JP4770249B2 - Polyester resin composition and molded product obtained therefrom - Google Patents

Description

  The present invention relates to a polyester resin composition containing a polyolefin-based compound having a saponification value of 20 to 80 mg KOH / g, and a resin molded body comprising the polyester resin composition.

  Lighting components, such as automotive headlamp extensions and facility lighting reflectors, have a high brightness, sharpness, uniform reflectivity, smoothness and light source heat for light source directionality, reflectivity, and design. High heat resistance is required. For such applications, molding made of a thermoplastic polyester resin such as polyethylene terephthalate or polybutylene terephthalate obtained in recent years, for example, by injection molding using a mold having a mirror finish using an abrasive of No. 6000 or more. Has been tried by the body. Conventionally, the surface of the molded body has been smoothed by molding with a mold polished with an abrasive of about No. 1200 and further applying an undercoat called an undercoat. However, when applying an undercoat (undercoat) to a molded product, it is necessary to design an undercoat material for each resin type, the organic solvent constituting the undercoat material has a problem in environmental protection, and an undercoat process. There were a number of problems, such as a significant increase in cost and a high defect rate in the undercoat process.

  In contrast to these conventional methods, the purpose of using a molded body obtained by a mold finished with a mirror finish using an abrasive of No. 6000 or more is to use a molded body having a smooth surface without using the undercoat material. In order to solve the above-mentioned various problems.

  However, when molding with a mirror-finished mold using an abrasive of No. 6000 or more, the polyester resin is in close contact with the mold surface and has a major problem that it cannot be released during molding. Although the problem of inferior releasability can be solved by applying a silicone-based or fluorine-based external mold release agent to the mold surface and molding, the surface gloss of the resulting molded product is impaired, and the headlamp extension of an automobile It cannot be used as a reflector for facility lighting.

  Conventionally, a technique of adding 0.1 ppb to 1000 ppm of a polyolefin compound to a polyester resin has been disclosed (Patent Document 1). However, the above technique is a method for accelerating crystallization of a hollow molded article, and the effect of improving the releasability is insufficient, so that it cannot be put into practical use.

As described above, the technology for obtaining a polyester resin composition which is excellent in releasability even in a mirror finish mold of No. 6000 or more, does not impair the gloss of the molded article, and does not deteriorate the surface gloss even when exposed to a high temperature of 150 ° C. or higher. The current situation has not yet been found.
JP 2003-0410103 A

  The object of the present invention is to improve such a conventional problem, even when molded using a mirror finish mold using an abrasive of No. 6000 or more, excellent in releasability, and exposed to high temperatures. An object of the present invention is to provide a polyester resin composition in which the surface gloss is not impaired, and a molded body comprising the polyester resin composition.

  As a result of intensive studies to achieve the above object, the present inventors have found that a polyester resin having excellent characteristics can be obtained by adding a polyolefin compound having a saponification value of 20 to 80 mgKOH / g to the polyester resin. The composition has been completed.

That is, the first is the present invention, a polyester resin, a polyolefin compound and the polyester resin composition containing a swellable layered silicate, saponification number of the polyolefin compound is 20~80mgKOH / g polyester An injection-molded article using a mold made of a resin composition and mirror-finished with an abrasive of No. 6000 or more, which satisfies the following conditions (a), (b) and (c) And a polyester resin injection molded body .
(A) The diffuse reflectance of the surface of the molded body on which the aluminum film has been applied without undercoating is 2.0% or less.
(B) The deflection temperature under load measured with a 0.45 MPa load is 150 ° C. or higher.
(C) The diffuse reflectance of the surface of the molded body after heat treatment at 150 ° C. for 10 hours is 150% or less after the molded body provided with the aluminum film without undercoating.

As a preferred embodiment, the present invention relates to the polyester resin injection-molded article as described above, wherein the swellable layered silicate is surface-treated with a polyether compound.

As a more preferred embodiment, the present invention relates to the polyester resin injection-molded article as described above, wherein the polyester resin is a polyalkylene terephthalate resin.

The second of the present invention relates to the above-described polyester resin injection-molded article, wherein the surface of the injection-molded molded article is provided with an aluminum film without undercoating.

Using a mirror mold finished by polishing with a polishing agent No. 6000 or more by blending a polyolefin compound having a saponification value of 20 to 80 mg KOH / g and a swellable layered silicate with respect to a polyester resin Even when it is molded, a polyester resin composition that is easy to release and does not reduce surface gloss even when exposed to high temperatures, and a resin molded body comprising the polyester resin composition are provided.

  The thermoplastic polyester resin used in the present invention includes a dicarboxylic acid compound and / or an acid component mainly composed of an ester-forming derivative of dicarboxylic acid, and a diol compound and / or an ester-forming derivative of a diol compound as a main component. It is a conventionally well-known arbitrary thermoplastic polyester resin obtained by reaction with a diol component.

  With the said main component, the ratio which occupies in an acid component or a diol component intends that it is 80 mol% or more, Furthermore, 90 mol% or more, and an upper limit is 100 mol%.

