CN101428478B - Light reflector and method for producing molded article for light reflector - Google Patents

Light reflector and method for producing molded article for light reflector Download PDF

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CN101428478B
CN101428478B CN 200810214826 CN200810214826A CN101428478B CN 101428478 B CN101428478 B CN 101428478B CN 200810214826 CN200810214826 CN 200810214826 CN 200810214826 A CN200810214826 A CN 200810214826A CN 101428478 B CN101428478 B CN 101428478B
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light reflector
thermoplastic resin
light
formed products
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CN101428478A (en
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白井安则
植田治夫
高木珠衣
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Mitsubishi Kasei Corp
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Mitsubishi Rayon Co Ltd
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Priority claimed from JP2003434916A external-priority patent/JP5284557B2/en
Priority claimed from JP2004235995A external-priority patent/JP4766585B2/en
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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 mum, 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 mum whose refractive index alpha is 1.61 <= alpha <= 2.5, per 100 parts by mass of a thermoplastic resin (A); and a thermoplastic resin composition for light reflectors 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 reflector 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 reflector and formed article for light reflector
The application is dividing an application of following application:
The applying date of original application (international filing date): on August 25th, 2004
The national applications of original application number: 200480024095.5 (international application no: PCT/JP2004/012605)
The denomination of invention of original application: the manufacture method of light-reflecting article thermoplastic resin composition, formed article for light reflector, light reflector and formed article for light reflector
Technical field
The present invention relates to the thermoplastic resin composition of the light reflectors such as a kind of cover that is used in lamps for vehicle, speculum, prolongation, ligthing paraphernalia, and the light reflector that directly forms the light reflective metal layer on this thermoplastic resin composition's formed products.And, the present invention relates to a kind of like this technology, in order to make this light reflector that directly forms have good outward appearance, to for the manufacture of injection molding forming carry out the polishing grain size number more than or equal to surface treatments such as the polishing of No. 5000 or chromium plating with the surface of metal pattern, the surface smoothness of formed products, lustrous surface, surperficial clarity increase, after evaporation and application, easily obtain good outward appearance.
The application requires to quote its content here take in No. 2003-301606, the Japanese patent application of application on August 26th, 2003 and No. 2003-301613, Japanese patent application, in No. 2003-434916, the Japanese patent application of application on December 26th, 2003 and in No. 2004-235995, the Japanese patent application of application on August 13rd, 2004 as priority.
Background technology
In the past, as the light-reflecting article material that is used in speculum on lamps for vehicle etc. and extension and grades, used the bulk molding composite (following abbreviation BMC) of thermosetting resin.Although BMC heat resistance, 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 the crystalline resins as representative such as the mylar of polybutylene terephthalate (PBT), PETG etc., and the noncrystalline resin take Merlon as representative etc. mixes the thermoplastic resin composition of various strengthening materials.
For example, someone proposes to use a kind of use PETG as thermoplastic resin, mixes therein the inorganic filling materials such as glass fibre and talcum as the method (with reference to Japanese Laid-Open Patent Unexamined Patent 6-203613 communique) of the composition of strengthening material.
Yet, in the method, because the flatness on the emersion of inorganic filling material and the molding bad formed products surface that causes is inadequate, so before forming the light reflective metal layer on the formation product, need to carry out priming coat and process, make the formed products surface smoothing.Process if do not carry out priming coat, neither minute surface even form the light reflective metal layer, can not obtain satisfied light reflector.Such priming coat is processed, because operation especially increases the processing problem of the solvent that uses with the priming coat material, even needs dry paint, so there is the energy that needs especially, returns the problem that environment increases burden.
Method as carrying out such priming coat processing proposes a kind of direct vapour deposition method in recent years.This direct vapour deposition method is by direct evaporation metal on formed products, or after carrying out on formed products that plasma is active and processing, then deposited metal film, takes this to not be used in the formed products surface and carries out priming coat and process, and directly forms the method for light reflective metal layer.In this direct vapour deposition method because on formed products surface direct formation metal level, so can obtain than flatness on good formed products surface all in the past.
Recently, in order to increase brightness, tend to use the lamp of high output, the temperature in headlamp rises, as the heat resisting temperature of 160～180 ℃ of the base material requires of emitter.Yet in the light reflector of being made by direct vapour deposition method, when using for a long time under the environment of such high temperature, the problem that the light reflective metal layer is fuzzy (heating fuzzy) is remarkable especially.This heating blooming has several types, the substrate resin that phenomenon (tangerine peel planar defect) that substrate resin that (1) caused by the thermal deformation (surface smoothness reduction) of substrate resin and metal level peel off, (2) cause by the heating decomposition gas of substrate resin for example, is arranged and metal level is peeled off or metaboly (whiting), (3) by the composition of additive in substrate resin etc. ooze out the substrate resin that causes and metal level is peeled off or metaboly (whiting) etc.
in order to address this problem, various trials have been carried out, for example being proposed to mix 3 mass parts average grain diameters in the thermoplastic resin that is comprised of polyalkylene terephthalates resin and polycarbonate resin of 100 mass parts by the people is that the surperficial untreated talcum of 0.3 μ m is as the resin combination (with reference to Japanese Laid-Open Patent Unexamined Patent 11-241006 communique) of strengthening material, and with respect to 100 mass parts mylar, mixing the average grain diameter that 12～25 mass parts processed through epoxy silane is the resin combination (with reference to Japanese Laid-Open Patent JP 2003-12903 communique) of the talcum of 2.6～3.8 μ m.For solving this heating fuzzy problem, also carry out other various trials, for example someone proposes to mix the resin combination (with reference to Japanese Laid-Open Patent JP 2000-35509 communique) of inorganic filler, antioxidant, internal lubricant in polybutylene terephthalate (PBT), and the resin combination (with reference to Japanese Laid-Open Patent JP 2002-179895 communique) that mixes inorganic strengthening material and paraffin in the resin that is comprised of polybutylene terephthalate (PBT) and poly-alkylene naphthalate.
Yet, the described resin combination of Japanese Laid-Open Patent Unexamined Patent 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 the particle that because use is very tiny is 0.3 μ m makes easily cohesion between inorganic filling material, has the inadequate problem of formed products surface smoothness.
Again, the described resin combination of Japanese Laid-Open Patent JP 2003-12903 communique because use average grain diameter at the larger inorganic filling material of 2.6～3.8 μ m scopes as strengthening material, so there is the inadequate problem of the surface smoothness of formed products.Again because using the epoxy silane inorganic agent as the surface conditioning agent of inorganic filling material, unreacted epoxy silane inorganic agent oozes out the formed products surface when being shaped, and with the metal pattern surface reaction, has the bad problem of liftability.Its result directly forms the occasion of light reflective metal layer in the formed products surface generation bad defective that causes of molding (molding vestige) on this formed products, exist and leave the molding vestige on reflection layer, produces the problem of defective.
