preferably 20 parts by weight or less based on 100 parts by weight of the resin component. (Production method of resin composition)
  • Arbitrary methods are employ
  • the premixing means include a Nauter mixer, a V-type blender, a Henschel mixer, a mechanochemical device, and an extrusion mixer.
  • granulation can be performed by an extrusion granulator, a briquetting machine, or the like, if necessary.
  • a master batch of an additive diluted with powder by blending a part of the powder and an additive to be blended is manufactured, and the master A method using a batch is mentioned.
  • the mixture is melt-kneaded by a melt-kneader represented by a vent type twin-screw extruder and pelletized by a device such as a pelletizer.
  • the melt kneader include a Banbury mixer, a kneading roll, and a constant temperature stirring vessel, but a vent type twin screw extruder is preferred.
  • a method of supplying each component independently to a melt-kneader represented by a twin-screw extruder without premixing each component can also be used.
  • the method of supplying to a melt-kneader independently of the remaining components is mentioned.
  • the inorganic filler is preferably supplied from a supply port in the middle of the extruder into the molten resin using a supply device such as a side feeder.
  • the premixing means and granulation are the same as described above.
  • a liquid injection apparatus or a liquid addition apparatus can be used for supply to a melt kneader.
  • a liquid injection apparatus or a liquid addition apparatus can be used for supply to a melt kneader.
  • the extruder one having a vent capable of degassing moisture in the raw material and volatile gas generated from the melt-kneaded resin can be preferably used. From the vent, a vacuum pump is preferably installed for efficiently discharging generated moisture and volatile gas to the outside of the extruder. It is also possible to remove a foreign substance from the resin composition by installing a screen for removing foreign substances and the like mixed in the extrusion raw material in the zone in front of the extruder die.
  • melt kneader examples include a banbury mixer, a kneading roll, a single screw extruder, a multi-screw extruder having three or more axes, in addition to a twin screw extruder. Furthermore, it is preferable that the moisture contained in the A component and the B component is small before melt kneading. Therefore, it is more preferable to melt-knead after drying either component A or component B or both by various methods such as hot air drying, electromagnetic wave drying, or vacuum drying.
  • the vent suction during melt-kneading is preferably in the range of 1 to 60 kPa, preferably 2 to 30 kPa.
  • the resin extruded as described above is directly cut into pellets, or after forming the strands, the strands are cut with a pelletizer to be pelletized.
  • a pelletizer to be pelletized.
  • various methods already proposed for polycarbonate resin for optical discs are used to narrow the shape distribution of pellets, reduce miscuts, and reduce fine powder generated during transportation or transportation.
  • bubbles vacuum bubbles
  • the shape of a pellet can take common shapes, such as a cylinder, a prism, and a spherical shape, it is a cylinder more suitably.
  • the diameter of such a cylinder is preferably 1 to 5 mm, more preferably 1.5 to 4 mm, and still more preferably 2 to 3.3 mm.
  • the length of the cylinder is preferably 1 to 30 mm, more preferably 2 to 5 mm, and still more preferably 2.5 to 3.5 mm.
  • injection molding not only ordinary molding methods, but also injection compression molding, injection press molding, gas-assisted injection molding, foam molding (including the method of injecting supercritical fluid), insert molding, in-mold coating molding, and heat insulation gold
  • injection molding not only ordinary molding methods, but also injection compression molding, injection press molding, gas-assisted injection molding, foam molding (including the method of injecting supercritical fluid), insert molding, in-mold coating molding, and heat insulation gold
  • mold molding rapid heating / cooling mold molding, two-color molding, multicolor molding, sandwich molding, and ultrahigh-speed injection molding.
  • a cold runner method or a hot runner method can be selected for molding.
  • extrusion molding various profile extrusion molded products, sheets, films, etc. are obtained. For forming sheets and films, an inflation method, a calendar method, a casting method, or the like can be used.
  • the resin composition of the present invention can also be formed into a molded product by rotational molding, blow molding or the like.
  • the form of the present invention considered to be the best by the present inventor is a collection of the preferred ranges of the above requirements. For example, typical examples are described in the following examples. Of course, the present invention is not limited to these forms.
  • test piece before the wet heat treatment was kept at a constant temperature and humidity of 80 ° C. and a relative humidity of 95%.
  • a test piece left again for 24 hours in an environment of a temperature of 23 ° C. and a relative humidity of 50% was used as a test piece after the wet heat treatment.
  • the test specimens before and after the wet heat treatment were pulverized so that no foreign matter was mixed in, and dried at 120 ° C. for about 5 hours to reduce the moisture content to 200 ppm or less.
  • MVR melt volume rate measurement was performed by a method based on ISO 1133 under the condition of 2.16 kgf. The measurement was performed with a semi-auto melt indexer 2A type manufactured by Toyo Seiki Co., Ltd. The wet heat resistance was calculated according to the following formula, and the rate of change ( ⁇ MVR) before and after wet heat treatment was calculated.
  • ⁇ MVR rate of change
  • a larger ⁇ MVR means that the resin deterioration of the molded product is larger and the heat and moisture resistance is inferior, and ⁇ MVR is preferably 200 or less, more preferably 170 or less.
