CN100537669C

CN100537669C - Thermoplastic resin composition for light reflector, formed article for light reflector, light reflector, and method for producing formed article for light reflector

Info

Publication number: CN100537669C
Application number: CNB2004800240955A
Authority: CN
Inventors: 白井安则; 植田治夫; 高木珠衣
Original assignee: Mitsubishi Rayon Co Ltd
Current assignee: Mitsubishi Chemical Corp
Priority date: 2003-08-26
Filing date: 2004-08-25
Publication date: 2009-09-09
Anticipated expiration: 2024-08-25
Also published as: JP2011168060A; JP5417374B2; CN101428478B; CN1839181A; CN101428478A

Abstract

Disclosed are a thermoplastic resin composition for light reflectors which contains 2-45 parts by mass of an inorganic filler (B1) which is treated with a fatty acid based surface-finishing agent and has an average particle diameter of not more than 3 m, per 100 parts by mass of a thermoplastic resin (A); a thermoplastic resin composition for light reflectors which contains 2-45 parts by mass of an inorganic filler (B2) with an average particle diameter of not more than 3 m whose refractive index a is 1.61 & a & 2.5, per 100 parts by mass of a thermoplastic resin (A); and a thermoplastic resin composition for light relectors which contains 0.01-3 parts by mass of a fatty acid glycerol triester and/or a fatty acid glycerol diester (C1) and 0.01-3 parts by mass of a fatty acid glycerol monoester (C2) per 100 parts by mass of a thermoplastic resin (A). Also disclosed are a formed article for light reflectors which is made of one of such thermoplastic resin compositions and a light relector obtained by directly forming a light-reflecting metal layer on at least a part of the surface of such a formed article for light reflectors.

Description

The manufacture method of light-reflecting article thermoplastic resin composition, formed article for light reflector, light emitter and formed article for light reflector

Technical field

The present invention relates to the thermoplastic resin composition of light reflectors such as a kind of cover that is used in lamps for vehicle, speculum, prolongation, lighting fixtures, and the light reflector that on this thermoplastic resin composition's molding, directly forms the luminous reflectance metal level.And, the present invention relates to a kind of like this technology, in order to make this light reflector that directly forms have good surface appearance, the injection molding forming that is used to make is polished grain size number more than or equal to surface treatments such as No. 5000 polishing or chromium plating with the surface of metal pattern, the surface smoothing of molding, surface luster, surperficial clarity increase, after evaporation and application, obtain good surface appearance easily.

The application requires to quote its content here with in Japanese patent application 2003-301606 number of application on August 26th, 2003 and Japanese patent application 2003-301613 number, in Japanese patent application 2003-434916 number of application on December 26th, 2003 and be right of priority in Japanese patent application 2004-235995 number of application on August 13rd, 2004.

Background technology

In the past, as being used in the light-reflecting article material that speculum on the lamps for vehicle etc. and extension grade, used the bulk molding composite (following abbreviation BMC) of thermosetting resin.Though BMC thermotolerance, excellent size stability, have that forming period is long, during the handling of burr when being shaped etc., problem that production efficiency is low.As the method that addresses these problems, consider to use thermoplastic resin.

As the example that uses thermoplastic resin, can use with crystalline resins such as the vibrin of polybutylene terephthalate, polyethylene terephthalate etc., and the noncrystalline resin that is representative with the polycarbonate etc. mixes the thermoplastic resin composition of various strengthening materials as representative.

For example, someone proposes to use a kind of use polyethylene terephthalate as thermoplastic resin, mixes the method for compositions (with reference to Japanese publication spy open flat 6-203613 communique) of inorganic filling materials such as glass fibre and talcum as strengthening material therein.

Yet, in the method,,, make the molding surface smoothing so before forming the luminous reflectance metal level on the product of formation, need carry out undercoat and handle because the smoothness on the bad molding surface that causes of the emersion of inorganic filling material and molding is not enough.Handle if do not carry out undercoat, neither minute surface even then form the luminous reflectance metal level, can not obtain satisfied light reflector.Such undercoat is handled, because operation especially increases with the handling problem of the employed solvent of undercoat material even needs dry paint, so there is the energy that needs especially, returns the problem that environment increases burden.

As carrying out the method that such undercoat is handled, a kind of direct vapour deposition method is proposed in recent years.This direct vapour deposition method is by direct evaporation metal on molding, or after carrying out the active processing of plasma body on the molding, deposited metal film is taken this to not be used in the molding surface and carried out the undercoat processing again, directly forms the method for luminous reflectance metal level.In this direct vapour deposition method, because directly form metal level, so can obtain smoothness than all good in the past molding surface on the molding surface.

Recently, in order to increase brightness, tend to use the lamp of high output, then the temperature in the headlamp rises, as the heat resisting temperature of 160～180 ℃ of the base material requires of radiator.Yet in the light reflector of being made by direct vapour deposition method, when using for a long time under such pyritous environment, the problem that the luminous reflectance metal level is fuzzy (heating is blured) is remarkable especially.This heating blooming has several types, the substrate resin that phenomenon (the planar defective of tangerine peel) that substrate resin that (1) caused by the thermal distortion (surface smoothing reduction) of substrate resin and metal level peel off, (2) cause by the thermal degradation gas of substrate resin for example, is arranged and metal level is peeled off or metamorphism (whiting), (3) by the composition of additive in the substrate resin etc. ooze out the substrate resin that causes and metal level is peeled off or metamorphism (whiting) etc.

In order to address this problem, various trials have been carried out, for example proposing to mix 3 mass parts median sizes by the people in the thermoplastic resin of being made up of polyalkylene terephthalates resin and polycarbonate resin of 100 mass parts is the resin combination (with reference to Japanese publication spy open flat 11-241006 communique) of the surperficial untreated talcum of 0.3 μ m as strengthening material, and with respect to 100 mass parts vibrin, mixing the median size that 12～25 mass parts handled through epoxy silane is the steatitic resin combination (opening the 2003-12903 communique with reference to Japanese publication spy) of 2.6～3.8 μ m.For solving this heating fuzzy problem, also carry out other various trials, for example the someone proposes to mix the resin combination (opening the 2000-35509 communique with reference to Japanese publication spy) of inorganic filler, oxidation inhibitor, internal lubricant in polybutylene terephthalate, and the resin combination (opening the 2002-179895 communique with reference to Japanese publication spy) that mixes inorganic strengthening material and paraffin in the resin of being made up of polybutylene terephthalate and poly-alkylene naphthalate.

Yet, Japan publication spy opens the described resin combination of flat 11-241006 communique, because use not surface treated inorganic filling material as strengthening material, so resin and inorganic filling material break-in are bad, and because of using very tiny is that the particle of 0.3 μ m makes cohesion easily between the inorganic filling material, has the not enough problem of molding surface smoothing.

Again, Japanese publication spy opens the described resin combination of 2003-12903 communique because use median size at the bigger inorganic filling material of 2.6～3.8 mu m ranges as strengthening material, so there is the not enough problem of the surface smoothing of molding.Because of using the surface treatment agent of epoxy silane treatment agent as inorganic filling material, then unreacted epoxy silane treatment agent oozes out the molding surface when being shaped, with the metal pattern surface reaction, have the bad problem of liftability again.Its result produces the bad defective that causes of molding (molding vestige) on the molding surface, directly forms the occasion of luminous reflectance metal level on this molding, exists in and leaves the molding vestige on the reflection layer, produces the problem of defective.

Again, Japan publication spy opens flat 11-241006 communique and the spy opens the described resin combination of 2003-12903 communique, because of using talcum as strengthening material, on the molding that uses this resin combination, directly form the luminous reflectance metal level, obtain the occasion of light reflector, have the unsharp problem of reflection appearance of light reflector.

Again, Japan publication spy opens the described resin combination of 2000-35509 communique, by the terminal carboxyl(group) amount is decided to be below the specified quantitative,, suppress heating fuzzy (whiting) by the generation (phenomenons of above-mentioned (2)) of inhibition as the thermolysis gas of the vibrin of substrate resin.Yet, the described resin combination of the document is such small-sized of the square flat board of shaping 50mm and during simple molding, no problem, but because of not containing molding agent composition, during the molding of the large-scale and complicated 3D shape of grading at shaping speculum and extension, the problem of the bad forming defects that causes of molding (surface smoothing of molding, molding vestige etc.) appears.

Japan publication spy opens the described resin combination of 2002-179895 communique, by using poly-alkylene naphthalate to improve the thermotolerance of base material, by suppressing to heat the decline (phenomenon of above-mentioned (1)) of the substrate surface smoothness that causes, suppress heating fuzzy (the planar defective of tangerine peel).Yet the described resin combination of the document because of using montanic acid calcium (HostalubCaV102) and tetramethylolmethane four montanates (Hostalub WE40) as molding agent paraffin, and the problem that (whiting), molding vestige are blured in heating occurs.Though use the resin combination liftability of montanic acid calcium good, but because of montanic acid calcium oozes out under hot environment, blur (whiting) and produce heating, in the occasion of using tetramethylolmethane four montanates, though heating fuzzy (whiting) is few, but because of the molding effect is little, the bad molding vestige that causes of molding appears then.

So, so far, do not see to satisfy simultaneously and solve the thermoplastic resin composition who heats fuzzy and liftability problem.

On the other hand, because of the structure of the headlamp of the automobile that uses reflective mirror and prolongation is to insert light supply apparatus, speculum, extension to grade in the container that seals with the shell (cover) of accommodating lens and parts, when light source is lit a lamp, the resin that is shone by high temperature produces volatile component, it is attached on the lens component, and the lens face fuzzy problem that hazes is arranged.Hazing of this lens face fuzzy is called as mist formation, improves this situation, and resin system speculum, prolongation material are the important technology problems.Have by in thermoplastic polyester, adding to contain epoxy, improve the research (opening the 2001-316573 communique) of mist formation with reference to Japanese publication spy.Yet Japanese publication spy opens the problem of fuzzy (heating is fuzzy) that also have above-mentioned luminous reflectance metal level in the described resin combination of 2001-316573 communique.