Again, Japanese Laid-Open Patent Unexamined Patent 11-241006 communique and the described resin combination of JP 2003-12903 communique, because using talcum as strengthening material, directly form the light reflective metal layer on the formed products that uses this resin combination, obtain the occasion of light reflector, have the unsharp problem of reflection appearance of light reflector.
Again, the described resin combination of Japanese Laid-Open Patent JP 2000-35509 communique, by the terminal carboxyl group amount is decided to be below specified quantitative, by the generation (phenomenons of above-mentioned (2)) of inhibition as the thermal decomposition gas of the mylar of substrate resin, suppress to heat fuzzy (whiting).Yet, the described resin combination of the document is such small-sized of the square flat board of shaping 50mm and during simple formed products, no problem, but because not containing molding agent composition, during the formed products 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 smoothness of formed products, molding vestige etc.) appears.
The described resin combination of Japanese Laid-Open Patent JP 2002-179895 communique, by using poly-alkylene naphthalate to improve the heat resistance of base material, heat the decline (phenomenon of above-mentioned (1)) of the substrate surface flatness that causes by inhibition, suppress to heat fuzzy (tangerine peel planar defect).Yet, the described resin combination of the document, because using montanic acid calcium (HostalubCaV102) and pentaerythrite four montanates (Hostalub WE40) as molding agent paraffin, and the problem of fuzzy (whiting), molding vestige appears heating.Although use the resin combination liftability of montanic acid calcium good, but ooze out under hot environment because of montanic acid calcium, heat fuzzy (whiting) and produce, in the occasion of using pentaerythrite four montanates, although heat fuzzy (whiting) less, but because the molding effect is little, the bad molding vestige that causes of molding appears.
So, so far there are no can satisfy the thermoplastic resin composition that fuzzy and liftability problem are heated in solution simultaneously.
On the other hand, because 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 ingredient, it is attached on lens component, and the lens face fuzzy problem that hazes is arranged.The fuzzy mist formation that is called as that hazes of this lens face improves this situation, and resin speculum, prolongation material are the important technology problems.Have by adding in thermoplastic polyester to contain epoxy, improve the research (with reference to Japanese Laid-Open Patent JP 2001-316573 communique) of mist formation.Yet, also have the problem of fuzzy (the heating fuzzy) of above-mentioned light reflective metal layer in the described resin combination of Japanese Laid-Open Patent JP 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 light reflective metal layer after processing through priming coat in the past can occur also.If it uses the words of metal pattern that have the surface state (surface roughness) of same degree with the metal pattern that carries out using when priming coat is processed the light reflector of class of being shaped, kind according to moulding material, existence stays the surface roughness (concavo-convex) of metal pattern on the formed products surface, make the bad problem of picture clarity.Because copying to the concavo-convex few of metal pattern on this formed products, so it is being carried out the occasion of priming coat, will make concavo-convex smoothing, thereby this problem is not special problem in the past.Yet, do not carrying out priming coat, directly form the occasion of light reflective metal layer on formed article for light reflector, copy to the concavo-convex reflection characteristic that affects light reflector on formed products, 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 light reflective metal layer on the formed products that is formed by the thermoplastic resin composition, formability (surface smoothness, liftability, shaping shrinkage rate) is good, heat resistance is good, even under hot environment, also be difficult for producing defective (tangerine peel planar defect, whiting) on the light reflective metal layer; The present invention also provides a kind of light-reflecting article thermoplastic resin composition who is fit to this reflector.
The 2nd purpose of the present invention is, a kind of light reflector is provided, it is directly to form the light reflective metal layer on the formed products that is formed by the thermoplastic resin composition, formability (surface smoothness, liftability, shaping shrinkage rate) is good, heat resistance is good, even under hot environment, also be difficult for producing defective (tangerine peel planar defect, whiting) on the light reflective metal layer, 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 reflector.
The 3rd purpose of the present invention is, a kind of light reflector is provided, it is directly to form the light reflective metal layer on the formed products that is formed by the thermoplastic resin composition, formability (surface smoothness, liftability, shaping shrinkage rate) is good, and the adherence of metal level/resin base material is good, and heat resistance is good, even under hot environment, also be difficult for producing defective (tangerine peel planar defect, whiting) on the light reflective metal layer, 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 reflector.
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 mylar, can make the manufacture method of the light reflector of the outward appearance with good picture clarity (imaging clearly).
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 that the average grain diameter of processing through the fatty acid series surface conditioning agent of 2～45 mass parts is less than or equal to the inorganic filling material (B1) of 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 1.61≤α≤2.5, average grain diameter are less than or equal to the inorganic filling material (B2) of 3 μ m with respect to the refractive index α that the thermoplastic resin (A) of 100 mass parts is 2～45 mass parts; A kind of light-reflecting article thermoplastic resin composition, described light-reflecting article thermoplastic resin composition contains thermoplastic resin (A), is (C1) composition of 0.01～3 mass parts with respect to the thermoplastic resin (A) of 100 mass parts, contains 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 is formed by these light-reflecting article resin combinations.The invention still further relates to a kind of light reflector, it is directly to form the light reflector of light reflective metal layer 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 mylar, be shaped less than 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 mylar, is shaped with the metal pattern of surface through carry out polishing more than or equal to the polishing grain size number of No. 5000; A kind of manufacture method of formed article for light reflector is characterized in that, uses the thermoplastic resin composition of containing mylar, uses the chrome-plated metal contour forming; Also relate to a kind of light reflector, it is directly to form the light reflector of light reflective metal layer on the surface of this formed article for light reflector at least a portion that obtains by these manufacture methods.
The specific embodiment
Below, light-reflecting article thermoplastic resin composition of the present invention is described.
The thermoplastic resin (A) that the present invention is used, be not particularly limited, have for example, as thermoplastic resins such as the mylar of polybutylene terephthalate (PBT), PETG 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 mobility, heat resistance aspect, take mylar (a) as main component, namely, it is desirable to the content of mylar (a) more than or equal to 50 quality % of thermoplastic resin (A) total amount.More preferably the lower limit of the content of mylar (a) is more than or equal to 85 quality %, particularly desirably 90 quality %.There is no particular limitation to the higher limit of the content of mylar (a).
As mylar (a), be the polyester that aromatic series or alicyclic dicarboxylic acids or derivatives thereof and polyalcohol (phenol) polycondensation obtain for example.As the example of dicarboxylic acids, terephthalic acid (TPA), M-phthalic acid, naphthalenedicarboxylic acid, cyclohexane cyclohexanedimethanodibasic etc. are arranged for example.As the example of polyalcohol, it is aklylene glycol, the polyethylene glycol of bisphenol-A and/or the addition polymers of polypropylene glycol etc. of 2～6 ethylene glycol, diethylene glycol, propane diols, butanediol etc. that methene chain is arranged for example.