  • ⁇ MVR (moisture and heat 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 reduce the moisture content in the pellets to 200 ppm or less, an injection molding machine (Sumitomo Heavy Industries, Ltd .: SG260M-HP) was used. Using 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, a test piece of length 70 mm ⁇ width 50 mm ⁇ thickness 2.0 mm was continuously injection molded.
  • the test piece of the continuous molded product was obtained (the quality of the test piece of the continuous molded product is substantially the same as the test piece before the wet heat treatment).
  • the molding machine was stopped for 10 minutes, and the molten resin was retained in the molding machine cylinder. 10 minutes after the molding machine was stopped, molding was started again, and the second shot from the re-molding was used as a test piece for the retained molded product.
  • the continuously molded product and the retained molded product are pulverized so that no foreign matter is mixed in, dried at 120 ° C. for about 5 hours to reduce the moisture content to 200 ppm or less, and each pulverized sample has a temperature of 280 ° C.
  • MVR melt volume rate
  • ISO1133 semi-auto melt indexer 2A type manufactured by Toyo Seiki Co., Ltd.
  • the thermal stability was calculated according to the following formula, and the MVR change rate ( ⁇ MVR (thermal stability)) before and after residence was calculated.
  • ⁇ MVR thermal stability
  • ⁇ MVR thermal stability
  • ⁇ MVR is preferably 150 or less, more preferably 130 or less.
  • ⁇ MVR (thermal stability) 100 ⁇ (MVR of test piece of staying molded product) / (MVR of test piece of continuous molded product) (Vi) Chemical resistance: (iii) A test piece prepared by Charpy impact test was subjected to a bending strain of 6 MPa, and immersed in commercial regular gasoline for 30 minutes in an environment of a temperature of 23 ° C. and a relative humidity of 50%. The appearance was visually observed and evaluated. The evaluation was performed according to the following criteria. ⁇ : No abnormality is observed. ⁇ : Appearance changes such as cracks and whitening are observed in the molded products.
  • Examples 1 to 12 and Comparative Examples 1 to 11 A polycarbonate resin, a polyester resin, a filler and various additives are mixed in the blending amounts shown in Tables 1 to 3 in a blender, and then melt-kneaded using a vent type twin screw extruder to obtain the resin composition of the present invention.
  • a pellet consisting of Various additives other than the filler were preliminarily prepared with a polycarbonate resin powder with a concentration of 10 to 100 times the blending amount as a guide, and then the whole was mixed by a blender.
  • the vent type twin screw extruder used was TEX30 ⁇ -31.5BW-2V (completely meshed, rotating in the same direction, two-thread screw) manufactured by Nippon Steel Works.
  • the kneading zone was of one type before the vent opening. Extrusion conditions were a discharge rate of 20 kg / h, a screw rotation speed of 130 rpm, a vent vacuum of 3 kPa, and an extrusion temperature of 270 ° C. from the first supply port to the die part.
  • the components indicated by symbols in Tables 1 to 3 are as follows.
  • a component Linear aromatic polycarbonate resin powder having a viscosity average molecular weight of 22,400 (component B) (B-1 component)
  • PBT-1 Polybutylene terephthalate resin having an IV value of 0.87 (Polyplastics Corporation DURANEX 500FP (trade name))
  • a catalyst was prepared. After producing an ester oligomer from ethylene glycol and terephthalic acid, a polycondensation reaction was carried out in a polycondensation reaction tank together with a catalyst. The degree of progress of the polycondensation was checked by monitoring the load on the stirring blade in the reaction system, and the reaction was terminated when the desired degree of polymerization was reached. Thereafter, the reaction mixture in the system was continuously extruded in a strand form from the discharge part, cooled and solidified, and cut to prepare polyethylene terephthalate granular pellets having a particle size of about 3 mm.
  • C component C-1 EXL2390: Acrylic core-shell polymer (Rohm and Haas Co., Ltd .: Paraloid EXL-2390 (trade name), core is about 50% by weight of butyl acrylate component and about 40% by weight of 2-ethylhexyl acrylate component, shell is Core-shell polymer that is about 10% by weight methyl methacrylate) C-2 (Comparison): EXL2388: Acrylic core-shell polymer (Rohm and Haas Co., Ltd .: Paraloid EXL-2388 (trade name), core is about 90% by weight of butyl acrylate component, shell is about 10% by weight of methyl methacrylate A core-shell polymer) C-3 (Comparison): EXL-2620: Styrenic rubber polymer (Rohm and Haas Co., Ltd .: Paraloid EXL-2620 (trade name), core is 70% polybutadiene, shell is styrene and methyl methacryl
  • D component Polymerized composite rubber graft copolymer (Metbrene S-2001 (trade name) manufactured by Mitsubishi Rayon Co., Ltd.)
  • D-1 Wollastonite with an average particle size of 4 ⁇ m (Kansai Matec Co., Ltd .: KGP-H40)
  • D-2 Wollastonite having an average particle diameter of 5 ⁇ m (manufactured by Kinsei Matech Corporation: SH-1250)
  • D-3 Compressed fine powder talc (Hayashi Kasei Co., Ltd .: Upn HS-T0.8)
  • D-4 wet-pulverized mica having an average particle size of 22 ⁇ m (Yamaguchi Mica Co., Ltd .: A-21)
  • AO-1 Bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite (manufactured by Adeka: Adeka Stub PEP-24G)
  • AO-2 Trimethyl phosphate
  • Example 2 is excellent in both tensile modulus and Charpy impact strength.
  • Example 12 is excellent in both tensile modulus and Charpy impact strength.
  • the resin composition of the present invention is excellent in both tensile elastic modulus and Charpy impact strength.
  • the resin composition of the present invention is excellent in thermal stability and further has good chemical resistance.
  • the resin composition of the present invention is widely useful in various fields such as buildings, building materials, agricultural materials, marine materials, vehicles, electric / electronic devices, machines, and the like.