Again, can understand, even the problems referred to above can solve with material face, but according to the difference of material, the new occasion unserious question that forms the luminous reflectance metal level after handling through undercoat in the past can take place also.If it use and the metal pattern that carries out using when undercoat is handled the light reflector of class of being shaped has the words of metal pattern of the condition of surface (surfaceness) of same degree, kind according to shaped material, exist in the surfaceness (concavo-convex) that the molding surface stays metal pattern, make the bad problem of picture clarity.Because of copying to the concavo-convex few of metal pattern on this molding, so it is being carried out the occasion of undercoat, will make concavo-convex smoothing, thereby this problem is not special problem in the past.Yet, do not carrying out undercoat, on formed article for light reflector, directly form the occasion of luminous reflectance metal level, copy to the concavo-convex reflection characteristic that influences light reflector on the molding, can only obtain the abominable light reflector of picture clarity of outward appearance.

Summary of the invention

The 1st purpose of the present invention is, a kind of light reflector is provided, it is directly to form the luminous reflectance metal level on the molding that is formed by the thermoplastic resin composition, plasticity (surface smoothing, liftability, shaping shrinkage rate) is good, thermotolerance is good, even under hot environment, on the luminous reflectance metal level, also be difficult for producing defective (the planar defective of tangerine peel, whiting); The present invention also provides a kind of light-reflecting article thermoplastic resin composition who is fit to this tamper.

The 2nd purpose of the present invention is, a kind of light reflector is provided, it is directly to form the luminous reflectance metal level on the molding that is formed by the thermoplastic resin composition, plasticity (surface smoothing, liftability, shaping shrinkage rate) is good, thermotolerance is good, even under hot environment, also is difficult for producing defective (the planar defective of tangerine peel, whiting) on the luminous reflectance metal level, and reflection appearance is clear, and the present invention also provides a kind of light-reflecting article thermoplastic resin composition who is fit to this tamper.

The 3rd purpose of the present invention is, a kind of light reflector is provided, it is directly to form the luminous reflectance metal level on the molding that is formed by the thermoplastic resin composition, plasticity (surface smoothing, liftability, shaping shrinkage rate) is good, and the adherence of metal level/resin base material is good, and thermotolerance is good, even under hot environment, on the luminous reflectance metal level, also be difficult for producing defective (the planar defective of tangerine peel, whiting), and mist formation is good, and the present invention also provides a kind of light-reflecting article thermoplastic resin composition who is fit to this tamper.

The 4th purpose of the present invention is, a kind of manufacture method of light reflector is provided, according to described method, using when making light reflector by the thermoplastic resin composition of containing vibrin, can make the manufacture method of the light reflector of outward appearance with good picture clarity (imaging clarity).

The present invention relates to a kind of light-reflecting article thermoplastic resin composition, described light-reflecting article thermoplastic resin composition is contained thermoplastic resin (A), and is the inorganic filling material (B1) of the median size of handling through the fatty acid series surface treatment agent of 2～45 mass parts smaller or equal to 3 μ m with respect to the thermoplastic resin (A) of 100 mass parts; A kind of light-reflecting article thermoplastic resin composition, described light-reflecting article thermoplastic resin composition are contained thermoplastic resin (A), and are that the specific refractory power α of 2～45 mass parts is 1.61≤α≤2.5, the median size inorganic filling material (B2) smaller or equal to 3 μ m with respect to the thermoplastic resin (A) of 100 mass parts; A kind of light-reflecting article thermoplastic resin composition, described light-reflecting article thermoplastic resin composition contains thermoplastic resin (A), be (C1) composition of 0.01～3 mass parts with respect to the thermoplastic resin (A) of 100 mass parts, contain fatty acid triglycercide and/or fatty acid diglyceride, and the fatty mono glyceride (C2) of 0.01～3 mass parts.The invention still further relates to a kind of formed article for light reflector that forms by these light-reflecting article resin combinations.The invention still further relates to a kind of light reflector, it is the light reflector that directly forms the luminous reflectance metal level on the surface of this formed article for light reflector at least a portion.

The invention still further relates to a kind of manufacture method of formed article for light reflector, it is characterized in that, use the thermoplastic resin composition of containing vibrin, be shaped smaller or equal to the metal pattern of 0.075 μ m with arithmetic mean surface roughness Ra; A kind of manufacture method of formed article for light reflector is characterized in that, uses the thermoplastic resin composition of containing vibrin, is shaped with the metal pattern of surface through polishing more than or equal to No. 5000 polishing grain size number; A kind of manufacture method of formed article for light reflector is characterized in that, uses the thermoplastic resin composition of containing vibrin, uses the chrome-plated metal contour forming; Also relate to a kind of light reflector, it is the light reflector that directly forms the luminous reflectance metal level on the surface of this formed article for light reflector at least a portion that obtains by these manufacture method.

Embodiment

Below, light-reflecting article thermoplastic resin composition of the present invention is described.

The thermoplastic resin (A) that the present invention is used, there is not special restriction, have for example, as thermoplastic resins such as the vibrin of polybutylene terephthalate, polyethylene terephthalate etc., polycarbonate resin, poly-propine sulfide resin, polyphenylene sulfide, polyphenylene oxide resin, polyimide resin, polysulfone resin, polyethersulfone resin, polyether ketone resin, polyacetal resins.These thermoplastic resins can use separately, also diverse thermoplastic resin more than 2 kinds can be used together.

In these thermoplastic resin kinds, from mobile, thermotolerance aspect, be main component with vibrin (a), just, it is desirable to the 50 quality %s of the content of vibrin (a) more than or equal to thermoplastic resin (A) total amount.The lower value of the content of better is vibrin (a) it is desirable to 90 quality % especially more than or equal to 85 quality %.There is no particular limitation to the higher limit of the content of vibrin (a).

As vibrin (a), be the polyester that aromatic series or alicyclic dicarboxylic acid or derivatives thereof and polyvalent alcohol (phenol) polycondensation obtain for example.As the example of dicarboxylic acid, terephthalic acid, m-phthalic acid, naphthalic acid, cyclohexane cyclohexanedimethanodibasic etc. are arranged for example.As the example of polyvalent alcohol, it is aklylene glycol, the polyoxyethylene glycol of dihydroxyphenyl propane and/or the addition polymer of polypropylene glycol etc. of 2～6 ethylene glycol, Diethylene Glycol, propylene glycol, butyleneglycol etc. that methene chain is arranged for example.

As the concrete example of vibrin (a), polyethylene terephthalate, polybutylene terephthalate, Polyethylene Naphthalate, poly-naphthalic acid fourth diester etc. are arranged for example.These monomers be can use, the different vibrin of composition and/or molecular weight and the mixture of usefulness also can be used.

Especially, from the viewpoint of plasticity, outward appearance, economy, it is desirable to and with polybutylene terephthalate (a-1) and polyethylene terephthalate (a-2).And with the blending ratio under the above-mentioned two kinds occasion, do not limit especially, it is desirable in vibrin (a) total amount, polybutylene terephthalate (a-1) is 55～95 quality %, polyethylene terephthalate (a-2) is 5～45 quality %.In the blending ratio of polybutylene terephthalate (a-1) occasion more than or equal to 55 mass parts %, then the forming period time is short, productivity is good; In the occasion smaller or equal to 95 mass parts %, the surface smoothing of molding is good.In the blending ratio of polyethylene terephthalate (a-2) occasion more than or equal to 5 mass parts %, the surface smoothing of molding is good; In the occasion smaller or equal to 45 mass parts %, then the forming period time is short, productivity is good.What (a-1) lower value of the blending ratio of composition was better is more than or equal to 60 mass parts %, and what (a-1) higher limit of the blending ratio of composition was better is smaller or equal to 90 mass parts %, it is desirable to especially smaller or equal to 85 quality %.What (a-2) lower value of the blending ratio of composition was better is more than or equal to 10 mass parts %, it is desirable to especially more than or equal to 15 mass parts %.What (a-1) higher limit of the blending ratio of composition was better is smaller or equal to 40 mass parts %.

(a-1) do not limit especially to polybutylene terephthalate, can be the unitary self-aggregate of butylene terephthalate, can be to contain to contain in repeating unit more than or equal to the unitary multipolymer of the polybutylene terephthalate of 70 quality % yet.As the monomer of copolymerization, as except that terephthalic acid with and low-carbon-ester dicarboxylic acid component, aromatic series or the aliphatics polyprotonic acid or their ester of m-phthalic acid, naphthalic acid, hexanodioic acid, sebacic acid, trihemellitic acid, succsinic acid etc. are arranged for example.As removing 1, the diol component outside the 4-butyleneglycol has ethylene glycol, diglycol ethylene, trimethylene glycol, propylene glycol, hexa-methylene glycol, season pentanediol, cyclohexanedimethanol, 1, aklylene glycols such as 3-ethohexadiol for example; Dihydroxyphenyl propane, 4, the alkylene oxide addition polymer alcohol of 3 moles of addition polymer of propylene oxide of 2 moles of addition polymer of the oxyethane of aromatic alcohols such as 4 '-dihydroxybiphenyl, dihydroxyphenyl propane, dihydroxyphenyl propane etc.; The poly hydroxyl compound of glycerine, tetramethylolmethane etc. or its ester formation property derivative.

Molecular weight to polybutylene terephthalate (a-1) does not limit especially, but 25 ℃ the reduced viscosity (η sp/C) that it is desirable to as the molecular weight index is 0.7～2.0.More than or equal to 0.7 occasion, then intensity is good in reduced viscosity; Smaller or equal to 2.0 occasion, then flowability and outward appearance are good in reduced viscosity.The lower value of this reduced viscosity, better is more than or equal to 0.8, it is desirable to more than or equal to 0.9 especially.The higher limit of this reducing viscosity, better is smaller or equal to 1.7, it is desirable to smaller or equal to 1.5 especially.