As the concrete example of mylar (a), PETG, polybutylene terephthalate (PBT), PEN, poly-naphthalenedicarboxylic acid fourth diester etc. are arranged for example.These monomers be can use, the different mylar of composition and/or molecular weight and the mixture of use also can be used.
Especially, from the viewpoint of formability, outward appearance, economy, it is desirable to and use polybutylene terephthalate (PBT) (a-1) and PETG (a-2).And with the mixed proportion under the occasion of above-mentioned two kinds, be not particularly limited, it is desirable in mylar (a) total amount, polybutylene terephthalate (PBT) (a-1) is 55～95 quality %, and PETG (a-2) is 5～45 quality %.In the mixed proportion of polybutylene terephthalate (PBT) (a-1) occasion more than or equal to 55 mass parts %, the forming period time is short, productivity is good; In the occasion less than or equal to 95 mass parts %, the surface smoothness of formed products is good.In the mixed proportion of PETG (a-2) occasion more than or equal to 5 mass parts %, the surface smoothness of formed products is good; In the occasion less than or equal to 45 mass parts %, the forming period time is short, productivity is good.(a-1) lower limit of the mixed proportion of composition is more preferably more than or equal to 60 mass parts %, and (a-1) higher limit of the mixed proportion of composition is more preferably less than or equal to 90 mass parts %, particularly desirably less than or equal to 85 quality %.(a-2) lower limit of the mixed proportion of composition is more preferably more than or equal to 10 mass parts %, particularly desirably more than or equal to 15 mass parts %.(a-1) higher limit of the mixed proportion of composition is more preferably less than or equal to 40 mass parts %.
(a-1) is not particularly limited to polybutylene terephthalate (PBT), can be the self-aggregate of butylene terephthalate unit, can be also to contain the copolymer that contains in repetitive more than or equal to the polybutylene terephthalate (PBT) unit of 70 quality %.As the monomer of copolymerization, as except terephthalic acid (TPA) with and low-carbon-ester dicarboxylic acid component, aromatic series or aliphatic polyacid or their ester of M-phthalic acid, naphthalenedicarboxylic acid, adipic acid, decanedioic acid, trihemellitic acid, butanedioic acid etc. are arranged for example.As the diol component except BDO, ethylene glycol, diglycol ethylene, trimethylene glycol, propane diols, hexa-methylene glycol, season pentanediol, cyclohexanedimethanol, 1 are arranged for example, the aklylene glycols such as 3-ethohexadiol; Bisphenol-A, 4, the alkylene oxide addition polymers alcohol of 3 moles of addition polymers of expoxy propane of 2 moles of addition polymers of the oxirane of the aromatic alcohols such as 4 '-dihydroxybiphenyl, bisphenol-A, bisphenol-A etc.; The poly hydroxyl compound of glycerine, pentaerythrite etc. or its ester formative derivative.
Molecular weight to polybutylene terephthalate (PBT) (a-1) is not particularly limited, but the reduced viscosity of 25 ℃ (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, intensity is good in reduced viscosity; Less than or equal to 2.0 occasion, mobility and outward appearance are good in reduced viscosity.The lower limit of this reduced viscosity is more preferably more than or equal to 0.8, particularly desirably more than or equal to 0.9.The higher limit of this reduced viscosity is more preferably less than or equal to 1.7, particularly desirably less than or equal to 1.5.
(a-2) is not particularly limited to PETG, can be the self-aggregate of PETP unit, can be the copolymer that contains in repetitive more than or equal to the PETG unit of 70 quality % yet.As the monomer of copolymerization, as except terephthalic acid (TPA) with and low-carbon-ester dicarboxylic acid component, aromatic series or aliphatic polyacid or the ester of M-phthalic acid, naphthalenedicarboxylic acid, adipic acid, decanedioic acid, trihemellitic acid, butanedioic acid etc. are arranged for example.As the diol component except ethylene glycol, diglycol ethylene, trimethylene glycol, butanediol, propane diols, hexa-methylene glycol, season pentanediol, cyclohexanedimethanol, 1 are arranged for example, the aklylene glycols such as 3-ethohexadiol; Bisphenol-A, 4, the alkylene oxide addition polymers alcohol of 3 moles of addition polymers of expoxy propane of 2 moles of addition polymers of the oxirane of the aromatic alcohols such as 4 '-dihydroxybiphenyl, bisphenol-A, bisphenol-A etc.; The poly hydroxyl compound of glycerine, pentaerythrite etc. or its ester formative derivative.
Molecular weight to PETG (a-2) is not particularly limited, but the inherent viscosity of 25 ℃ ([η]) that it is desirable to as the molecular weight index is 0.4～1.0.More than or equal to 0.4 occasion, intensity is good in inherent viscosity; Less than or equal to 1.0 occasion, mobility and outward appearance are good in inherent viscosity.The lower limit of this inherent viscosity is more preferably more than or equal to 0.45, particularly desirably more than or equal to 0.5.The higher limit of this inherent viscosity is more preferably less than or equal to 0.9, particularly desirably less than or equal to 0.8.
In the present invention, from the shrinkage factor of formed products and the angle of surface smoothness, thermoplastic resin (A) it is desirable to also contain ethene based thermoplastic resin (x) except above-mentioned mylar (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 the shrinkage factor of formed products is little, surface smoothness is good, and less than or equal to the occasion of 20 quality %, the mechanical strength of formed products and heat resistance are good.
The lower limit of ethene based thermoplastic resin (x) content is more preferably more than or equal to 3 quality %, particularly desirably more than or equal to 4 quality %.The higher limit of this content is more preferably less than or equal to 15 quality %, particularly desirably less than or equal to below 10 quality.
As ethene based thermoplastic resin (x), be not particularly limited, 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 radicals (x-2), the noncrystalline resin such as maleimide based copolymerized resin (x-3), this is not particularly limited, but it is desirable to select at least a from (x-1)～(x-3).
As acrylonitrile-styrene copolymerized resin (x-1), be not particularly limited, it is desirable to acrylonitrile and cinnamic mass ratio in the scope of acrylonitrile/styrene=20/80～45/55, more preferably in 25/75～35/65 scope.Manufacture method as acrylonitrile-styrene copolymerized resin (x-1) is not particularly limited, and suspension polymerisation, emulsion polymerisation, polymerisation in solution, polymerisation in bulk etc. are arranged for example.Molecular weight to acrylonitrile-styrene copolymerized resin (x-1) is not particularly limited, and the weight average molecular weight that to it is desirable in order to oxolane be the gel permeation chromatography of solvent is the scope of 50000～200000 (being scaled polystyrene).