  Examples of the aromatic dicarboxylic acid in the acid component in the present invention include terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, and 4,4′-diphenylether dicarboxylic acid. Acid, 4,4′-diphenylmethanedicarboxylic acid, 4,4′-diphenylsulfonedicarboxylic acid, 4,4′-diphenylisopropylidenedicarboxylic acid, etc., and substituted products thereof (for example, alkyl groups such as methylisophthalic acid) Substituents and the like) and derivatives (alkyl ester compounds such as dimethyl terephthalate and dimethyl 2,6-naphthalenedicarboxylate) can also be used. Oxy acids such as p-oxybenzoic acid and p-hydroxyethoxybenzoic acid and ester-forming derivatives thereof can also be used. These monomers may be used alone or in combination of two or more. Furthermore, aliphatic dicarboxylic acids such as adipic acid, azelaic acid, dodecanedioic acid, sebacic acid and the like can be used together with these aromatic dicarboxylic acids if the amount is small enough not to impair the properties of the resulting thermoplastic polyester resin composition. One or more kinds can be mixed and used.

  Among the acid components, terephthalic acid and its ester-forming derivatives are preferable from the viewpoint of crystallinity, strength, and elastic modulus of the obtained thermoplastic polyester resin.

  Examples of the diol component in the present invention include aliphatic glycols such as ethylene glycol, propylene glycol, butylene glycol, hexylene glycol and neopentyl glycol, and alicyclic glycols such as 1,4-cyclohexanedimethanol. These substituents and derivatives can also be used. Cyclic esters such as ε-caprolactone can also be used. These monomers may be used alone or in combination of two or more. Further, if the amount is small enough not to significantly reduce the elastic modulus of the thermoplastic polyester resin, a long-chain diol compound (for example, polyethylene glycol, polytetramethylene glycol), an alkylene oxide addition polymer of bisphenols, etc. ( For example, an ethylene oxide addition polymer of bisphenol A) may be used in combination.

  Among the diol components, ethylene glycol, butylene glycol, 1,4-cyclohexanedimethanol and 2,2-bis are preferred in terms of easy availability, handleability, strength of the resulting thermoplastic polyester resin, and elastic modulus. (4-Hydroxyphenyl) propane is preferred.

  Specific examples of the thermoplastic polyester resin include, for example, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polycyclohexane-1,4-dimethyl terephthalate, neopentyl terephthalate, polyethylene isophthalate, polyethylene naphthalate, poly Examples include butylene naphthalate, polyhexamethylene naphthalate, and the like, or a copolymer polyester thereof. They may be used alone or in combination of two or more.

  Among the above polyester resins, polyalkylene terephthalate resins such as polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, or copolymers of these resins with bisphenol A polyethylene oxide addition compound or polytetramethylene glycol are easy to handle. From the viewpoints of rigidity, crystallinity, heat resistance and surface properties. It should be noted that polyalkylene isophthalate, polyalkylene naphthalate, and the like may be mixed and used as long as the amount is small enough not to significantly reduce the heat resistance or elastic modulus of the polyester resin.

  The molecular weight of the thermoplastic polyester resin in the present invention is selected in consideration of the molding fluidity in the molding process and various physical properties of the final product, and it is not preferable whether it is too low or too high. That is, the molecular weight of the thermoplastic polyester resin is preferably 0.3 to 2.0 dl / g in logarithmic viscosity measured at 25 ° C. using a phenol / tetrachloroethane (5/5 weight ratio) mixed solvent, and 0.35. -1.9 dl / g is more preferable, and 0.4-1.8 dl / g is still more preferable. When the logarithmic viscosity of the thermoplastic polyester resin is less than 0.3 dl / g, the mechanical properties of the molded article made of the thermoplastic polyester resin composition obtained may be low, and the value exceeds 2.0 dl / g. However, there may be a problem in workability such as poor fluidity during molding.

  In the present invention, by blending a polyolefin compound having a saponification value of 20 to 80 mgKOH / g with respect to the polyester resin, even when molded using a mirror mold, it is easy to release and is exposed to high temperatures. However, it is possible to provide a polyester resin composition having no reduction in surface gloss.

  The polyolefin-based compound used in the present invention is a polyolefin-based copolymer having a saponification value of 20 to 80 mgKOH / g, and examples thereof include a saponified product of an ethylene-vinyl ester copolymer. The lower limit of the saponification value of the polyolefin compound is 20 mgKOH / g, preferably 25 mgKOH / g, more preferably 30 mgKOH / g. If the saponification value is less than 20 mgKOH / g, the releasability and gloss of the polyester resin composition of the present invention may be impaired. The upper limit of the saponification value is 80 mgKOH / g. Even if the saponification value is larger than 80 mg / KOH, the effect does not change, so it is not necessary to make it larger than 80 mg / KOH. The upper limit of the saponification value is preferably 75 mgKOH / g, more preferably 70 mgKOH / g, from the viewpoint of keeping the gloss at the time of heat resistance high.

  A typical example of the vinyl ester is vinyl acetate, but other fatty acid vinyl esters such as vinyl propionate and vinyl pivalate can also be used.

  Moreover, as a copolymerization component, a vinyl silane compound can also be used besides vinyl ester. Here, examples of the vinylsilane compound include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (β-methoxy-ethoxy) silane, and γ-methacryloxypropylmethoxysilane. Of these, vinyltrimethoxysilane and vinyltriethoxysilane are preferably used.