(a-2) do not limit especially to polyethylene terephthalate, can be the unitary self-aggregate of ethylene glycol terephthalate, can be to contain in repeating unit more than or equal to the unitary multipolymer of the polyethylene terephthalate of 70 quality % yet.As the monomer of copolymerization, as except that terephthalic acid with and low-carbon-ester dicarboxylic acid component, aromatic series or the aliphatics polyprotonic acid or the ester of m-phthalic acid, naphthalic acid, hexanodioic acid, sebacic acid, trihemellitic acid, succsinic acid etc. are arranged for example.As the diol component except that ethylene glycol, diglycol ethylene, trimethylene glycol, butyleneglycol, propylene glycol, hexa-methylene glycol, season pentanediol, cyclohexanedimethanol, 1 are arranged for example, aklylene glycols such as 3-ethohexadiol; Dihydroxyphenyl propane, 4, the alkylene oxide addition polymer alcohol of 3 moles of addition polymer of propylene oxide of 2 moles of addition polymer of the oxyethane of aromatic alcohols such as 4 '-dihydroxybiphenyl, dihydroxyphenyl propane, dihydroxyphenyl propane etc.; The poly hydroxyl compound of glycerine, tetramethylolmethane etc. or its ester formation property derivative.

Molecular weight to polyethylene terephthalate (a-2) does not limit especially, but 25 ℃ the limiting viscosity ([η]) that it is desirable to as the molecular weight index is 0.4～1.0.More than or equal to 0.4 occasion, then intensity is good in limiting viscosity; Smaller or equal to 1.0 occasion, then flowability and outward appearance are good in limiting viscosity.The lower value of this limiting viscosity, better is more than or equal to 0.45, it is desirable to more than or equal to 0.5 especially.The higher limit of this limiting viscosity, better is smaller or equal to 0.9, it is desirable to smaller or equal to 0.8 especially.

In the present invention, from the shrinking percentage of molding and the angle of surface smoothing, thermoplastic resin (A) it is desirable to also contain ethene based thermoplastic resin (x) except above-mentioned vibrin (a).Content to ethene based thermoplastic resin (x) does not limit especially, but it is desirable to account for 2～20 quality % in thermoplastic resin (A) total amount.This content is more than or equal to the occasion of 2 quality %, and then the shrinking percentage of molding is little, surface smoothing is good, and smaller or equal to the occasion of 20 quality %, then the physical strength of molding and thermotolerance are good.

The lower value of ethene based thermoplastic resin (x) content, better is more than or equal to 3 quality %, it is desirable to especially more than or equal to 4 quality %.The higher limit of this content, better is smaller or equal to 15 quality %, it is desirable to especially smaller or equal to below 10 quality.

As ethene based thermoplastic resin (x), do not limit especially, can use and know ethene based thermoplastic resin.Acrylonitrile-styrene copolymerized resin (x-1) arranged for example, contain the acrylonitrile-styrene copolymerized resin of epoxy group(ing) (x-2), maleimide based copolymerized resin noncrystalline resins such as (x-3), this is not limited especially, but it is desirable to select at least a from (x-1)～(x-3).

As acrylonitrile-styrene copolymerized resin (x-1), do not limit especially, it is desirable to vinyl cyanide and cinnamic mass ratio scope in vinyl cyanide/vinylbenzene=20/80～45/55, better is in 25/75～35/65 scope.Manufacture method as acrylonitrile-styrene copolymerized resin (x-1) does not limit especially, and suspension polymerization, letex polymerization, solution polymerization, mass polymerization etc. are arranged for example.Molecular weight to acrylonitrile-styrene copolymerized resin (x-1) does not limit especially, and it is desirable in order to tetrahydrofuran (THF) is that the weight-average molecular weight of the gel permeation chromatography of solvent is the scope of 50000～200000 (being scaled polystyrene).

As containing the acrylonitrile-styrene copolymerized resin of epoxy group(ing) (x-2), do not limit especially, it is desirable to the copolymer resins that the epoxy group(ing) ethylene monomer unit is formed that contains by the aromatic vinyl monomer unit of the acrylonitrile monemer unit of 15～40 quality %, 60～84.9 quality % and 0.1～0.4 quality %.Manufacture method as containing the acrylonitrile-styrene copolymerized resin of epoxy group(ing) (x-2) does not limit especially, and suspension polymerization, letex polymerization, solution polymerization, mass polymerization etc. are arranged for example.

As maleimide based copolymerized resin (x-3), do not limit especially, for example by being the copolymer resins that monomeric unit and/or other vinyl monomer unit are formed by maleimide monomer unit and aromatic vinyl, maleimide is that the content of monomeric unit is 15～65 quality %, it is desirable to the scope of 20～50 quality %.As maleimide is monomer, it is desirable to N-cyclohexyl maleimide, N-Chloro-O-Phenyl maleimide, the adjacent bromo maleimide of N-, N-phenylmaleimide, it is desirable to N-phenylmaleimide especially.These maleimides are that monomer can be a kind of or be used in combination of two or more.As aromatic vinyl is monomer, vinylbenzene, alpha-methyl styrene is arranged for example, to (p-) vinyl toluene, uncle (t-) butylstyrene, it is desirable to vinylbenzene especially.These aromatic vinyls are that monomeric unit can be used in combination more than a kind or 2 kinds.Aromatic vinyl is the content of monomeric unit, it is desirable to 35～85 quality %, and that better is 40～70 quality %.As other vinyl monomer, it is monomer etc. that acrylic monomer, acrylic ester monomer, methacrylate ester monomer, unsaturated dioctyl phthalate are arranged for example, especially it is desirable to vinyl cyanide.

Below, the inorganic filling material that the present invention is used describes.

In the present invention, inorganic filling material play a part to improve physical strength material (strengthening material), give thermotolerance material, low mould shrinkage formed material, nuclei of crystallization material etc.

Inorganic filling material used in the present invention, in above-mentioned effect, as strengthening material, give the occasion that thermotolerance material or low mould shrinkage formed material use, its median size is smaller or equal to 3 μ m.In the occasion of median size smaller or equal to 3 μ m, especially the luminous reflectance metal level directly is being formed in the method for molding, then the appearance of luminous reflectance metal level is good; Median size surpasses the occasion of 3 μ m, and then the surface smoothing of molding is abominable, the appearance that can not obtain expecting.

With inorganic filling material as strengthening material, give the higher limit of the median size of the occasion that thermotolerance material or low mould shrinkage formed material use, it is desirable to smaller or equal to 1 μ m, better is smaller or equal to 0.7 μ m, it is desirable to very much it is desirable to especially smaller or equal to 0.4 μ m smaller or equal to 0.5 μ m.

The occasion that inorganic filling material is used as nuclei of crystallization material is not particularly limited the median size of inorganic filling material.

Lower value for the median size of inorganic filling material used in the present invention is not particularly limited, and it is desirable to more than or equal to 0.05 μ m.Median size is more than or equal to the occasion of 0.05 μ m, and then the dispersiveness of inorganic filling material becomes good.The lower value of this median size, better is more than or equal to 0.07 μ m, it is desirable to especially more than or equal to 0.1 μ m.

Specific refractory power α to inorganic filling material is not particularly limited, with inorganic filler as strengthening material, give the occasion that thermotolerance material or low mould shrinkage formed material use, it is desirable to scope in 1.61≤α≤2.5.Specific refractory power α is in this scope, directly forms the luminous reflectance metal level and obtain the occasion of light reflector on the resin combination that will use this inorganic filling material is shaped the molding that obtains, and then the reflection appearance of light reflector becomes clear, and it is good that outward appearance becomes.The lower value of specific refractory power α it is desirable to more than or equal to 1.62, and better is more than or equal to 1.63, it is desirable to more than or equal to 1.64 especially.The higher limit of specific refractory power α it is desirable to smaller or equal to 2.45, and better is smaller or equal to 2.43, it is desirable to smaller or equal to 2.40 especially.

As employed inorganic filling material among the present invention, do not have special restriction, for example can use zinc sulphide, weisspiessglanz, zinc oxide, white lead, lithopone, zinc subcarbonate, magnesium oxide, barium sulfate, ground barium sulfate, lime carbonate, pure aluminium silicate, quartz, talcum, mica, clay, hydrotalcite, graphite, granulated glass sphere, calcium sulfate, magnesiumcarbonate, sal epsom, Calucium Silicate powder, titanium oxide, silicon oxide, calcium titanate, magnesium titanate, barium titanate, white carbon black, boron-moisten soil, zeolite, rhombspar, silk Muscovitum etc.

Wherein, as the inorganic filling material (B2) of specific refractory power α in above-mentioned scope, for example, zinc sulphide (specific refractory power=2.37～2.43), weisspiessglanz (specific refractory power=2.09～2.29), zinc oxide (specific refractory power=2.01～2.03), white lead (specific refractory power=1.94～2.09), lithopone (specific refractory power=1.84), zinc subcarbonate (specific refractory power=1.70), magnesium oxide (specific refractory power=1.64～1.74), barium sulfate (specific refractory power=1.64～1.65), ground barium sulfate (specific refractory power=1.64～1.65) etc. are arranged for example, because of above-mentioned reason ideal.

In (B-2) composition, (the planar defective of tangerine peel, whiting) aspect is blured in the heating under surface smoothing, physical strength and hot environment, it is desirable to barium sulfate.As barium sulfate, do not limit especially, process white, winnowing with a dustpan property barium sulfate etc. are arranged for example.Wherein, because of using process white, the appearance of molding is good, and desirable especially.As the concrete example of process white, 300R, the SS-50 of bounded chemical industry (strain) system of giving an example, B-30, B-30NC, B-34, B-54, BF-21F etc.

In above-mentioned inorganic filling material,, it is desirable to lime carbonate or pure aluminium silicate from the aspect of surface smoothing, physical strength.As lime carbonate, do not limit especially, water-ground limestone, precipitated chalk, sulfo group calcium aluminate, organic boron-moisten soil etc. are arranged for example.Wherein, because of the appearance that uses the precipitated chalk molding is good, so desirable especially.As the object lesson of precipitated chalk, カ Le シ-ズ P that Vigot-10, Vigot-10S, Vigot-15, the refreshing island chemical industry (strain) that has white lapicide's industry (strain) to make is for example made etc.As pure aluminium silicate, do not limit especially, for example, moisture china clay arranged for example, burn till china clay, clay etc.As the object lesson of moisture china clay, ASP101, ASP102 that ENGELHARD makes, ASP170 etc. are arranged for example, as the object lesson that burns till china clay, サチ Application ト Application 5 that ENGELHARD makes, ウ Le トレ Star Network ス 98 etc. are arranged for example.Wherein, use the appearance of moisture china clay molding to become well, and desirable especially.