As containing the acrylonitrile-styrene copolymerized resin of epoxy radicals (x-2), be not particularly limited, it is desirable to the copolymer resins that the epoxy radicals ethylene monomer unit forms 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 radicals (x-2) is not particularly limited, and suspension polymerisation, emulsion polymerisation, polymerisation in solution, polymerisation in bulk etc. are arranged for example.
As maleimide based copolymerized resin (x-3), be not particularly limited, for example by by maleimide monomer unit and aromatic vinyl being the copolymer resins that monomeric unit and/or other vinyl monomer unit form, maleimide is that the content of monomeric unit is 15～65 quality %, it is desirable to the scope of 20～50 quality %.Be monomer as maleimide, it is desirable to N-N-cyclohexylmaleimide, N-Chloro-O-Phenyl maleimide, the adjacent bromo maleimide of N-, N-phenylmaleimide, particularly desirably N-phenylmaleimide.These maleimides are that monomer can be a kind of or be used in combination of two or more.Be monomer as aromatic vinyl, styrene, AMS arranged for example, to (p-) methyl styrene, uncle (t-) butylstyrene, particularly desirably styrene.These aromatic vinyls are that monomeric unit can one kind or two or morely be used in combination.Aromatic vinyl is the content of monomeric unit, it is desirable to 35～85 quality %, more preferably 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 acrylonitrile.
Below, the inorganic filling material that the present invention is used describes.
In the present invention, inorganic filling material play a part to improve mechanical strength material (strengthening material), give the heat resistance material, the low shaping shunk formed material, nuclei of crystallization material etc.
Inorganic filling material used in the present invention, in above-mentioned effect, as strengthening material, give the heat resistance material or low the shaping shunk the occasion that formed material uses, its average grain diameter is less than or equal to 3 μ m.In the occasion of average grain diameter less than or equal to 3 μ m, especially in the light reflective metal layer directly was formed at the method for formed products, the appearance of light reflective metal layer was good; Average grain diameter surpasses the occasion of 3 μ m, and the surface smoothness of formed products is abominable, the appearance that can not obtain expecting.
With inorganic filling material as strengthening material, give the higher limit of heat resistance material or the low average grain diameter of shrinking the occasion that formed material uses of being shaped, it is desirable to less than or equal to 1 μ m, more preferably less than or equal to 0.7 μ m, ideal is less than or equal to 0.5 μ m, particularly desirably less than or equal to 0.4 μ m.
With the occasion of inorganic filling material as nuclei of crystallization materials'use, the average grain diameter of inorganic filling material is not particularly limited.
Lower limit for the average grain diameter 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.Average grain diameter is more than or equal to the occasion of 0.05 μ m, and the dispersiveness of inorganic filling material becomes good.The lower limit of this average grain diameter is more preferably more than or equal to 0.07 μ m, particularly desirably more than or equal to 0.1 μ m.
Refractive index α to inorganic filling material is not particularly limited, with inorganic filler as strengthening material, give the heat resistance material or low the shaping shunk the occasion that formed material uses, it is desirable to the scope in 1.61≤α≤2.5.Refractive index α is in this scope, directly forms the light reflective metal layer and obtain the occasion of light reflector on the resin combination that will use this inorganic filling material is shaped the formed products that obtains, and the reflection appearance of light reflector becomes clear, and it is good that outward appearance becomes.The lower limit of refractive index α it is desirable to more than or equal to 1.62, more preferably more than or equal to 1.63, particularly desirably more than or equal to 1.64.The higher limit of refractive index α it is desirable to less than or equal to 2.45, more preferably less than or equal to 2.43, particularly desirably less than or equal to 2.40.
As the inorganic filling material that uses in the present invention, be not particularly limited, such as using zinc sulphide, antimony oxide, zinc oxide, white lead, lithopone, basic zinc carbonate, magnesia, barium sulfate, blanc fixe, calcium carbonate, alumina silicate, quartz, talcum, mica, clay, hydrotalcite, graphite, bead, calcium sulfate, magnesium carbonate, magnesium sulfate, calcium silicates, titanium oxide, silica, calcium titanate, magnesium titanate, barium titanate, White Carbon black, boron-moisten soil, zeolite, dolomite, sericite mica etc.
wherein, as the inorganic filling material (B2) of refractive index α in above-mentioned scope, for example, zinc sulphide (refractive index=2.37～2.43) is arranged for example, antimony oxide (refractive index=2.09～2.29), zinc oxide (refractive index=2.01～2.03), white lead (refractive index=1.94～2.09), lithopone (refractive index=1.84), basic zinc carbonate (refractive index=1.70), magnesia (refractive index=1.64～1.74), barium sulfate (refractive index=1.64～1.65), blanc fixe (refractive index=1.64～1.65) etc., because of above-mentioned reason ideal.
In (B-2) composition, the heating under surface smoothness, mechanical strength and hot environment fuzzy (tangerine peel planar defect, whiting) aspect it is desirable to barium sulfate.As barium sulfate, be not particularly limited, blanc fixe, winnowing with a dustpan property barium sulfate etc. are arranged for example.Wherein, because using blanc fixe, the appearance of formed products is good, and desirable especially.As the concrete example of blanc fixe, 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, from the aspect of surface smoothness, mechanical strength, it is desirable to calcium carbonate or alumina silicate.As calcium carbonate, be not particularly limited, powdered whiting, winnofil, sulfo group calcium aluminate, organic boron-moisten soil etc. are arranged for example.Wherein, because the appearance that uses the winnofil formed products is good, so desirable especially.As the object lesson of winnofil, the カ Le シ that Vigot-10, Vigot-10S, Vigot-15, refreshing island chemical industry (strain) that white lapicide's industry (strain) is made makes-ズ P etc. is arranged for example.As alumina silicate, be not particularly limited, 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 formed products to become well, and desirable especially.
Surface treatment for inorganic filling material used in the present invention is not particularly limited, with inorganic filling material as strengthening material, give the heat resistance material or low the shaping shunk the occasion that formed material uses, 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 process with the fatty acid series surface conditioning agent.Here, the aliphatic acid surface conditioning agent is at least a kind of compound that is selected from aliphatic acid, fatty acid ester, soap.
As aliphatic acid, be not particularly limited, be exemplified as carbon number and be 12～22 aliphatic acid.Specifically, rosin acid, laurate, myristic acid, stearic acid, oleic acid, palmitic acid, behenic acid etc. are arranged for example.Wherein, particularly desirably stearic acid, behenic acid.
As fatty acid ester, be not particularly limited, be exemplified as the aliphatic acid of above-mentioned carbon number 12～22 and the ester of glycerine.Specifically, fatty mono glyceride, fatty acid diglyceride, fatty acid triglycercide etc. are arranged for example, wherein, particularly desirably fatty acid diglyceride.