  The olefin component of the polyolefin compound is not particularly limited, but ethylene, propylene, 1-butene, isobutene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 3-methyl-1-butene, 4-methyl Examples include -1-pentene and 4,4-dimethyl-1-pentene. Of these, ethylene and propylene are preferable from the viewpoints of cost and releasability. The polyolefin compound may be a copolymer. The component to be copolymerized is not particularly limited. For example, ethylene, propylene, 1-butene, isobutene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 3-methyl-1-butene, 4-methyl In addition to various α-olefins such as -1-pentene and 4,4-dimethyl-1-pentene, olefins other than α-olefins such as 2-butene, styrene, and the like may be copolymerized. Among these, α-olefin is preferable from the viewpoint of ease of copolymerization and cost.

  The content of the olefin component is 20 to 90 mol%, preferably 25 to 85 mol%, more preferably 30 to 85 mol%, and still more preferably 35 to 80 mol%, from the viewpoint of releasability of the obtained polyester resin composition. It is in the range of mol%.

  The content and saponification value of the olefin component of the polyolefin compound can be determined by a nuclear magnetic resonance (NMR) method, and the melting point can be determined by a differential thermal analysis (DSC) method (temperature increase rate: 10 ° C./min). .

  The above polyolefin compounds may be used alone or in combination of two or more.

  In the present invention, the addition amount of the polyolefin-based compound is preferably 0.01 parts by weight, more preferably 0.05 parts by weight, and still more preferably 0.1 parts by weight with respect to 100 parts by weight of the polyester resin. If the lower limit of the amount of polyolefin compound added is less than 0.01 parts by weight, the effect of improving the releasability may not be sufficient. Moreover, 3 weight part is preferable as an upper limit of the addition amount of a polyolefin-type compound, 2 weight part is more preferable, and 1 weight part is further more preferable. If the addition amount upper limit exceeds 3 parts by weight, the surface gloss of the resulting molded product may be impaired.

  The production method of the polyester resin composition of the present invention is not particularly limited, and examples thereof include a method of melt-kneading a polyester resin and a polyolefin compound using various general kneaders. Examples of the kneader include a single screw extruder, a twin screw extruder, a roll, a Banbury mixer, a kneader, and the like, and a kneader with high shear efficiency is particularly preferable. The polyester resin and the polyolefin-based compound may be melted and kneaded in a lump in the above-mentioned kneader, or may be melt-kneaded by adding the polyolefin-based compound to a polyester resin that has been previously melted.

  In the present invention, an inorganic compound can be added for the purpose of improving the heat resistance, elastic modulus or molding shrinkage of the polyester resin composition.

Inorganic compounds used in the present invention are known in the art, such as silicates such as swellable mica, smectite, talc and kaolin, phosphates such as zirconium phosphate, titanates such as potassium titanate, and tungstic acid. Tungstates such as sodium, uranates such as sodium uranate, vanadates such as potassium vanadate, molybdates such as magnesium molybdate, niobates such as potassium niobate, graphite layered compounds, magnesium hydroxide In addition to metal hydroxides such as silicon oxide, titanium oxide and alumina, carbonate compounds such as calcium carbonate and barium carbonate, sulfate compounds such as calcium sulfate and barium sulfate, zinc sulfide and calcium phosphate are mentioned. However, it is not limited to these. On the other hand, in the present invention, carbon black, wood powder and the like can be used although they are not inorganic compounds. These may be used alone or in combination of two or more.
Among the above inorganic compounds, swellable mica, smectite, kaolin, talc, mica, titanium oxide, silicon oxide, calcium carbonate, barium sulfate, and zinc sulfide are preferable from the viewpoint of easy availability and handling. Preferably, swellable layered silicates such as swellable mica and smectite can be used in terms of surface gloss and molding shrinkage.

  When the polyester resin composition of the present invention is used for applications requiring surface smoothness or surface gloss such as lighting parts, the inorganic compound is preferably finer, and in that case, the average particle size is 5 μm or less. Preferably, it is 3 μm or less, more preferably 1 μm or less. The addition amount of the inorganic compound in the present invention also depends on the intended heat resistance and surface gloss, but the addition amount is preferably 20 parts by weight or less, more preferably 15 parts by weight or less, and even more preferably 10 parts by weight or less.

  In the present invention, a surface treating agent can be used for the purpose of uniformly dispersing the inorganic compound. Examples of the surface treatment agent include a silane compound or a polyether compound.

  In the present invention, the surface treatment method of the inorganic compound using the surface treatment agent is not particularly limited. For example, a method of directly treating the inorganic compound with the treatment agent (dry method), a treatment agent, A method of spraying a solution containing (a spray method), a method of adding a surface treatment agent after dispersing an inorganic compound in a polar solvent compatible with water in an arbitrary ratio or a polar solvent containing water (wet method) Law). Among these, the wet method is preferable from the viewpoint of the efficiency of the surface treatment. The polar solvent used at this time will be described later.

As the silane compound, any one generally used is generally used, and the following general formula (1):
Y _n SiX _4-n (1)
It is represented by N in General formula (1) is an integer of 0-3, Y is a C1-C25 hydrocarbon group which may have a substituent.