Surface treatment for inorganic filling material used in the present invention does not limit especially, with inorganic filling material as strengthening material, give the occasion that thermotolerance material or low mould shrinkage formed material use, it is desirable to carry out surface treatment.At this moment, inorganic filling material is carried out the surface-treated occasion, it is desirable to handle with the fatty acid series surface treatment agent.Here, the lipid acid surface treatment agent is at least a kind of compound that is selected from lipid acid, fatty acid ester, the soap.

As lipid acid, do not limit especially, be exemplified as carbonatoms and be 12～22 lipid acid.Specifically, sylvic acid, lauric acid, tetradecanoic acid, stearic acid, oleic acid, palmitinic acid, docosoic etc. are arranged for example.Wherein, it is desirable to stearic acid, docosoic especially.

As fatty acid ester, do not limit especially, be exemplified as the lipid acid of above-mentioned carbonatoms 12～22 and the ester of glycerine.Specifically, fatty mono glyceride, fatty acid diglyceride, fatty acid triglycercide etc. are arranged for example, wherein, it is desirable to fatty acid diglyceride especially.

As soap, do not limit especially, it is the calcium or the zinc salt of 12～22 lipid acid that above-mentioned carbonatoms is arranged for example.Specifically, calcium stearate, Zinic stearas etc. are arranged for example.Wherein, it is desirable to calcium stearate especially.

These fatty acid series surface treatment agents can be used alone or two or more kinds may be used.

The fatty acid series compound of above-mentioned lipid acid, fatty acid ester, soap etc., except as the fatty acid series surface treatment agent, can also be as the molding agent.Therefore, by using the inorganic filling material of handling through the fatty acid series surface treatment agent, the dispersiveness that not only improves inorganic filling material makes the surface smoothing of molding good, also make the liftability of molding become good, can on molding, not produce the molding vestige, on molding, directly form the occasion of luminous reflectance metal level, can access good luminous reflectance metal level.

Just, from the liftability aspect, it is desirable to use the inorganic filler of handling through the fatty acid series surface treatment agent (B1).

Adhesion amount to the fatty acid series surface treatment agent does not limit especially, it is desirable to the total amount with respect to inorganic filling material amount and fatty acid series surface treatment dosage, in 0.1～3 quality % scope.This adhesion amount can demonstrate fully surface treatment effect more than or equal to the occasion of 0.1 quality %, the favorable dispersity of inorganic filling material in resin, and the smoothness on molding surface is good.Again, this adhesion amount is smaller or equal to the occasion of 3 quality %, and the molding that directly forms the luminous reflectance metal level is not easy to produce fuzzy after the heating.The lower value of this adhesion amount, better is more than or equal to 0.3 quality %, it is desirable to especially more than or equal to 0.5 quality %.This higher limit, better is smaller or equal to 2.7 quality %, it is desirable to especially smaller or equal to 2.5 quality %.

Method for handle inorganic filling material with surface treatment agent does not limit especially, can handle with known method.For example, can carry out surface treatment by inorganic filling material and surface treatment agent are put into Henschel mixer blended method.Also can be in lime carbonate, carrying out the successive carbonation reaction and obtain in the operation of precipitated chalk, in this reaction emulsion, add treatment agent by in the carbonic acid air-flow, spraying reaction emulsion, carry out the surface-treated method.

The content of inorganic filling material used in the present invention, do not limit especially, with inorganic filling material as strengthening material, give the occasion that thermotolerance material or low mould shrinkage formed material use, it is desirable to respect to the scope of 100 mass parts thermoplastic resins (A) in 2～45 mass parts.More than or equal to the occasion more than 2 mass parts, it is big that physical strength becomes at this content, and thermotolerance becomes well, and shaping shrinkage rate diminishes.In the occasion of this content smaller or equal to 45 mass parts, the dispersion state of inorganic filling material is good, and it is good that the surface smoothing of molding becomes.The lower value of the content of inorganic filling material it is desirable to it is desirable to especially more than or equal to 4 mass parts more than or equal to 3 mass parts.The higher limit of the content of inorganic filling material it is desirable to it is desirable to especially smaller or equal to 15 mass parts smaller or equal to 30 mass parts.

The shaping shrinkage rate of this molding is in the occasion of 1.2～1.6% scope, and liftability, low bendability are good and desirable.The lower value of better is shaping shrinkage rate is more than or equal to 1.25%.The higher limit of better is shaping shrinkage rate it is desirable to it is desirable to smaller or equal to 1.45% especially smaller or equal to 1.5% smaller or equal to 1.55% very much.

With the occasion of inorganic filling material, the content of inorganic filling material is not limited especially as nuclei of crystallization material.

Below, fatty acid triglycercide and/or fatty acid diglyceride (C1) are described.

In the present invention, (C1) composition plays a part the molding agent.By when being shaped, outside the molding surface forms, sliding the property film, to form good liftability.Also have, should (C1) composition, the light reflector that will directly form metallic reflector on the molding surface remain on the occasion under the hot environment, make the thicken situation of (heating is fuzzy) of metallic reflector few.

In the ester that lipid acid and glycerine obtain 3 kinds (monoesters, diester, three esters) are arranged, (C1) composition is wherein three esters and diester at least a.Find that respectively three esters, diester have the molding effect, the molding effect of monoester is little.In three esters and diester, from the liftability aspect, three esters are desirable especially.

The lipid acid that constitutes (C1) composition ester is not limited especially.The higher fatty acid that C18 (stearic acid)～C32 (lacceroic acid) etc. for example, is arranged for example.Wherein,, it is desirable to C22 (docosoic from the liftability aspect)～C32 (lacceroic acid), C29 (montanic acid)～C32 (lacceroic acid).

The alcohol that constitutes (C1) composition ester is glycerine.In the present invention,, and have good liftability, and few appearance heating is fuzzy because of ester has glycerol backbone.At alcohol is the occasion of glycol such as ethylene glycol, though have liftability, it is fuzzy to produce heating, and also the occasion of the tetrol of promising tetramethylolmethane etc. though the situation that heating is blured is few, is difficult to find liftability, can not reach purpose of the present invention.

(C1) content of composition with respect to 100 mass parts thermoplastic resins (A), is 0.01～3 mass parts.When (C1) content of composition was more than or equal to 0.01 mass parts, liftability became well, during smaller or equal to 3 mass parts, heated ambiguous situation and became good.The lower value of this content it is desirable to it is desirable to especially more than or equal to 0.05 mass parts more than or equal to 0.03 mass parts.The higher limit of this content it is desirable to it is desirable to especially smaller or equal to 2 mass parts smaller or equal to 2.5 mass parts.

As mentioned above, (C1) the molding agent composition of composition for the heating ambiguity is taken place in not making the fuzzy scope that is worse off of heating, also can contain molding agent except that (C1) composition light-reflecting article thermoplastic resin composition of the present invention.

Below, (C2) describes to fatty mono glyceride.

Fatty mono glyceride (C2) as inner lubrication prescription, has the effect of improving mist formation.Be because (C2) composition improves inner sliding property, so when hybridization or when being shaped, the resin that can suppress the melting mixing state decomposes, and reduces the volatile component (lower molecular weight resolvent) when being shaped overheated (aging).

In the present invention, it is desirable to and with (C1) composition and (C2) composition.If also usefulness (C1) composition and (C2) composition then can improve the metal pattern liftability and improve mist formation.This be because, (C1) composition molding effect is big and inner sliding property effect is little, relatively the sliding property effect in the inside of (C2) composition is big and the molding effect is little.Thereby, and if with (C1) composition and (C2) composition, then one side can keep good molding outward appearance, one side can be improved liftability and mist formation.Importantly keep extension to grade the lamp part with good balance between outward appearance, liftability and the mist formation of material.Especially the occasion of the maximization/complicated molding that grades at shaping headlamp extension, because of the effect of finding (C2) composition (improving the effect of the Resin Flow when being shaped as inner lubrication prescription), and desirable.

Constitute the lipid acid of the ester of (C2) composition, do not limit especially.The higher fatty acid etc. that C12 (lauric acid)～C28 (montanic acid) for example, is arranged for example.Wherein, it is desirable to C16 (palmitinic acid)～C22 (docosoic), it is desirable to C18 (stearic acid)～C20 (eicosanoic acid) especially.Lipid acid is that unsaturated acid is also passable, for example also can use the monoglyceride of C18 (oleic acid).

(C2) content of composition and without particular limitation is preferably, and with respect to 100 mass parts thermoplastic resins (A), is 0.01～3 mass parts.When (C2) content of composition was more than or equal to 0.01 mass parts, sliding property became well, and during smaller or equal to 3 mass parts, it is good that the molding outward appearance becomes.The lower value of this content it is desirable to it is desirable to especially more than or equal to 0.05 mass parts more than or equal to 0.03 mass parts.The higher limit of this content it is desirable to it is desirable to especially smaller or equal to 2 mass parts smaller or equal to 2.5 mass parts.

In light-reflecting article thermoplastic resin composition of the present invention,,, also can mix other and mix known material usually in thermoplastic resin for giving desired characteristic according to the difference of purpose.Softening agent, fire retardant, static inhibitor etc. that the tinting material of dyestuff and pigment etc., the oxidation inhibitor that is used to improve thermostability, UV light absorber, photostabilizer, the pyromellitic acid alkyl ester that is used to improve liquidity or epoxidised soybean oil etc. for example, are arranged for example.

Light-reflecting article thermoplastic resin composition of the present invention because of having above-mentioned described speciality, so molding need not be done metal evaporation, by mixing so-called metallic pigment, then in the occasion of giving molding gloss, designability, also can obtain suitable characteristic.Similarly, because of having an above-mentioned described feature, by painted and give metalluster and have appearance design, occasion then to carrying out application in the part of the enterprising row metal evaporation of molding, or the occasion of not carrying out metal evaporation, direct application on molding, can both obtain suitable characteristic.

Below, light-reflecting article thermoplastic resin composition's of the present invention manufacture method is described.

Light-reflecting article thermoplastic resin composition's of the present invention manufacture method does not limit especially, for example, can make by the melting mixing method.Device as being used for melting mixing does not limit especially, can use known device, for example, can use extrusion machine, Banbury, rolling mill, kneader etc.