As soap, be not particularly limited, it is calcium or the zinc salt of 12～22 aliphatic acid that above-mentioned carbon number is arranged for example.Specifically, calcium stearate, zinc stearate etc. are arranged for example.Wherein, particularly desirably calcium stearate.
These fatty acid series surface conditioning agents can be used alone or two or more kinds may be used.
The fatty acid series compound of above-mentioned aliphatic acid, fatty acid ester, soap etc., except as the fatty acid series surface conditioning agent, can also be as the molding agent.Therefore, by using the inorganic filling material of processing through the fatty acid series surface conditioning agent, the dispersiveness that not only improves inorganic filling material makes the surface smoothness of formed products good, also make the liftability of formed products become good, can not produce the molding vestige on formed products, directly form the occasion of light reflective metal layer on formed products, can access good light reflective metal layer.
Namely, from the liftability aspect, it is desirable to use the inorganic filler (B1) of processing through the fatty acid series surface conditioning agent.
Adhesion amount to the fatty acid series surface conditioning agent is not particularly limited, and 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 dispersibility of inorganic filling material in resin, and the flatness on formed products surface is good.Again, this adhesion amount is less than or equal to the occasion of 3 quality %, and the formed products that directly forms the light reflective metal layer is not easy to produce fuzzy after heating.The lower limit of this adhesion amount is more preferably more than or equal to 0.3 quality %, particularly desirably more than or equal to 0.5 quality %.This higher limit is more preferably less than or equal to 2.7 quality %, particularly desirably less than or equal to 2.5 quality %.
For process the method for inorganic filling material with surface conditioning agent, be not particularly limited, can process with known method.For example, can by inorganic filling material and surface conditioning agent are put into the method that Henschel mixer mixes, carry out surface treatment.Also can be in calcium carbonate, being undertaken adding inorganic agent during continuous carbonation reaction is precipitated the operation of calcium carbonate in this reaction emulsion by spray reaction emulsion in the carbonic acid air-flow, carry out the surface-treated method.
The content of inorganic filling material used in the present invention, be not particularly limited, with inorganic filling material as strengthening material, give the heat resistance material or low the shaping shunk the occasion that formed material uses, 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 large that mechanical strength becomes at this content, and heat resistance becomes well, and shaping shrinkage rate diminishes.In the occasion of this content less than or equal to 45 mass parts, the dispersity of inorganic filling material is good, and it is good that the surface smoothness of formed products becomes.The lower limit of the content of inorganic filling material it is desirable to more than or equal to 3 mass parts, particularly desirably more than or equal to 4 mass parts.The higher limit of the content of inorganic filling material it is desirable to less than or equal to 30 mass parts, particularly desirably less than or equal to 15 mass parts.
The shaping shrinkage rate of this formed products is in the occasion of 1.2～1.6% scope, and liftability, low bendability are good and desirable.More preferably the lower limit of shaping shrinkage rate is more than or equal to 1.25%.More preferably the higher limit of shaping shrinkage rate is less than or equal to 1.55%, and ideal is less than or equal to 1.5%, particularly desirably less than or equal to 1.45%.
With the occasion of inorganic filling material as nuclei of crystallization material, the content of inorganic filling material is not particularly limited.
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 formed products surface forms the slip film, to form good liftability.Also have, should (C1) composition, the light reflector that will directly form on the formed products surface metallic reflector remain on the occasion under hot environment, make the thicken situation of (heating fuzzy) of metallic reflector few.
In the ester that aliphatic 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 aliphatic acid that consists of (C1) composition ester is not particularly limited.The higher fatty acids that C18 (stearic acid)～C32 (lacceroic acid) etc. for example, is arranged for example.Wherein, from the liftability aspect, it is desirable to C22 (behenic acid)～C32 (lacceroic acid), C29 (montanic acid)～C32 (lacceroic acid).
The alcohol that consists of (C1) composition ester is glycerine.In the present invention, because ester has glycerol backbone, and have good liftability, and few appearance heating is fuzzy.Be the occasion of the glycol such as ethylene glycol at alcohol, though have liftability, produce heating fuzzy, also the occasion of the tetrol of promising pentaerythrite etc., although it is few to heat fuzzy situation, be 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 less than or equal to 3 mass parts, heated ambiguous situation and became good.The lower limit of this content it is desirable to more than or equal to 0.03 mass parts, particularly desirably more than or equal to 0.05 mass parts.The higher limit of this content it is desirable to less than or equal to 2.5 mass parts, particularly desirably less than or equal to 2 mass parts.
As mentioned above, (C1) the molding agent composition of composition for the heating ambiguity is occured, in not making the fuzzy scope that is worse off of heating, also can contain molding agent except (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.Because (C2) composition improves inner slip, so when hybridization or when being shaped, the resin that can suppress the melting mixing state decomposes, and reduces the volatile ingredient (low-molecular-weight analyte) when being shaped overheated (aging).
In the present invention, it is desirable to and use (C1) composition and (C2) composition.If also use (C1) composition and (C2) composition can improve the metal pattern liftability and improve mist formation.This be because, (C1) the large and inner slip effect of composition molding effect is little, relatively the inside slip effect of (C2) composition is large and the molding effect is little.Thereby, and if with (C1) composition and (C2) composition, one side can keep good formed products 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.The occasion of the maximization that especially grades at shaping headlamp extension/complicated formed products, because of the effect (effect of the Resin Flow when improving shaping as inner lubrication prescription) of finding (C2) composition, and desirable.
Consist of the aliphatic acid of the ester of (C2) composition, be not particularly limited.The higher fatty acids etc. that C12 (laurate)～C28 (montanic acid) for example, is arranged for example.Wherein, it is desirable to C16 (palmitic acid)～C22 (behenic acid), particularly desirably C18 (stearic acid)～C20 (arachidic acid).Aliphatic acid is that unsaturated acids is also passable, for example also can use the monoglyceride of C18 (oleic acid).
(C2) content of composition is not particularly limited, be preferably, and with respect to 100 mass parts thermoplastic resins (A), be 0.01～3 mass parts.When (C2) content of composition was more than or equal to 0.01 mass parts, slip became well, and during less than or equal to 3 mass parts, it is good that the formed products outward appearance becomes.The lower limit of this content it is desirable to more than or equal to 0.03 mass parts, particularly desirably more than or equal to 0.05 mass parts.The higher limit of this content it is desirable to less than or equal to 2.5 mass parts, particularly desirably less than or equal to 2 mass parts.