  Examples of the substituent when the hydrocarbon group having 1 to 25 carbon atoms in Y has a substituent include a group bonded by an ester bond, a group bonded by an ether bond, an epoxy group, and an amino group. , Carboxyl group, group having carbonyl group at the end, amide group, mercapto group, group bonded by sulfonyl bond, group bonded by sulfinyl bond, nitro group, nitroso group, nitrile group, halogen group, hydroxyl group, etc. Is mentioned. The hydrocarbon group having 1 to 25 carbon atoms may be substituted with one of these, or may be substituted with two or more.

  X in the general formula (1) is a hydrolyzable group and / or a hydroxyl group. Examples of the hydrolyzable group include an alkoxy group, an alkenyloxy group, a ketoxime group, an acyloxy group, an amino group, and an aminoxy group. Amide group, halogen group and the like.

  In general formula (1), when n or 4-n is 2 or more, n Y or 4-n X may be the same or different.

  In the above general formula (1), specific examples of the silane compound when Y is a hydrocarbon group having 1 to 25 carbon atoms include those having a linear long-chain alkyl group such as decyltrimethoxysilane. , Having a lower alkyl group such as methyltrimethoxysilane, having an unsaturated hydrocarbon group such as 2-hexenyltrimethoxysilane, and having an alkyl group having a side chain such as 2-ethylhexyltrimethoxysilane Those having a phenyl group such as phenyltriethoxysilane, those having a naphthyl group such as 3-β-naphthylpropyltrimethoxysilane, and those having an aralkyl group such as p-vinylbenzyltrimethoxysilane. Can be mentioned. Examples of the case where Y is a group having a vinyl group among hydrocarbon groups having 1 to 25 carbon atoms include vinyltrimethoxysilane, vinyltrichlorosilane, and vinyltriacetoxysilane. An example of the case where Y is a group having a group substituted with an ester group is γ-methacryloxypropyltrimethoxysilane. Examples of the case where Y is a group having a group substituted with a group bonded with an ether group include γ-polyoxyethylenepropyltrimethoxysilane and 2-ethoxyethyltrimethoxysilane. An example of the case where Y is a group substituted with an epoxy group includes γ-glycidoxypropyltrimethoxysilane. Examples of when Y is a group substituted with an amino group include γ-aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, and γ-anilinopropyltrimethoxysilane. Can be mentioned. An example of the case where Y is a group substituted with a group having a carbonyl group at the terminal includes γ-ureidopropyltriethoxysilane. An example of the case where Y is a group substituted with a mercapto group includes γ-mercaptopropyltrimethoxysilane. An example of the case where Y is a group substituted with a halogen atom includes γ-chloropropyltriethoxysilane. An example of the case where Y is a group having a group substituted with a group bonded with a sulfonyl group includes γ-phenylsulfonylpropyltrimethoxysilane. An example of the case where Y is a group having a group substituted with a group bonded with a sulfinyl group includes γ-phenylsulfinylpropyltrimethoxysilane. An example of the case where Y is a group substituted with a nitro group includes γ-nitropropyltriethoxysilane. An example of the case where Y is a group substituted with a nitroso group includes γ-nitrosopropyltriethoxysilane. Examples of the case where Y is a group substituted with a nitrile group include γ-cyanoethyltriethoxysilane and γ-cyanopropyltriethoxysilane. An example of the case where Y is a group substituted with a carboxyl group includes γ- (4-carboxyphenyl) propyltrimethoxysilane. In addition to the above, a silane compound in which Y is a group having a hydroxyl group can also be used. Such an example includes N, N-di (2-hydroxyethyl) amino-3-propyltriethoxysilane. The hydroxyl group can also be in the form of a silanol group (SiOH).

  In the present invention, a substituted product or derivative of the above silane compound can also be used. These silane compounds may be used alone or in combination of two or more.

  The usage-amount of the silane type compound in this invention can be prepared so that the dispersibility of the inorganic compound in a polyester resin molded object may fully increase. If necessary, a plurality of types of silane compounds having different functional groups can be used in combination. Therefore, the amount of the silane compound used is not generally limited by numerical values, but the lower limit of the amount of the silane compound used relative to 100 parts by weight of the inorganic compound is 0.1 parts by weight, preferably 0.2. Parts by weight, more preferably 0.3 parts by weight, still more preferably 0.4 parts by weight, and particularly preferably 0.5 parts by weight. The upper limit of the amount of the silane compound used relative to 100 parts by weight of the inorganic compound is 200 parts by weight, preferably 180 parts by weight, more preferably 160 parts by weight, still more preferably 140 parts by weight, 120 parts by weight is preferable. If the lower limit of the amount of silane compound used is less than 0.1 parts by weight, the effect of finely dispersing the inorganic compound may be insufficient. Further, when the amount of the silane compound is 200 parts by weight or more, the effect of fine dispersion does not change, so it is not necessary to use more than 200 parts by weight.

  The polyether compound in the present invention is preferably a compound whose main chain is polyoxyalkylene such as polyoxyethylene or polyoxyethylene-polyoxypropylene copolymer, and the number of repeating units of oxyalkylene is 2. To about 100 is preferable.