Below, light-reflecting article thermoplastic resin composition's of the present invention manufacturing process is described.

Light-reflecting article thermoplastic resin composition's of the present invention manufacturing process, do not limit especially, can use injection moulding method, known method such as the assist formation method of calming the anger, cold cycling moulding method, blow-moulding process, extruding formation method, by these methods, can obtain molding.Wherein, from the popularity aspect, it is desirable to injection moulding method.If polishing grain size number in the polishing of metal pattern location more than or equal to No. 5000 or carry out surface treatment such as chromium plating, then can be increased surface smoothing, the gloss of molding, after evaporation or application, obtain good surface appearance easily.

Below, formed article for light reflector of the present invention is described.

The reflectivity on formed article for light reflector of the present invention surface does not limit especially, and it is desirable keeping in 420～700nm scope more than or equal to 65%.

In 420～700nm scope, reflectivity directly formed the luminous reflectance metal level more than or equal to 65% o'clock on this molding, obtain reflection appearance clearly, and it is good and desirable that reflection appearance becomes.

In addition, in the present invention, reflectivity is that マくベスカラ-アイ CE-3000 spectrophotometer is connected with the COLOR SCOPE of CCM system that firmly changes カラ-Co., Ltd.'s manufacturing, the surface of molding is measured in 400nm～700nm scope with the D light source 10 degree visuals field.

For the lower value of this reflectivity, better is more than or equal to 66%, it is desirable to very much it is desirable to more than or equal to 70% especially more than or equal to 68%.Higher limit for reflectivity does not limit especially.

Formed article for light reflector with such reflectivity, can by to foregoing contain thermoplastic resin (A) and with respect to the thermoplastic resin (A) of 100 mass parts be 2～45 mass parts, to be 1.61≤α≤2.5, median size smaller or equal to the light-reflecting article thermoplastic resin composition of the inorganic filling material (B2) of 3 μ m form specific refractory power obtains.

The linear shrinkage ratio of formed article for light reflector of the present invention does not limit especially, it is desirable to smaller or equal to 1.6%.Smaller or equal to 1.6%, then liftability, low bendability become good and desirable as linear shrinkage ratio.Lower value for linear shrinkage ratio does not limit especially, it is desirable to more than or equal to 0.6%.The lower value of better is linear shrinkage ratio is more than or equal to 0.8%, and what higher limit was better is smaller or equal to 1.55%, it is desirable to very much it is desirable to smaller or equal to 1.45% especially smaller or equal to 1.50%.

In addition, in the present invention, shrinking percentage is after being cooled to room temperature by the molding that will obtain, the size L under the size L of mensuration molding, the room temperature of metal pattern ₀, try to achieve from following formula.

The linear shrinkage ratio of molding (%)={ (L ₀-L)/L ₀} * 100 (%)

The picture clarity of formed article for light reflector of the present invention does not limit especially, it is desirable to more than or equal to 90%.More than or equal to 90% occasion, the clarity that then directly forms the light reflector of luminous reflectance metal level at least a portion surface of this molding becomes good at the picture clarity of formed article for light reflector.

Here, the picture clarity of formed article for light reflector is according to JISH8686, uses スガ trier Co., Ltd. system to write picture property tester ICM-1DP, measures with the wide 0.5mm of optical comb (Network シ).

The picture clarity of formed article for light reflector, better is more than or equal to 93%, better is more than or equal to 95%, it is desirable to especially it would be desirable more than or equal to 97% more than or equal to 96%.

Have the formed article for light reflector of such picture clarity, can use the specific metal pattern of aftermentioned to obtain by shaping.

Below, the manufacture method of light reflex body and function molding describes.

The manufacturing process of formed article for light reflector, do not limit especially, can use injection moulding method, known method such as the assist formation method of calming the anger, cold cycling moulding method, blow-moulding process, extruding formation method, by these methods, can obtain molding.Wherein, from the popularity aspect, it is desirable to injection moulding method.

In the present invention,, use the thermoplastic resin composition's of containing vibrin occasion, it is desirable to make formed article for light reflector smaller or equal to the metal pattern of 0.075 μ m with arithmetic mean surface roughness Ra as the thermoplastic resin composition.Here, arithmetic mean surface roughness Ra defines with JISB0601, and the non-contact three-dimensional determinator NH-3 that uses three hawk light device companies to make with evaluation length 2mm, cut off value 0.8mm, evaluation speed 0.3mm/sec, measures the metal pattern surface and obtains.

Use the thermoplastic resin composition, at formed article for light reflector, especially directly form the occasion of the formed article for light reflector of luminous reflectance metal level, thermoplastic resin composition's kind is particularly important with the combination of the metal pattern of its usefulness that is shaped.

Contain the thermoplastic resin composition's of polyester occasion in shaping, especially the condition of surface of metal pattern (surfaceness) can influence the condition of surface of formed article for light reflector.This is to result from the flow characteristics of vibrin, because the good fluidity of vibrin, so all have resin to flow to small concavo-convex of metal pattern surface, causes molding can directly duplicate the condition of surface of metal pattern.

This tendency ties up in the thermoplastic resin that constitutes the thermoplastic resin composition, when the content of polyester is found for more than or equal to 10 quality % the time; More remarkable during more than or equal to 30 quality % in described amount of polyester; More remarkable during more than or equal to 50 quality %; Remarkable especially during more than or equal to 80 quality %; The most remarkable during more than or equal to 100 quality %.

Therefore, it is desirable to,, select the arithmetic mean surface roughness Ra of suitable metal pattern according to the content of vibrin.For example, in the content of the vibrin occasion more than or equal to 10 quality %, the arithmetic mean surface roughness Ra that it is desirable to metal pattern is smaller or equal to 0.07 μ m; In the occasion of amount of polyester, it is desirable to Ra smaller or equal to 0.065 μ m more than or equal to 30 quality %; In the occasion of amount of polyester, it is desirable to Ra smaller or equal to 0.06 μ m more than or equal to 50 quality %; In the occasion of amount of polyester, it is desirable to Ra smaller or equal to 0.055 μ m more than or equal to 80 quality %; In amount of polyester is the occasion of 100 quality %, it is desirable to Ra smaller or equal to 0.05 μ m.

As the method that the metal pattern surface is decided to be the scope of such arithmetic mean surface roughness Ra, do not limit especially, by with diamond file, grinding stone, vitrified pulpstone, ruby grinding stone, GC grinding stone etc., the metal pattern surface is polished, can be adjusted into desired arithmetic surface roughness Ra with ultrasonic polishing shredder or manual manipulation.For example, it is desirable to more than or equal to No. 4000 the metal pattern surface be polished, so that the arithmetic surface roughness Ra of metal pattern is smaller or equal to 0.07 μ m with the polishing grain size number; The metal pattern surface is polished more than or equal to No. 5000 with the polishing grain size number, so that the arithmetic surface roughness Ra of metal pattern is smaller or equal to 0.06 μ m; The metal pattern surface is polished more than or equal to No. 6000 with the polishing grain size number, so that the arithmetic surface roughness Ra of metal pattern is smaller or equal to 0.05 μ m; The metal pattern surface is polished more than or equal to No. 8000 with the polishing grain size number, so that the arithmetic surface roughness Ra of metal pattern is smaller or equal to 0.04 μ m; The metal pattern surface is polished more than or equal to No. 14000 with the polishing grain size number, so that the arithmetic surface roughness Ra of metal pattern is smaller or equal to 0.03 μ m.

In the present invention, the occasion use the thermoplastic resin composition of containing vibrin as the thermoplastic resin composition also can replace the metal pattern that carries out above-mentioned polishing with chromed metal pattern.Can also carry out chromium plating again to metal pattern through above-mentioned polishing.Certainly, directly use the metal pattern that carries out above-mentioned polishing also out of question.

Like this, by making formed article for light reflector with such method, as mentioned above, can make becoming as clarity of formed article for light reflector well is more than or equal to 90%.

Below, light reflector of the present invention is described.

Light reflector of the present invention is directly to form the luminous reflectance metal level on the surface of at least a portion of above-mentioned formed article for light reflector.

The diffusion of light reflector (diffusion) reflectivity does not limit especially, it is desirable to diffuse reflectance behind initial stage or the heat-resistant experiment smaller or equal to 3%.Under this occasion, has excellent function as light reflector.In addition, in the present invention, the diffuse reflectance of light reflector is measured with the reflection transmittance instrument HR-100 of color technical institute in (strain) village.

Again, the picture clarity of light reflector does not limit especially, it is desirable to more than or equal to 90%, and better is more than or equal to 93%, it is desirable to especially it would be desirable more than or equal to 97% more than or equal to 95%.

Method as directly form the luminous reflectance metal level on molding does not limit especially, can form with known method such as evaporations.For example, the method shown in following is arranged for example.

(1) at first, molding is placed in the evaporation coating device under the vacuum state,, the plasma body sensitization is carried out on the molding surface handled by importing the rare gas element and the oxygen of argon etc.(2) then, in evaporation coating device, carry the electrifying electrodes of holding target compound by making, by the plasma body at indoor induction discharge, the splash particle (aluminum particulate etc.) that makes splash is attached on the molding.(3) then, as the protective membrane of metal evaporation films such as aluminium, to siliceous gas carry out that plasma polymerization is handled or with silicon oxide by on the surface of ion plating method attached to the aluminium-vapour deposition film.

Embodiment

Below, with embodiment, the present invention will be described in more detail for comparative example, but the invention is not restricted to this.

The evaluation method of the surfaceness of metal pattern

The non-contact three-dimensional determinator NH-3 that uses three hawk light devices to make under the condition of evaluation length 2mm, cut off value 0.8mm, evaluation speed 0.3mm/sec, measures the metal pattern surface, according to the JISB0601 standard, tries to achieve arithmetic mean surface roughness Ra.

The evaluation method of resin

(1) reduced viscosity (η sp/C)

The mixed solvent of the phenol of the 1:1 (mass ratio) of interpolation 50ml and tetrachloroethane in 0.25g polybutylene terephthalate resin (Northeast chemistry (strain) manufacturing, trade(brand)name " PTM11 "), dissolving obtained solution in 10～30 minutes under 140 ℃.Its temperature adjustment in 25 ℃ of Water Tanks with Temp.-controlled by the time between graticule, was tried to achieve reduced viscosity (η sp/C) with ウベロ-デ type viscometer determining after 3 minutes.