In light-reflecting article thermoplastic resin composition of the present invention, according to the difference of purpose, for giving desired characteristic, also can mix other and usually mix known material in thermoplastic resin.For example, the colouring agent of dyestuff and pigment etc., the antioxidant that is used for improved hot stability, ultra-violet absorber, light stabilizer, the plasticizer for the pyromellitic acid Arrcostab that improves liquidity or epoxidised soybean oil etc., fire retardant, antistatic additive etc. are arranged for example.
Light-reflecting article thermoplastic resin composition of the present invention because having speciality described above, so formed body need not be done metal evaporation, by mixing so-called metallic pigments, in the occasion of giving formed body gloss, design, also can obtain suitable characteristic.Similarly, because having a feature described above, by painted and give metallic luster and have appearance design, the occasion to carrying out application in the part of the enterprising row metal evaporation of formed body, or the occasion of not carrying out metal evaporation, direct application on formed products, can 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 is not particularly limited, and for example, can make by the melting mixing method.Device as being used for melting mixing is not particularly limited, and can use known device, for example, can use extruder, 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, be not particularly limited, can use injection moulding method, the known method such as the assist formation method of calming the anger, cold cycling forming process, blow-moulding process, extruding formation method, by these methods, can obtain formed products.Wherein, from the popularity aspect, it is desirable to injection moulding method.If the polishing of metal pattern location polishing grain size number more than or equal to No. 5000 or carry out the surface treatment such as chromium plating, can be increased surface smoothness, the gloss of formed products, easily obtain good outward appearance after evaporation or application.
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 is not particularly limited, and it is desirable keeping in 420～700nm scope more than or equal to 65%.
In 420～700nm scope, reflectivity directly forms the light reflective metal layer more than or equal to 65% the time on this formed products, obtain reflection appearance clearly, and it is good and desirable that reflection appearance becomes.
In addition, in the present invention, reflectivity be with マ く ベ ス カ ラ-ア イ CE-3000 spectrophotometer with firmly change the CCM COLOR SCOPE of system that カ ラ one Co., Ltd. makes and be connected, spend the visual field with D light source 10 and in 400nm～700nm scope, the surface of formed products measured.
For the lower limit of this reflectivity, more preferably more than or equal to 66%, ideal is more than or equal to 68%, particularly desirably more than or equal to 70%.Higher limit for reflectivity is not particularly limited.
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, average grain diameter form less than or equal to the light-reflecting article thermoplastic resin composition of the inorganic filling material (B2) of 3 μ m refractive index obtains.
The linear shrinkage ratio of formed article for light reflector of the present invention is not particularly limited, and it is desirable to less than or equal to 1.6%.Less than or equal to 1.6%, liftability, low bendability become good and desirable as linear shrinkage ratio.Lower limit for linear shrinkage ratio is not particularly limited, and it is desirable to more than or equal to 0.6%.More preferably the lower limit of linear shrinkage ratio is more than or equal to 0.8%, and higher limit is more preferably less than or equal to 1.55%, and ideal is less than or equal to 1.50%, particularly desirably less than or equal to 1.45%.
In addition, in the present invention, shrinkage factor is after being cooled to room temperature by the formed products that will obtain, the size L under the size L of mensuration formed products, the room temperature of metal pattern 0, try to achieve from following formula.
The linear shrinkage ratio of formed products (%)={ (L 0-L)/L 0} * 100 (%)
The picture clarity of formed article for light reflector of the present invention is not particularly limited, and it is desirable to more than or equal to 90%.More than or equal to 90% occasion, the clarity that directly forms the light reflector of light reflective metal layer at least a portion surface of this formed products 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 testing machine Co., Ltd. system to write picture property analyzer ICM-1DP, measures with the wide 0.5mm of optical comb (Network シ).
The picture clarity of formed article for light reflector more preferably more than or equal to 93%, more preferably more than or equal to 95%, particularly desirably more than or equal to 96%, it would be desirable more than or equal to 97%.
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 formed article for light reflector is described.
The manufacturing process of formed article for light reflector, be not particularly limited, can use injection moulding method, the known method such as the assist formation method of calming the anger, cold cycling forming process, blow-moulding process, extruding formation method, by these methods, can obtain formed products.Wherein, from the popularity aspect, it is desirable to injection moulding method.
In the present invention, as the thermoplastic resin composition, use the thermoplastic resin composition's of containing mylar occasion, it is desirable to make formed article for light reflector with arithmetic mean surface roughness Ra less than or equal to the metal pattern of 0.075 μ m.Here, arithmetic mean surface roughness Ra is with JISB0601 definition, 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, estimate 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 light reflective metal layer, thermoplastic resin composition's kind is particularly important with the combination of the metal pattern of its use that is shaped.
The occasion that contains the thermoplastic resin composition of polyester in shaping, especially the surface state of metal pattern (surface roughness) can affect the surface state of formed article for light reflector.This is to result from the flow behavior of mylar, because the good fluidity of mylar, so have resin to flow to small concavo-convex of metal pattern surface, causes formed products can directly copy the surface state of metal pattern.
This tendency ties up in the thermoplastic resin that consists of the thermoplastic resin composition, is found for more than or equal to 10 quality % the time when the content of polyester; 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, according to the content of mylar, select the arithmetic mean surface roughness Ra of suitable metal pattern.For example, in the content of the mylar occasion more than or equal to 10 quality %, it is desirable to the arithmetic mean surface roughness Ra of metal pattern less than or equal to 0.07 μ m; In the occasion of amount of polyester more than or equal to 30 quality %, it is desirable to Ra less than or equal to 0.065 μ m; In the occasion of amount of polyester more than or equal to 50 quality %, it is desirable to Ra less than or equal to 0.06 μ m; In the occasion of amount of polyester more than or equal to 80 quality %, it is desirable to Ra less than or equal to 0.055 μ m; Be the occasion of 100 quality % in amount of polyester, it is desirable to Ra less than or equal to 0.05 μ m.
As the metal pattern surface being decided to be the method for the scope of such arithmetic mean surface roughness Ra, be not particularly limited, by with diamond file, grinding stone, vitrified pulpstone, ruby grinding stone, GC grinding stone etc., with ultrasonic polishing grinder or hand operated, polishing is carried out on the metal pattern surface, can be adjusted into desired arithmetic surface roughness Ra.For example, it is desirable to more than or equal to No. 4000, polishing be carried out on the metal pattern surface with the polishing grain size number, so that the arithmetic surface roughness Ra of metal pattern is less than or equal to 0.07 μ m; More than or equal to No. 5000, polishing is carried out on the metal pattern surface with the polishing grain size number, so that the arithmetic surface roughness Ra of metal pattern is less than or equal to 0.06 μ m; More than or equal to No. 6000, polishing is carried out on the metal pattern surface with the polishing grain size number, so that the arithmetic surface roughness Ra of metal pattern is less than or equal to 0.05 μ m; More than or equal to No. 8000, polishing is carried out on the metal pattern surface with the polishing grain size number, so that the arithmetic surface roughness Ra of metal pattern is less than or equal to 0.04 μ m; More than or equal to No. 14000, polishing is carried out on the metal pattern surface with the polishing grain size number, so that the arithmetic surface roughness Ra of metal pattern is less than or equal to 0.03 μ m.