  The polyether compound may have an arbitrary substituent in the side chain and / or main chain as long as it does not adversely affect the polyester resin or the inorganic compound. Examples of the substituent include, for example, a hydrocarbon group, a group bonded by an ester bond, an epoxy group, an amino group, a carboxyl group, a group having a carbonyl group at the terminal, an amide group, a mercapto group, and a sulfonyl bond. Functional groups that can form Si—O— bonds such as nitro groups, nitroso groups, nitrile groups, alkoxysilyl groups, silanol groups, halogen groups, hydroxyl groups Etc. One of these may be substituted, and two or more may be substituted.

  The hydrocarbon group is a straight chain or branched chain (that is, having a side chain), saturated or unsaturated, monovalent or polyvalent aliphatic hydrocarbon group, aromatic hydrocarbon group or alicyclic group. It means a hydrocarbon group, and examples thereof include an alkyl group, an alkenyl group, an alkynyl group, a phenyl group, a naphthyl group, and a cycloalkyl group. In the present invention, the term “alkyl group” includes polyvalent hydrocarbon groups such as “alkylene group” unless otherwise specified. Similarly, the alkenyl group, alkynyl group, phenyl group, naphthyl group, and cycloalkyl group each include an alkenylene group, an alkynylene group, a phenylene group, a naphthylene group, a cycloalkylene group, and the like.

  The composition ratio of the substituents in the polyether compound is not particularly limited, but the polyether compound used in the present invention contains water, a polar solvent compatible with water at an arbitrary ratio, or water. It is desirable to be soluble in a polar solvent. Specifically, for example, the solubility of the polyether compound in 100 g of water at room temperature is preferably 1 g or more, more preferably 2 g or more, still more preferably 5 g or more, and particularly preferably 10 g or more. Most preferably, it is 20 g or more.

  Examples of the polar solvent include alcohols such as methanol, ethanol and isopropanol, glycols such as ethylene glycol, propylene glycol and 1,4-butanediol, ketones such as acetone and methyl ethyl ketone, ethers such as diethyl ether and tetrahydrofuran. Amide compounds such as N, N-dimethylformamide and N, N-dimethylacetamide, and other solvents include pyridine, dimethyl sulfoxide and N-methylpyrrolidone. Carbonic acid diesters such as dimethyl carbonate and diethyl carbonate can also be used. These polar solvents may be used alone or in combination of two or more.

  Specific examples of the polyether compound used in the present invention include, for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyethylene glycol-polypropylene glycol, polyethylene glycol-polytetramethylene glycol, polyethylene glycol monomethyl ether, polyethylene glycol dimethyl ether, Polyethylene glycol monoethyl ether, polyethylene glycol diethyl ether, polyethylene glycol monoallyl ether, polyethylene glycol diallyl ether, polyethylene glycol monophenyl ether, polyethylene glycol diphenyl ether, polyethylene glycol octyl phenyl ether, polyethylene glycol methyl ethyl ether , Polyethylene glycol methyl allyl ether, polyethylene glycol glyceryl ether, polyethylene glycol monomethacrylate, polyethylene glycol monoacrylate, polypropylene glycol monomethacrylate, polypropylene glycol monoacrylate, polyethylene glycol-polypropylene glycol monomethacrylate, polyethylene glycol-polypropylene glycol monoacrylate, polyethylene glycol -Polytetramethylene glycol monomethacrylate, polyethylene glycol-Polytetramethylene glycol monoacrylate, methoxypolyethylene glycol monomethacrylate, methoxypolyethylene glycol monoacrylate, octoxypolyethylene glycol- Ripropylene glycol monomethacrylate, octoxy polyethylene glycol-polypropylene glycol monoacrylate, lauroxy polyethylene glycol monomethacrylate, lauroxy polyethylene glycol monoacrylate, stearoxy polyethylene glycol monomethacrylate, stearoxy polyethylene glycol monoacrylate, allyloxy polyethylene glycol monomethacrylate , Allyloxy polyethylene glycol monoacrylate, nonylphenoxy polyethylene glycol monomethacrylate, nonylphenoxy polyethylene glycol monoacrylate, polyethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol-polytetramethylene glycol Coal dimethacrylate, polyethylene glycol-polytetramethylene glycol diacrylate, bis (polyethylene glycol) butylamine, bis (polyethylene glycol) octylamine, polyethylene glycol bisphenol A ether, polyethylene glycol-polypropylene glycol bisphenol A ether, ethylene oxide modified bisphenol A di Methacrylate, ethylene oxide modified bisphenol A diacrylate, ethylene oxide-propylene oxide modified bisphenol A dimethacrylate, polyethylene glycol diglycidyl ether, polyethylene glycol ureidopropyl ether, polyethylene glycol mercaptopropyl ether, polyethylene glycol phenyls E sulfonyl propyl ether, polyethylene glycol phenylsulfinyl propyl ether, polyethylene glycol nitro propyl ether, polyethylene glycol nitroso propyl ether, polyethylene glycol cyanoethyl ethers, polyethylene glycol cyanoethyl ether. These polyether compounds may be used alone or in combination of two or more.