ηsp/C＝(ηrel-1)/C＝(T/T ₀-1)/C

T: the passing through the time (second) of the kapillary graticule of sample solution

T ₀: only the kapillary graticule during mixed solvent passes through the time (second)

C: sample solution concentration (g/dl)

(2) limiting viscosity ([η])

Use the phenol of 1:1 (mass ratio) and the mixed solvent of tetrachloroethane, compound concentration is 0.2,0.3, the pet resin solution of 0.4g/dl, with the viscosity of ウベロ-デ type automatic viscometer (SAN DENSHI (strain) manufacturing, AVL-2C) at 25 ℃ of following each concentration solution of mensuration of temperature, the value that obtains is schemed to be inserted to concentration 0g/dl outward with the Huggins, try to achieve limiting viscosity ([η]).

(3) acid value

Make polybutylene terephthalate be dissolved in phenylcarbinol,, measure with the NaOH benzyl alcohol solution titration of 1/50N.The evaluation method of molding

(1) liftability: evaluation method 1

Visual outward appearance to molding is estimated, and estimates whether the molding vestige takes place.

Zero: liftability is good, can not confirm the molding defectiveness.

*: because molding is bad, the molding vestige has taken place in molding.

(2) liftability: evaluation method 2

Behind the melting mixing particle drying with each composition, with injection molding machine (SANJECT360160T that the accurate society in mountain city makes), under the condition in 260 ℃ of cylinder temperature, 80 ℃ of metal pattern temperature, 20 seconds cooling times, 35 seconds cycles, with the round shape molding of long 50mm, internal diameter 45mm, thick 3mm～4mm, the outstanding power (molding power) by the pressure center during to molding is measured.Molding power is little, and the liftability of metal pattern is good.

In addition, this molding power smaller or equal to 500N then as the part forming of various lamps the time, have good liftability.When molding power surpasses 500N, the molding difficulty, productivity reduces, and has problems when the molding of molding large or the molding of complicated shape.

(3) shaping shrinkage rate

After the shaping, wait the molding cool to room temperature after, measure the size L of molding, by the size L0 under the room temperature of metal pattern, try to achieve shaping shrinkage rate (linear shrinkage ratio) from following formula.

The linear shrinkage ratio of molding (%)={ (L ₀-L)/L ₀} * 100 (%)

(4) mist formation

Cut out the small pieces of about 20mm * 10mm from molding,, place it in temperature regulation and be 160 ℃ mist formation trier (the mist formation experiment WSF-2 modified form that the gas test machine is made) the 6g test tube (φ 30 * 200) of packing into.(behind テ Application パ Star Network ス glass 55 * 55 * 3mmt) lid, carry, under 160 ℃, carry out thermal treatment in 20 hours covering thermal glass on the above-mentioned test tube again to adjust the temperature to 25 ℃, to pass to the aluminium block (ア Le ミ Block ロ Star Network) of water coolant.After carrying out this thermal treatment, separate out dirt settling from the resolvent of resin combination distillation etc. at the sheet glass inwall.Measure the mist (permeability of light) on these sheet glass with reflection transmittance instrument (HR-100 that color technical institute makes in (strain) village).

In addition, the sheet glass after the heating in 160 ℃ * 20 hours hazes and surpasses 45% occasion, as the various parts that wait problem is arranged in practicality.Sheet glass hazes smaller or equal to 45% occasion, can reach the function as the part of various lamps, and is good and desirable, it is desirable to smaller or equal to 20% especially.

(5) reflectivity on molding surface

マくベスカラ-アイ CE-3000 spectrophotometer is connected with the COLOR SCOPE of CCM system that firmly changes カラ-Co., Ltd.'s manufacturing, the surface of molding is measured in 400nm～700nm scope with the D light source 10 degree visuals field and tried to achieve reflectivity.

(6) as clarity (imaging definition)

According to JISH8686, use スガ trier Co., Ltd. system to write picture property tester ICM-1DP, measure the picture boldness of molding with the wide 0.5mm of optical comb.

The evaluation method of light reflector

(1) visual ocular estimate

For the outward appearance of the luminous reflectance metal level of light reflector, before and after heat-resistant experiment, visual valuation outward appearance (planar defective, whiting, the reflection appearance of defective, tangerine peel that causes by the molding vestige).

1) molding vestige

◎: the white apperance of the fluffing shape concavo-convex (corrugated) that causes by the white apperance of duplicating (mould is concavo-convex to be duplicated) of the bad mould concave-convex surface that causes of the liftability of resin and by the contraction of resin completely without.

Zero: mould is concavo-convex to duplicate the white apperance that the white apperance that causes or corrugated cause, only is can recognize a little from visual angle, level out of question in practicality.

△: mould is concavo-convex to duplicate the white apperance that the white apperance that causes or corrugated cause has from the teeth outwards.

*: mould is concavo-convex, and to duplicate the white apperance that the white apperance that causes or corrugated cause very obvious.

2) the planar defective of tangerine peel

◎: surface irregularity (rough, a lot of pimple sense) completely without.

Zero: surface irregularity (rough, a lot of pimple sense) only is can recognize a little from visual angle, level out of question in practicality.

△: surface irregularity (rough, a lot of pimple sense) has.

*: surface irregularity (rough, a lot of pimple sense) is very obvious.

3) whiting (before the heat-resistant experiment)

◎: additive oozes out the whiting of the inhomogenous shape that causes (mottled etc.) to the molding surface during shaping, completely without.

Zero: only be can recognize that from visual angle additive when being shaped oozes out the whiting of the inhomogenous shape that causes (mottled etc.) to the molding surface, level out of question in practicality.

△: the whiting that additive oozes out the inhomogenous shape that causes (mottled etc.) to the molding surface during shaping can be confirmed.

*: the whiting that additive oozes out the inhomogenous shape that causes (mottled etc.) to the molding surface during shaping is very obvious.

4) whiting (behind the heat-resistant experiment)

◎: additive oozes out the whiting of the inhomogenous shape that causes (mottled etc.) to the molding surface during shaping, or the whiting that additive oozes out the inhomogenous shape that causes (mottled etc.) to the molding surface during oven test completely without.

Zero: only be to recognize that from visual angle additive when being shaped oozes out the whiting of the inhomogenous shape that causes (mottled etc.) to the molding surface, or additive oozes out the whiting of the inhomogenous shape that causes (mottled etc.) to the molding surface during oven test, level out of question in practicality.

△: additive oozes out the whiting of the inhomogenous shape that causes (mottled etc.) to the molding surface during shaping, or the whiting that additive oozes out the inhomogenous shape that causes (mottled etc.) to the molding surface during oven test can be confirmed.

*: additive oozes out the whiting of the inhomogenous shape that causes (mottled etc.) to the molding surface during shaping, or additive oozes out the whiting of the inhomogenous shape that causes (mottled etc.) to the molding surface during oven test, and is very obvious.

5) reflection appearance

Zero: reflection appearance is clear.

*: reflection appearance is unintelligible.

(2) diffuse reflectance

Measure the diffuse reflectance of the light reflector of heat-resistant experiment front and back with the reflection transmittance instrument HR-100 of color technical institute in (strain) village.

(3) metallic membrane bonding strength

Peel off experiment (stripping test of the basal disc order) initial stage of light reflex body and the metal bonding layer intensity behind the heat-resistant experiment is estimated by fritter.Fritter is peeled off the glass paper tape that experiment is to use ニチバ Application the to make ((Article Number: CT-24), carry out 1mm fritter number at interval and be 100 fritter and peel off experiment of セロ Ha Application テ-プ).Estimate with remaining in the percentage (%) of the fritter number on molding surface whole fritter numbers.In the early stage 100% and after oven test more than or equal to 80% o'clock, reach as the effect of light reflector and good.

In addition, it is after formed article for light reflector carries out aluminium-vapour deposition that the fritter at the initial stage of light reflector is peeled off experiment, carries out after room temperature is placed more than 24 hours.It is behind heat-resistant experiment that fritter behind the heat-resistant experiment is peeled off experiment, and light reflector is carried out after room temperature is placed more than 24 hours.

(4) as clarity

According to the JISH8686 standard, use スガ trier Co., Ltd. system to reflect look tester ICM-1DP, measure the imaging boldness of molding with the wide 0.5mm of optical comb.

(5) heat-resistant experiment

Lucky inferior thermostat container (the ギヤオ-Block Application) GPH (H)-100 that uses バイエスベ Star Network (strain) to make places light reflector 24 hours in 160 ℃ hot blast, heat-treats.

[Production Example of ethene based thermoplastic resin]

Production Example 1 (acrylonitrile-styrene copolymerized resin (x-1))

With the distilled water of 115 mass parts, phosphoric acid (three) calcium of 1 mass parts, デモ-Le water system dispersion agent P (flower king (strain) makes) retort of packing into and the stirring of 0.001 mass parts.The vinyl cyanide, the vinylbenzene of 75 mass parts, the t-dodecyl mercaptans of 0.5 mass parts, the Diisopropyl azodicarboxylate of 0.17 mass parts, the 0.003 mass parts ガ Off ア Star Network GB-520 (eastern nation chemical industry (strain) manufacturing) that add 25 alkene mass parts again, become after the suspension, be warming up to 75 ℃, keep finishing polymerization in 240 minutes, obtain acrylonitrile-styrene copolymerized resin (x-1).Resulting (x-1) resin consist of vinyl cyanide/vinylbenzene=34/66 (mass ratio).

Production Example 2 (containing the acrylonitrile-styrene copolymerized resin of epoxy group(ing) (x-2))

With 115 mass parts distilled water, 1 mass parts phosphoric acid (three) calcium, 0.001 mass parts デモ-Le water system dispersion agent P (flower king (strain) makes) retort of packing into and stirring.Add 23 mass parts vinyl cyanide, 76.7 mass parts vinylbenzene, 0.3 mass parts glycidyl methacrylate, 0.5 mass parts t-dodecyl mercaptans, 0.17 mass parts Diisopropyl azodicarboxylate, 0.003 mass parts ガ Off ア Star Network GB-520 (eastern nation chemical industry (strain) manufacturing) again, become after the suspension, be warming up to 75 ℃, keep finishing polymerization in 240 minutes, obtain containing the acrylonitrile-styrene copolymerized resin of epoxy group(ing) (x-2).Resulting (x-2) resin consist of vinyl cyanide/styrene/methacrylic acid glycidyl ester=24.9/74.7/0.4 (mass ratio).