In the present invention, use the thermoplastic resin composition's of containing mylar occasion as the thermoplastic resin composition, also can replace the metal pattern that carries out above-mentioned polishing with the metal pattern of chromium plating.Can also carry out again chromium plating to the 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 is well 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 light reflective metal layer on the surface of at least a portion of above-mentioned formed article for light reflector.
The diffusion of light reflector (diffusion) reflectivity is not particularly limited, and it is desirable to diffuse reflectance after initial stage or heat-resistant experiment less than or equal to 3%.Under this occasion, has good function as light reflector.In addition, in the present invention, the diffuse reflectance of light reflector is measured with the reflection light transmittance instrument HR-100 of color technical research institute in (strain) village.
Again, the picture clarity of light reflector is not particularly limited, and it is desirable to more than or equal to 90%, more preferably more than or equal to 93%, particularly desirably more than or equal to 95%, it would be desirable more than or equal to 97%.
As directly form the method for light reflective metal layer on formed products, be not particularly limited, can form with known methods such as evaporations.For example, the method shown in following is arranged for example.
(1) at first, formed products is placed in evaporation coating device under vacuum state, by importing inert gas and the oxygen of argon etc., to the formed products surface carrying out the plasma activation.(2) then, in evaporation coating device, by making the electrifying electrodes that is holding object, by the plasma at indoor induction discharge, the splash particle (aluminum particulate etc.) of splash is attached on formed body.(3) then, as the diaphragm of the metal steam plated films such as aluminium, siliceous gas is carried out plasma polymerization process or silica is attached on the surface of aluminium-vapour deposition film by the ion plating method.
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 surface roughness 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 metal pattern surperficial, according to the JISB0601 standard, tries to achieve arithmetic mean surface roughness Ra.
The evaluation method of resin
(1) reduced viscosity (η sp/C)
Add the phenol of 1:1 (mass ratio) of 50ml and the mixed solvent of tetrachloroethanes (Northeast chemistry (strain) is made, trade name " PTM11 ") in 0.25g polybutylene terephthalate (PBT) resin, dissolve under 140 ℃ and obtained solution in 10～30 minutes.Its temperature adjustment in 25 ℃ of Water Tanks with Temp.-controlled after 3 minutes, by the time between graticule, is tried to achieve reduced viscosity (η sp/C) with ウ ベ ロ-デ type viscometer determining.
ηsp/C＝(ηrel-1)/C＝(T/T 0-1)/C
T: the passing through the time (second) of the capillary graticule of sample solution
T 0: only the capillary graticule during mixed solvent passes through the time (second)
C: sample solution concentration (g/dl)
(2) inherent viscosity ([η])
Use the phenol of 1:1 (mass ratio) and the mixed solvent of tetrachloroethanes, compound concentration is 0.2,0.3, the pet resin solution of 0.4g/dl, measure the viscosity of each concentration solution at 25 ℃ of temperature with ウ ベ ロ-デ type automatic viscometer (SAN DENSHI (strain) make, AVL-2C), be inserted to concentration 0g/dl outside the value that obtains is schemed with the Huggins, try to achieve inherent viscosity ([η]).
(3) acid value
Make polybutylene terephthalate (PBT) be dissolved in phenmethylol, with the NaOH benzyl alcohol solution titration of 1/50N, measure.
The evaluation method of formed products
(1) liftability: evaluation method 1
Visual outward appearance to formed products is estimated, and estimates whether the molding vestige occurs.
Zero: liftability is good, can not confirm the formed products defectiveness.
*: because molding is bad, the molding vestige has occured in formed products.
(2) liftability: evaluation method 2
After melting mixing particle drying with each composition, with injection molding machine (the SANJECT3601 60T that the accurate society in mountain city makes), under the condition in 260 ℃ of cylinder temperature, 80 ℃ of metal pattern temperature, 20 seconds cool times, 35 seconds cycles, with the cylindrical shape formed products of long 50mm, internal diameter 45mm, thick 3mm～4mm, the outstanding power (molding power) by the Center of Pressure during to molding is measured.Molding power is little, and the liftability of metal pattern is good.
In addition, this molding power less than or equal to 500N as the part forming of various lamps the time, have good liftability.When molding power surpassed 500N, molding was difficult, and productivity reduces, and has problems when the formed products of molding large or the formed products of complicated shape.
(3) shaping shrinkage rate
After shaping, after waiting the formed products cool to room temperature, measure the size L of formed products, by the size L under the room temperature of metal pattern 0, try to achieve shaping shrinkage rate (linear shrinkage ratio) from following formula.
The linear shrinkage ratio of formed products (%)={ (L 0-L)/L 0} * 100 (%)
(4) mist formation
Cut out the small pieces of about 20mm * 10mm from formed products, with the 6g test tube (φ 30 * 200) of packing into, place it in adjustment and be the mist formation testing machine (the mist formation experiment WSF-2 modified form that the gas test machine is made) of 160 ℃.(after テ Application パ Star Network ス glass 55 * 55 * 3mmt) lid, carry to adjust the temperature to 25 ℃, to pass to the aluminium block (ア Le ミ Block ロ Star Network) of cooling water, carry out heat treatment in 20 hours under 160 ℃ covering heat resistant glass on above-mentioned test tube again.After carrying out this heat treatment, separate out attachment from the analyte of resin combination distillation etc. at the glass plate inwall.(HR-100 that in (strain) village, color technical research institute makes) measures the mist (permeability of light) on these glass plates with reflection light transmittance instrument.
In addition, the glass plate after heating in 160 ℃ * 20 hours hazes and surpasses 45% occasion, as the various parts that wait, problem is arranged in practical.Glass plate hazes less than or equal to 45% occasion, can reach the function as the part of various lamps, and is good and desirable, particularly desirably less than or equal to 20%.
(5) reflectivity on formed products surface
With マ く ベ ス カ ラ-ア イ CE-3000 spectrophotometer with firmly change the CCM COLOR SCOPE of system that カ ラ-Co., Ltd. makes and be connected, spend the visual field with D light source 10 and in 400nm～700nm scope, the surface of formed products measured and tried to achieve reflectivity.
(6) as clarity (imaging definition)
According to JISH8686, use ス ガ testing machine Co., Ltd. system to write picture property analyzer ICM-1DP, measure the picture vividness of formed products with the wide 0.5mm of optical comb.