  As a polyether compound used by this invention, what has cyclic hydrocarbon groups, such as an aromatic hydrocarbon group and an alicyclic hydrocarbon group, is preferable, and the following general formula (2):

（一般式（２）中、−Ａ−は、−Ｏ−、−Ｓ−、−ＳＯ−、−ＳＯ₂-、−ＣＯ−、炭素数１〜２０のアルキレン基、または炭素数６〜２０のアルキリデン基であり、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷およびＲ⁸は、いずれも水素原子、ハロゲン原子、または炭素数１〜５の１価の炭化水素基であり、それらはそれぞれ同一であっても異なっていても良い。）
で表される単位を有するものが好ましい。
さらには、下記一般式（３）：

(In the general formula (2), -A- is, -O -, - S -, - SO -, - SO 2 -, - CO-, an alkylene group having 1 to 20 carbon atoms or 6 to 20 carbon atoms, An alkylidene group, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are all hydrogen atoms, halogen atoms, or monovalent hydrocarbons having 1 to 5 carbon atoms And they may be the same or different.)
What has a unit represented by these is preferable.
Furthermore, the following general formula (3):

（一般式（３）中、−Ａ−は、−Ｏ−、−Ｓ−、−ＳＯ−、−ＳＯ₂-、−ＣＯ−、炭素数１〜２０のアルキレン基、または炭素数６〜２０のアルキリデン基であり、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷およびＲ⁸は、いずれも水素原子、ハロゲン原子、または炭素数１〜５の１価の炭化水素基であり、それらはそれぞれ同一であっても異なっていても良い。Ｒ⁹、Ｒ¹⁰はいずれも炭素数１〜５の２価の炭化水素基であり、それらはそれぞれ同一であっても異なっていても良い。Ｒ¹¹、Ｒ¹²はいずれも水素原子、炭素数１〜２０の１価の炭化水素基であり、それらはそれぞれ同一であっても異なっていても良い。ｍおよびｎはオキシアルキレン単位の繰り返し単位数を示し、１≦ｍ≦２５、１≦ｎ≦２５、２≦ｍ＋ｎ≦５０である。）で表されるものが、無機化合物の分散性および熱安定性の点から好ましい。

(In the general formula (3), -A- is, -O -, - S -, - SO -, - SO 2 -, - CO-, an alkylene group having 1 to 20 carbon atoms or 6 to 20 carbon atoms, An alkylidene group, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are all hydrogen atoms, halogen atoms, or monovalent hydrocarbons having 1 to 5 carbon atoms R ⁹ and R ¹⁰ are each a divalent hydrocarbon group having 1 to 5 carbon atoms, and they may be the same or different. R ¹¹ and R ¹² are each a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different, and m and n are oxy Indicates the number of repeating units of alkylene units, 1 ≦ m ≦ 25, 1 ≦ n ≦ 25, 2 ≦ m + n ≦ 50.) Those represented is preferable from the viewpoint of dispersibility and thermal stability of inorganic compounds.

  The amount of the polyether compound used in the present invention can be adjusted so that the affinity between the inorganic compound and the polyester resin and the dispersibility of the inorganic compound in the polyester resin composition are sufficiently enhanced. If necessary, a plurality of types of polyether compounds having different functional groups can be used in combination. Accordingly, the amount of the polyether compound used is not generally limited by numerical values, but the lower limit of the amount of the polyether compound used relative to 100 parts by weight of the inorganic compound is 0.1 parts by weight, preferably 0.2 Parts by weight, more preferably 0.3 parts by weight, still more preferably 0.4 parts by weight, and particularly preferably 0.5 parts by weight. The upper limit of the amount of the polyether compound used relative to 100 parts by weight of the inorganic compound is 200 parts by weight, preferably 180 parts by weight, more preferably 160 parts by weight, still more preferably 140 parts by weight, 120 parts by weight is preferable. If the lower limit of the amount of the polyether compound used is less than 0.1 parts by weight, the effect of finely dispersing the inorganic compound tends to be insufficient. Further, if the upper limit of the amount of polyether compound used is 200 parts by weight or more, the effect of fine dispersion does not change, so it is not necessary to use more than 200 parts by weight.

  In the polyester resin composition of the present invention, polybutadiene, butadiene-styrene copolymer, acrylic rubber, ionomer, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, natural rubber, as long as the quality is not impaired. Chlorinated butyl rubber, homopolymer of α-olefin, copolymer of two or more α-olefins (including any copolymer such as random, block, graft, etc., or a mixture thereof), or Impact resistance improvers such as olefinic elastomers can be added. These may be modified with an acid compound such as maleic anhydride or an epoxy compound such as glycidyl methacrylate.

  Further, the polyester resin composition of the present invention may be any other thermoplastic resin or thermosetting resin, for example, unsaturated polyester resin, polyester carbonate resin, liquid crystal polyester resin, polyolefin resin, as long as the quality is not impaired. Polyamide resins, rubbery polymer reinforced styrene resins, polyphenylene sulfide resins, polyphenylene ether resins, polyacetal resins, polysulfone resins, polyarylate resins, and the like may be used alone or in combination of two or more.

  Furthermore, depending on the purpose, the polyester resin composition of the present invention may contain pigments, dyes, heat stabilizers, antioxidants, UV absorbers, light stabilizers, plasticizers, flame retardants, antistatic agents, and the like. An agent can be added.