Production Example 3 (maleimide based copolymerized resin (x-3))

Toward polymerization reactor with 20 liters of whipping apptss that carried out the nitrogen replacement operator, supply with continuously vinyl cyanide, 20 mass parts of vinylbenzene, 20 mass parts of N-phenylmaleimide, 40 mass parts of 20 mass parts ethyl methyl ketone, 0.01 mass parts 1, the t-dodecyl mercaptans of 1-azo (hexanaphthene-1-formic acid), 0.05 mass parts.One side remains 110 ℃ with the temperature in the polymerization reactor, and one side extracts polymerization liquid continuously by the toothed gear pump that the bottom had of polymerization reactor, so that average retention time is 2 hours.Then, make this polymerization liquid be detained about 20 minutes with the heat exchanger that remains on 150 ℃ after, import two extrusion machines of 30mm φ that the cylinder temperature is controlled to be 230 ℃ 2 outlet duct types.First exhaust portion is decided to be normal atmosphere, and second exhaust portion is decided to be under the decompression of 2.7Kpa, removes volatile component, with its granulating, obtains maleimide based copolymerized resin (x-3) with nodulizer.(x-3) resin that obtains consist of N-phenylmaleimide/styrene/acrylonitrile=27/56/17 (mass ratio).

Embodiment 1

(Mitsubishi's レイヨ Application (strain) is made as the polybutylene terephthalate (a-1) of 76.2 mass parts of thermoplastic resin (A) in fusion, commodity are called " Off ペ Star ト N1100 ", reduced viscosity η sp/C=1.14, the polyethylene terephthalate (a-2) of acid value=62meq/kg), 19 mass parts (make by Mitsubishi's レイヨ Application (strain), commodity are called " ダイヤ Na イト MA580D ", limiting viscosity [η]=0.570), and the acrylonitrile-styrene copolymerized resin (x-1) that obtains of the above-mentioned Production Example of 4.8 mass parts; As 4.8 mass parts of inorganic filler with surface-treated (the adhesion amount 2.2 quality %) precipitated chalk (B1-1) of stearic acid (refreshing island chemical industry (strain) is made, trade(brand)name " カ Le シ-ズ ", median size 0.15 μ m); As the montanic acid of 0.19 mass parts carbonatoms 24～34 of molding agent and three ester paraffin of glycerine (Network ラリア Application トジヤパ Application (strain) is made, trade(brand)name " Licolub WE4 "); And (change firmly that カラ-(strain) make as the carbon black of 0.25 mass parts of pigment, trade(brand)name " Block ラ Star Network BPM-8E756 "), mixed 5 minutes with the V-type mixing tank, make it mix homogenization, under 260 ℃ of temperature cylinders, drop into two extrusion machines of the band outlet duct of diameter 30mm, obtain particle.

With the particle injection molding machine (IS80FPB that (strain) Toshiba makes) that obtains, under the condition of 260 ℃ of temperature cylinders, 80 ℃ of metal pattern temperature, go up injection molding forming at the flat board that 100mm is square with metal pattern (polish with #14000 number polishing granularity on the metal pattern surface), the linear shrinkage ratio that obtains molding (100mm * 100mm, thick 3mm) molding is 1.40%.

Below, on the molding that obtains according to the direct AM aluminum metallization of following method.

At first, import rare gas element and oxygen in the evaporation coating device under the vacuum state, indoor is plasmoid, and the plasma body sensitization of molding surface activation is handled.Then, AM aluminum metallization in the evaporation coating device under the vacuum state.By in evaporation coating device, making the electrifying electrodes of carrying target compound, produce plasma body indoor by induction discharge, ion in the plasma body makes the target compound splash, make the splash particle that flies out from target compound, be aluminum particulate attached on the molding surface, form the aluminium-vapour deposition film comprehensively.The thickness of aluminium-vapour deposition film is 80nm.Then, as the protective membrane of metal evaporation faces such as aluminium, carry out plasma polymerization and handle.Plasma polymerization film is under the vacuum plasma state, imports cyclohexanedimethanol, forms the silica polymerization film.The thickness of silica polymerization film is 50nm.

Like this, obtain on the thermoplastic polyester resin molding, directly forming the light reflector of luminous reflectance metal level.The diffuse reflectance of measuring resulting light reflector is 1.2%, and is good.

Then, carry out the heat-resistant experiment of resulting light reflector, the diffuse reflectance behind the determination test is 1.9%, and is good.

Embodiment 2～10

Except that thermoplastic resin composition's the composition that consists of table 1, the method that other is used similarly to Example 1 obtains particle, molding, light reflector.Evaluation result is as shown in table 1.

Comparative example 1～6

Except that thermoplastic resin composition's the composition that consists of table 2, the method that other is used similarly to Example 1 obtains particle, molding, light reflector.Evaluation result is as shown in table 2.

Table 2

In addition, in embodiment and comparative example that table 1 and table 2 are put down in writing, use be the material of following record.

(B1-1) precipitated chalk: with the precipitated chalk (refreshing island chemical industry (strain) is made, trade(brand)name " カ Le シ-ズ P ") that stearic acid is crossed surface treatment (2.2 quality %), median size=0.15 μ m (infiltration type electron microscope method);

(B1-2) china clay: with the moisture china clay (ENGELHARD society makes, trade(brand)name " ASP101 ") that stearic acid is crossed surface treatment (0.5 quality %), median size (median)=0.4 μ m (measured value of laser diffractometry);

(b1-3) talcum: surperficial untreated talcum (woods changes into the manufacturing of (strain) society, trade(brand)name " #5000S "), median size (median)=5.3 μ m (measured value of laser diffractometry);

(b1-4) water-ground limestone: surperficial untreated water-ground limestone (Japan's 7 アイ Application ケミカ Le (strain) are made, trade(brand)name " ホワイト Application P-70 "), median size=2.31 μ m (BET specific surface area scaled value);

(b1-5) precipitated chalk: surperficial untreated precipitated chalk (white lapicide's industry (strain) is made, trade(brand)name " Brilliant-1500 "), median size=0.2 μ m (BET specific surface area scaled value);

(b1-6) talcum: (woods changes into the manufacturing of (strain) society to the talcum of crossing through γ-glycidoxypropyltrime,hoxysilane (epoxy silane) surface treatment (0.5 quality %), trade(brand)name " CHC-13S-05E "), median size (median)=5.3 μ m (measured value of laser diffractometry);

The montanate paraffin Network ラリカ Application トジヤパ Application (strain) of carbonatoms 24～34 is made, trade(brand)name " LicolubWE4 ";

Fatty mono glyceride: reason grinds that PVC ミ Application (strain) makes, trade(brand)name " リケマ-Le S100A ";

The montanic acid sodium salt Network ラリカ Application トジヤパ Application (strain) of carbonatoms 24～34 is made, trade(brand)name " LicomontNaV101 ".

Embodiment 14

(Mitsubishi's レイヨ Application (strain) is made as the polybutylene terephthalate (a-1) of 76.2 mass parts of thermoplastic resin (A) in fusion, commodity are called " Off ペ Star ト N1100 ", reduced viscosity η sp/C=1.14, the polyethylene terephthalate (a-2) of acid value=62meq/kg), 19 mass parts (make by Mitsubishi's レイヨ Application (strain), commodity are called " ダイヤ Na イト MA580D ", limiting viscosity [η]=0.570), and the acrylonitrile-styrene copolymerized resin (x-1) that obtains of the above-mentioned Production Example of 4.8 mass parts; Process white (B2-1) (boundary's chemical industry (strain) is made, trade(brand)name " B-30NC ", median size 0.3 μ m, specific refractory power 1.64) as 4.8 mass parts of inorganic filler; As the montanic acid of the carbonatoms 24～34 of 0.19 mass parts of molding agent and the three ester paraffin (C1-1) (Network ラリア Application トジヤパ Application (strain) is made, trade(brand)name " Licolub WE4 ") of glycerine; And (change firmly that カラ-(strain) make as the carbon black of 0.25 mass parts of pigment, trade(brand)name " Block ラ Star Network BPM-8E756 "), made it mix homogenization in 5 minutes with the V-type mixing tank, under 260 ℃ of temperature cylinders, drop into two extrusion machines of the band outlet duct of diameter 30mm, obtain particle.

With the particle injection molding machine (IS80FPB that (strain) Toshiba makes) that obtains, under the condition of 260 ℃ of temperature cylinders, 80 ℃ of metal pattern temperature, go up injection molding forming at the flat board that 100mm is square with metal pattern (polished with #14000 polishing grain size number on the metal pattern surface), the linear shrinkage ratio that obtains molding (100mm * 100mm, thick 3mm) molding is 1.4%.

At first, import rare gas element and oxygen in the evaporation coating device under the vacuum state, indoor is plasmoid, and the plasma body sensitization of molding surface activation is handled.Then, AM aluminum metallization in the evaporation coating device under the vacuum state.By in evaporation coating device, making the electrifying electrodes of carrying object, produce plasma body indoor by induction discharge, ion in the plasma body makes the object splash, make the splash particle that flies out from target compound, be aluminum particulate attached on the molding surface, form the aluminium-vapour deposition film comprehensively.The thickness of aluminium-vapour deposition film is 80nm.Then, as the protective membrane of metal evaporation faces such as aluminium, carry out plasma polymerization and handle.Plasma polymerization film is under the vacuum plasma state, imports cyclohexanedimethanol, forms the silica polymerization film.The thickness of silica polymerization film is 50nm.

Then, carry out the heat-resistant experiment of resulting light reflector, the diffuse reflectance behind the determination test is 1.9% and good.

Embodiment 2～10

Except that thermoplastic resin composition's the composition that consists of table 3, the method that other is used similarly to Example 14 obtains particle, molding, light reflector.Evaluation result is as shown in table 3.