Abstract

Le but de la présente invention est de proposer une composition de résine thermoplastique ayant une exceptionnelle stabilité thermique ainsi qu'une excellente résistance mécanique et une résistance chimique exceptionnelle. La présente invention est une composition de résine contenant 1 à 10 parties en poids de (C) un polymère de type noyau-enveloppe (composant C) qui comprend un noyau (composant C-1) comprenant un matériau élastique à base d'ester d'acide acrylique réticulé configuré à partir d'un ester d'acide acrylique ayant des groupes alkyle en C1-C4 et un ester d'acide acrylique comportant des groupes alkyle en C5-C8, et une enveloppe (composant C-2) comportant un ester d'acide méthacrylique en tant que composant principal, et 8 à 15 parties en poids de (D) une charge (composant D), pour 100 parties en poids d'un composant de résine comprenant 80 à 50 parties en poids de (A) une résine de polycarbonate (composant A) et de 20 à 50 parties en poids de (B) une résine de polyester (composant B).
PCT/JP2015/062628 2014-04-23 2015-04-21 Composition de résine WO2015163479A1 (fr)

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US20200165445A1 (en) * 2015-12-03 2020-05-28 Sabic Global Technologies B.V. Heat resistant, weatherable polyester - polycarbonate composition
CN116675836A (zh) * 2023-08-02 2023-09-01 宁波聚嘉新材料科技有限公司 一种液晶聚合物、薄膜及其制备方法、太阳能电池背板

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KR102221425B1 (ko) * 2017-11-30 2021-02-26 롯데케미칼 주식회사 색상 및 내열성이 우수한 폴리에스테르 수지 제조용 조성물
CN112266598B (zh) * 2020-10-28 2022-08-30 武汉金发科技有限公司 一种滑石粉填充pc/pbt合金材料及其制备方法

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