  Since the molded product obtained from the polyester resin composition of the present invention is excellent in surface gloss and heat resistance, it can be used in various lighting parts such as automotive lamp parts such as headlamp extensions, headlamp reflectors, rear lamp handling, and reflectors for facility lighting. It can be used suitably.

  As a manufacturing method for obtaining a molded body from the polyester resin composition in the present invention, for example, it is preferable to mold the molded body using a mold having a mirror finish by polishing with an abrasive of No. 6000 or more. As a molding method, a normal molding method can be employed. For example, a hot melt molding method such as injection molding, extrusion molding, or blow molding can be employed. Of these, the injection molding method is preferable.

  In the present invention, the diffuse reflectance of the molded product surface measured in accordance with JIS D5705 when the aluminum film is applied without undercoating or the like to the obtained molded product surface is 2.0% or less. Preferably, it is 1.8% or less, more preferably 1.5% or less. When the diffuse reflectance exceeds 2.0%, the gloss is not sufficient, which may cause problems in lighting component applications. The lower limit of the diffuse reflectance is not particularly limited, but is about 0.6%.

  The load deflection temperature measured under the condition of 0.45 MPa load of the obtained molded product in the present invention is preferably 150 ° C. or higher, more preferably 155 ° C. or higher, and further preferably 160 ° C. or higher. When the deflection temperature under load is lower than 150 ° C., the molded product may be deformed by the heat of the light source. Although there is no upper limit of the deflection temperature under load, it is about 180 ° C.

  Since the polyester molded body obtained from the polyester resin composition of the present invention is excellent in heat resistance, the surface of the molded body even if the molded body on which the aluminum film is applied without undercoating or the like under the surface is exposed to a high temperature. It is possible to keep the diffuse reflectance of the low.

  In the present invention, the diffuse reflection of the surface of the molded article when the molded article obtained by subjecting the polyester molded article surface obtained from the polyester resin composition to an aluminum film without undercoating or the like undercoating for 10 hours at 150 ° C. The rate is preferably 3.0% or less, more preferably 2.8% or less, and further preferably 2.5% or less.

  In addition, the method to apply | coat an aluminum film with respect to a molded object surface is not specifically limited, A conventionally well-known method can be used. As a method for applying the aluminum film, for example, there is a dry plating method (PVD method). Among the dry plating methods, a vacuum deposition method or a sputtering method is desirable. Furthermore, as a method for obtaining a light reflecting surface having high brightness, the surface activation treatment was performed by exposing the surface of the resin molded product to the obtained argon plasma by previously converting the argon gas into plasma by direct current or high frequency. Thereafter, a method of forming an aluminum film is also used. Further, after the surface activation treatment, the active molecular film or the hydrophilic polymer film is formed on the surface after introducing functional groups on the surface of the molded article by exposure to oxygen, nitrogen or a mixed gas thereof, or by exposing to a reactive monomer. There is a method of forming an aluminum film after application, and by using this method, a molded article having a high brightness feeling and a good light reflecting surface can be obtained.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.

The main raw materials used in Examples and Comparative Examples are summarized below. Unless otherwise noted, the raw materials are not purified.
(material)
Polyester resin A1: Polybutylene terephthalate resin (manufactured by KOLON, KP210)
Polyester resin A2: Polyethylene terephthalate resin (manufactured by Kanebo Synthetic Co., Ltd., EFG70)
Polyolefin compound B1: VESTOWAX J324 from degussa (saponification number = 27 mgKOH / g)
Polyolefin compound B2: VESTOWAX E421R manufactured by degussa (saponification value = 43 mgKOH / g)
Polyolefin compound B3: VESTOWAX AS1550 from degussa (saponification number = 50 mgKOH / g)
Polyolefin-based compound B4: VESTOWAX AO1570 (degussa) (saponification number = 70 mgKOH / g)
Comparative additive C1: Vestowax A616 from degussa (saponification number = 0 mgKOH / g)
Inorganic compound D1: Kaolin (ASP170, manufactured by Engelhard)
Inorganic compound D2: Talc (manufactured by IMI FABI, HTPultra 5C)
Inorganic compound D3: Surface-treated swelling mica obtained in Production Example 1 Inorganic compound D4: Surface-treated montmorillonite obtained in Production Example 2 (Production Example 1)
Using a wet mixer, 8 parts of swellable fluorinated mica (manufactured by Co-op Chemical Co., Ltd., Somasif ME100) was mixed with 100 parts by weight of pure water. Next, 1.3 parts of a polyether compound (Toho Chemical Co., Ltd., bisol) was added, and the mixture was treated by continuing mixing for 15 to 30 minutes. Thereafter, it was dried and pulverized to obtain a polyether-treated swelling mica.

(Production Example 2)
Using a wet mixer, 5 parts of montmorillonite (Kunimine F, Kunipia F) was mixed with 100 parts by weight of pure water. Then, 1 part of a silane compound (manufactured by Nippon Unicar Co., Ltd., A1120) was added and the mixture was treated by continuing mixing for 15 to 30 minutes. Thereafter, it was dried and pulverized to obtain a silane-treated montmorillonite.

  The evaluation methods of various physical properties relating to the polyester resin compositions obtained in Examples and Comparative Examples are as follows.