Comparative example 1～6

Except that thermoplastic resin composition's the composition that consists of table 4, the method that other is used similarly to Example 14 obtains particle, molding, light reflector.Evaluation result is as shown in table 4.

Table 4

In addition, in embodiment and comparative example that table 3 and table 4 are put down in writing, use be the material of following record.

(B2-1) process white: boundary's chemical industry (strain) is made, trade(brand)name " B-30NC "), median size=0.3 μ m (infiltration type electron microscope method) specific refractory power 1.64;

(B2-2) process white: boundary's chemical industry (strain) is made, trade(brand)name " SS-50 "), median size=0.1 μ m (infiltration type electron microscope method) specific refractory power 1.64;

(b2-3) talcum: surperficial untreated talcum (woods changes into the manufacturing of (strain) society, trade(brand)name " #5000S "), median size (median)=5.3 μ m (measured value of laser diffractometry) specific refractory power 1.56;

Embodiment 27

(Mitsubishi's レイヨ Application (strain) is made as the polybutylene terephthalate (a-1) of 80 mass parts of thermoplastic resin (A) in fusion, commodity are called " Off ペ Star ト N1100 ", reduced viscosity η sp/C=1.14, the polyethylene terephthalate (a-2) of acid value=62meq/kg), 20 mass parts (make by Mitsubishi's レイヨ Application (strain), commodity are called " ダイヤ Na イト MA580D ", limiting viscosity [η]=0.570), and the acrylonitrile-styrene copolymerized resin (x-1) that obtains of the above-mentioned Production Example of 4.8 mass parts; (C1-1) montanic acid monoglyceride (Network ラリア Application トジヤパ Application (strain) is made, trade(brand)name " Licolub WE4 ") as 0.2 mass parts of (C1) composition; (C2-1) stearic acid triglyceride level (reason is ground PVC ミ Application (strain) manufacturing, trade(brand)name " リケマ-Le S100A ") as 0.3 mass parts of (C2) composition; (woods changes into (strain) society and makes as the talcum of 1 mass parts of crossing through γ-glycidoxypropyltrime,hoxysilane surface treatment (0.5 quality %) of nuclei of crystallization material, trade(brand)name " #SG200 "), and (change firmly that カラ-(strain) make as the carbon black of 0.24 mass parts of pigment, trade(brand)name " Block ラ Star Network BPM-8E756 "), made it mix homogenization in 5 minutes with the mixing of V-type mixing tank, under 260 ℃ of temperature cylinders, drop into two extrusion machines of the band outlet duct of diameter 30mm, obtain particle.

The particle that use obtains confirms that by the method for evaluation method 2 liftability is good.

Also have, with the particle injection molding machine (IS80FPB that (strain) Toshiba makes) that obtains, under the condition of 260 ℃ of temperature cylinders, 80 ℃ of metal pattern temperature, (polished with #14000 number polishing granularity by the metal pattern surface with metal pattern for the flat board square at 100mm, arithmetic mean surface roughness Ra=0.03 μ m) goes up injection molding forming, obtain molding (100mm * 100mm, thick 3mm).The plate forming product that obtain be 98.2% as clarity.

Then, the square plate forming product of the 100mm that obtains are estimated mist formation after, the value of mist is 27%.

Like this, obtain on the thermoplastic polyester resin molding, directly forming the light reflector of luminous reflectance metal level.The evaluation result of the light reflector that obtains is shown in table 5 and the table 7.

Then, carry out the heat-resistant experiment of resulting light reflector, the evaluation result of light reflector after the experiment is shown in the table 5.

Embodiment 28～31

Except that thermoplastic resin composition's the composition that consists of table 5, the method that other is used similarly to Example 27 obtains particle, molding, light reflector.Evaluation result is as shown in table 5.

Comparative example 10～20

Except that thermoplastic resin composition's the composition that consists of table 6, the method that other is used similarly to Example 27 obtains particle, molding, light reflector.Evaluation result is as shown in table 6.

Table 5

In addition, in embodiment and comparative example that table 5 and table 6 are put down in writing, use be the material of following record.

(C1-1) montanic acid triglyceride level: Network ラリカ Application トジヤパ Application (strain) is made, trade(brand)name " Licolub WE4 ";

(C2-1) stearic acid monoglyceride: reason grinds that PVC ミ Application (strain) makes, trade(brand)name " リケマ-Le S100A ";

(c-3) montanic acid sodium: Network ラリカ Application トジヤパ Application (strain) is made, trade(brand)name " Licomont NaV "

(c-4) montanic acid calcium: Network ラリカ Application トジヤパ Application (strain) is made, trade(brand)name " Licomont CaV102 ";

(c-5) montanic acid tetramethylolmethane four esters: Network ラリカ Application トジヤパ Application (strain) is made, trade(brand)name " LicolubWE40 ";

(c-6) montanic acid ethylene glycol diester: Network ラリカ Application トジヤパ Application (strain) is made, trade(brand)name " LicowaxE ";

(c-7) the montanic acid ester (mixture of montanic acid butanediol ester and montanic acid calcium) that partly alkalizes: Network ラリカ Application トジヤパ Application (strain) is made, trade(brand)name " Licowax OP ";

Talcum (median size 4.4 μ m): woods changes into (strain) and makes, trade(brand)name " #SG2000 ") carry out the talcum that γ-surface treatment (0.5 quality %) is crossed;

Talcum (median size 0.9 μ m): woods changes into (strain) and makes, to trade(brand)name " #SG2000 ") carry out the talcum that γ-glycidoxypropyltrime,hoxysilane (epoxy silane) surface treatment (0.5 quality %) is crossed;

China clay (0.4 μ m): carry out the moisture china clay that surface treatment (0.5 quality %) is crossed with stearic acid, ENGELHARD makes, trade(brand)name " ASP-101 ".

Embodiment 32

The particle that embodiment 27 is obtained is with injection molding machine (IS80FPB that (strain) Toshiba makes), under the condition of 260 ℃ of temperature cylinders, 80 ℃ of metal pattern temperature, (polished with #8000 polishing granularity by the metal pattern surface with metal pattern for the flat board square at 100mm, arithmetic mean surface roughness Ra=0.04 μ m) goes up injection molding forming, obtain the molding (100mm * 100mm) of light-reflecting article.On the square plate forming product of the 100mm that obtains,, obtain light reflector with similarly to Example 27 the direct AM aluminum metallization of method.The light reflector that obtains is shown in table 7 as clarity.

Embodiment 33

Remove as the dull and stereotyped metal pattern of use, outside the metal pattern (arithmetic average roughness Ra=0.06 μ m) that polished with #5000 on usefulness metal pattern surface, other uses the method same with embodiment 32, obtains light reflector.The light reflector that obtains be shown in table 7 as clarity.

Comparative example 21

Remove as the dull and stereotyped metal pattern of use, outside the metal pattern (arithmetic average roughness Ra=0.08 μ m) that polished with #3000 on usefulness metal pattern surface, other uses the method same with embodiment 32, obtains light reflector.The light reflector that obtains be shown in table 7 as clarity.

Comparative example 22

Remove as the dull and stereotyped metal pattern of use, outside the metal pattern (arithmetic average roughness Ra=0.13 μ m) that polished with #800 on usefulness metal pattern surface, other uses the method same with embodiment 32, obtains light reflector.The light reflector that obtains be shown in table 7 as clarity.

Table 7

The possibility of utilizing on the industry

The surface smoothness of light reflector of the present invention is good. And light emitter of the present invention is characterised in that, even 160 Heat under ℃ condition, the light reflective metal layer that forms by direct vapour deposition method occur the heating ambiguity (tangerine peel is planar, Whiting) few; Light reflector of the present invention has feature good aspect mist formation; Outside the reflection of light reflector of the present invention It is clear to see, good appearance; The picture clarity of light emitter of the present invention is good; Light emitter of the present invention rises with formed products Mould is good; Again, formed article for light reflector of the present invention has the little feature of shaping shrinkage rate.

Thereby light reflector of the present invention is as cover, speculum, prolongation or the household electrical appliances illuminator lamp case etc. of automobile etc. Light reflector can use suitably. And because this light-reflecting article thermoplastic resin composition's of the present invention shaping adds The good fluidity in man-hour, the setting of speed is few, has the free degree of design of light reflector and the metal pattern freedom when making The advantage that degree increases.

Claims

1. light-reflecting article thermoplastic resin composition, it is characterized in that, described light-reflecting article thermoplastic resin composition is contained thermoplastic resin, and is that the specific refractory power α of 2～45 mass parts is 1.61≤α≤2.5, the median size barium sulfate smaller or equal to 3 μ m with respect to the thermoplastic resin of 100 mass parts, this thermoplastic resin contains the above vibrin of 50 quality % that accounts for the thermoplastic resin total amount, and this vibrin is polyethylene terephthalate and/or polybutylene terephthalate.

2. light-reflecting article thermoplastic resin composition as claimed in claim 1 is characterized in that, the median size of described barium sulfate is smaller or equal to 1 μ m.

3. light-reflecting article thermoplastic resin composition as claimed in claim 1 is characterized in that, thermoplastic resin contains the ethene based thermoplastic resin of 2～20 quality %.

4. light-reflecting article thermoplastic resin composition as claimed in claim 3, it is characterized in that ethene based thermoplastic resin is to be selected from acrylonitrile-styrene copolymerized resin, to contain at least a in acrylonitrile-styrene copolymerized resin of epoxy group(ing) or the maleimide based copolymerized resin.

5. a formed article for light reflector is characterized in that, described formed article for light reflector is by forming as claim 1 or 4 described light-reflecting article thermoplastic resin compositions.

6. formed article for light reflector as claimed in claim 5 is characterized in that, in the scope of 420～700nm, the reflectivity on molding surface keeps more than or equal to 65%, and linear shrinkage ratio is more than or equal to 0.6%, smaller or equal to 1.6%.

7. formed article for light reflector as claimed in claim 6 is characterized in that, in the scope of 420～700nm, the reflectivity on molding surface keeps more than or equal to 70%.

8. a light reflector is characterized in that, it is the light reflector that directly forms the luminous reflectance metal level on the surface of at least a portion of the described formed article for light reflector of claim 6.