(Releasability)
The obtained polyester resin composition has a cylindrical shape with a diameter of about 70 mm, a depth of about 80 mm, a thickness of about 2.5 mm, and a draft angle of 3 degrees, and is polished using a polishing agent having a surface of No. 6000 and mirror-finished. Using the mold, injection molding (resin temperature setting 270 ° C. and mold temperature setting 80 ° C.) was performed. The evaluation of releasability was evaluated by the number of times of releasable at a mold temperature of 80 ° C. The more times the mold can be released, the better.

(Load deflection temperature)
The obtained polyester resin composition was used for injection molding (resin temperature setting 270 ° C. and mold temperature setting 80 ° C.). The deflection temperature under load of the obtained sample for measurement was measured according to ASTM D-648 under the condition of a load of 0.45 MPa. It should be noted that the deflection temperature under load is preferably as high as possible.

(Surface gloss / diffuse reflectance)
The surface appearance was evaluated by the diffuse reflectance of the surface of the molded article formed with aluminum. Using the obtained polyester resin composition, a flat-plate test piece (resin temperature setting 270 ° C. and mold temperature setting 80 ° C.) was molded by using a mold polished with a No. 14000 abrasive and mirror finished. About 80 mm × about 50 mm × about 2 mm thick). Aluminum was formed on the surface of the test piece so as to have a thickness of about 800 mm.

  The diffuse reflectance of the surface of the test piece immediately after forming the aluminum film was measured using a mirror reflectometer (manufactured by Tokyo Denshoku Co., Ltd., TR-1100AD). In addition, a diffuse reflectance is so preferable that a value is small.

(Heat resistance of surface gloss)
The heat resistance of the surface gloss was evaluated by measuring the diffuse reflectance on the surface of the test piece after heat-treating the test piece on which the aluminum film was formed (160 ° C. × 50 hours). The heat resistance of the surface gloss is better as the diffuse reflectance is smaller even after heat treatment.

(Examples 1-9 ; Reference Example )
After blending the polyester resin and the polyolefin-based compound at the composition ratio shown in Table 1, using a twin screw extruder (manufactured by Nippon Steel Co., Ltd., TEX44), melt-kneading at a resin temperature setting of 220 to 250 ° C. A polyester resin composition was obtained and various physical properties were evaluated. The results are shown in Table 1.

(Comparative Examples 1-3)
A polyester resin composition was obtained in the same manner as in Example 1 except that a comparative additive was used in place of the polyolefin compound, and various physical properties were evaluated. The results are shown in Table 1.

（実施例１０〜１７）
ポリエステル樹脂、ポリオレフィン系化合物および無機化合物を表２に示した組成比にてブレンドした後、二軸押出機（日本製鋼（株）製、ＴＥＸ４４）を用い、樹脂温度設定約２２０〜２５０℃で溶融混練することによりポリエステル樹脂組成物を得、各種物性を評価した。結果を表２に示す。

(Examples 10 to 17)
After blending the polyester resin, polyolefin compound and inorganic compound in the composition ratio shown in Table 2, using a twin screw extruder (manufactured by Nippon Steel Co., Ltd., TEX44), melt at a resin temperature setting of about 220 to 250 ° C. By kneading, a polyester resin composition was obtained, and various physical properties were evaluated. The results are shown in Table 2.

(Comparative Examples 4-7)
A polyester resin composition was obtained in the same manner as in Example 10, 12, 14 or 16 except that a comparative additive was used in place of the polyolefin compound, and various physical properties were evaluated. The results are shown in Table 2.

  Since the polyester resin composition obtained by the present invention is excellent in releasability and surface gloss, it is used for lighting applications and appearance parts. The processing method for obtaining a molded body from the polyester resin composition can be applied to injection molding or hot press molding, and can also be applied to blow molding. The obtained molded article is excellent in surface glossiness, and the surface gloss does not decrease even when treated at a high temperature. In addition to the above-mentioned lighting component applications, it has features such as excellent heat distortion resistance, etc. In addition to parts that emphasize the appearance, it also includes automotive parts, household electrical appliance parts, household daily goods, packaging materials, and other general industrial use. It is suitably used for materials.

Claims (4)

A polyester resin composition comprising a polyester resin, a polyolefin compound and a swellable layered silicate, comprising a polyester resin composition having a saponification value of 20 to 80 mg KOH / g of the polyolefin compound, and having a number of 6000 or more A polyester resin injection-molded article using a mold that is mirror-finished using the above-mentioned abrasive and satisfying the following conditions (a), (b), and (c):
(A) The diffuse reflectance of the surface of the molded body on which the aluminum film has been applied without undercoating is 2.0% or less.
(B) The deflection temperature under load measured with a 0.45 MPa load is 150 ° C. or higher.
(C) The diffuse reflectance of the surface of the molded body after heat treatment at 150 ° C. for 10 hours is 150% or less after the molded body provided with the aluminum film without undercoating. The polyester resin injection-molded article according to claim 1, wherein the swellable layered silicate is surface-treated with a polyether compound . The polyester resin injection-molded article according to claim 1 or 2, wherein the polyester resin is a polyalkylene terephthalate resin. The polyester resin molded product according to any one of claims 1 to 3, wherein an aluminum film is applied to the surface of the injection molded product without undercoating.