The evaluation method of light reflector
(1) visual ocular estimate
For the outward appearance of the light reflective metal layer of light reflector, before and after heat-resistant experiment, visual valuation outward appearance (planar defective, whiting, the reflection appearance of defective, tangerine peel that is caused by the molding vestige).
1) molding vestige
◎: the white apperance of the fluffing shape concavo-convex (corrugated) that causes by the white apperance that copies (mould is concavo-convex to be copied) 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 copies the white apperance that the white apperance that causes or corrugated cause, is only can recognize a little from visual angle, in practical level out of question.
△: mould is concavo-convex copies the white apperance that the white apperance that causes or corrugated cause has from the teeth outwards.
*: mould is concavo-convex, and to copy the white apperance that the white apperance that causes or corrugated cause very obvious.
2) the planar defective of tangerine peel
◎: rough surface (rough, a lot of pimple sense) completely without.
Zero: rough surface (rough, a lot of pimple sense) is only can recognize a little from visual angle, in practical level out of question.
△: rough surface (rough, a lot of pimple sense) has.
*: rough surface (rough, a lot of pimple sense) is very obvious.
3) whiting (before heat-resistant experiment)
◎: during shaping, additive oozes out the whiting of the inhomogenous shape that causes (mottled etc.) to the formed products surface, completely without.
Zero: be only can recognize that from visual angle additive when being shaped oozes out the whiting of the inhomogenous shape that causes (mottled etc.), level out of question in practical to the formed products surface.
△: the whiting that during shaping, additive oozes out the inhomogenous shape that causes (mottled etc.) to the formed products surface can be confirmed.
*: it is very obvious that during shaping, additive oozes out the whiting of the inhomogenous shape that causes (mottled etc.) to the formed products surface.
4) whiting (after heat-resistant experiment)
◎: during shaping, additive oozes out the whiting of the inhomogenous shape that causes (mottled etc.) to the formed products surface, or the whiting that additive oozes out the inhomogenous shape that causes (mottled etc.) to the formed products surface during heat resistant test completely without.
Zero: be only can recognize that from visual angle additive when being shaped oozes out the whiting of the inhomogenous shape that causes (mottled etc.) to the formed products surface, or additive oozes out the whiting of the inhomogenous shape that causes (mottled etc.), level out of question in practical to the formed products surface during heat resistant test.
△: during shaping, additive oozes out the whiting of the inhomogenous shape that causes (mottled etc.) to the formed products surface, or the whiting that additive oozes out the inhomogenous shape that causes (mottled etc.) to the formed products surface during heat resistant test can be confirmed.
*: during shaping, additive oozes out the whiting of the inhomogenous shape that causes (mottled etc.) to the formed products surface, or additive oozes out the whiting of the inhomogenous shape that causes (mottled etc.) to the formed products surface during heat resistant 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 before and after heat-resistant experiment with the reflection light transmittance instrument HR-100 of color technical research institute in (strain) village.
(3) metal film adhesive strength
By fritter peel test (disbonded test of basal disc order), the initial stage of light reflector and the metal bonding layer intensity after heat-resistant experiment are estimated.The fritter peel test is that ((Article Number: CT-24), the fritter number that carries out the 1mm interval is 100 fritter peel test for セ ロ Ha Application テ-プ) for the glass paper tape that uses ニ チ バ Application to make.Estimate with the percentage (%) of the fritter number that remains in the formed products surface to whole fritter numbers.In the early stage 100% and after heat resistant test more than or equal to 80% the time, reach as the effect of light reflector and good.
In addition, the fritter peel test at the initial stage of light reflector is after formed article for light reflector carries out aluminium-vapour deposition, carries out after room temperature is placed more than 24 hours.Fritter peel test after heat-resistant experiment is after heat-resistant 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 testing machine Co., Ltd. system to reflect look analyzer ICM-1DP, measure the imaging vividness of formed products with the wide 0.5mm of optical comb.
(5) heat-resistant experiment
Lucky inferior insulating box (the ギ ヤ オ-Block Application) GPH (H)-100 that uses タ バ イ エ ス ベ Star Network (strain) to make places light reflector 24 hours in the hot blast of 160 ℃, heat-treats.
[Production Example of ethene based thermoplastic resin]
Production Example 1 (acrylonitrile-styrene copolymerized resin (x-1))
With phosphoric acid (three) calcium of the distilled water of 115 mass parts, 1 mass parts, the デ モ of 0.001 mass parts-Le water system dispersant P (flower king (strain) makes) retort of packing into and stir.The acrylonitrile, the styrene of 75 mass parts, the t-dodecyl mercaptans of 0.5 mass parts, the azodiisobutyronitrile 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 again 25 alkene mass parts, after becoming suspension, be warming up to 75 ℃, keep completing polymerization in 240 minutes, obtain acrylonitrile-styrene copolymerized resin (x-1).Resulting (x-1) resin consist of acrylonitrile/styrene=34/66 (mass ratio).
Production Example 2 (containing the acrylonitrile-styrene copolymerized resin of epoxy radicals (x-2))
With 115 mass parts distilled water, 1 mass parts phosphoric acid (three) calcium, 0.001 mass parts デ モ-Le water system dispersant P (flower king (strain) makes) retort of packing into and stirring.Add again 23 mass parts acrylonitrile, 76.7 mass parts styrene, 0.3 mass parts GMA, 0.5 mass parts t-dodecyl mercaptans, 0.17 mass parts azodiisobutyronitrile, 0.003 mass parts ガ Off ア Star Network GB-520 (eastern nation chemical industry (strain) manufacturing), after becoming suspension, be warming up to 75 ℃, keep completing polymerization in 240 minutes, obtain containing the acrylonitrile-styrene copolymerized resin of epoxy radicals (x-2).Resulting (x-2) resin consist of acrylonitrile/styrene/methacrylic acid ethylene oxidic ester=24.9/74.7/0.4 (mass ratio).
Production Example 3 (maleimide based copolymerized resin (x-3))
Toward the polymer reactor with 20 liters of agitating devices that carried out the nitrogen replacement operator, supply with continuously acrylonitrile, 20 mass parts of styrene, 20 mass parts of N-phenylmaleimide, 40 mass parts of 20 mass parts methyl ethyl ketone, 0.01 mass parts 1, the t-dodecyl mercaptans of 1-azo (cyclohexane-1-formic acid), 0.05 mass parts.One side remains 110 ℃ with the temperature in polymer reactor, and the gear pump that the bottom of one side by polymer reactor has extracts polymerization liquid continuously, so that mean residence time is 2 hours.Then, after making this polymerization liquid be detained about 20 minutes with the heat exchanger that remains on 150 ℃, import the two axle extruders of 30mm φ that the cylinder temperature is controlled to be the 2 outlet duct types of 230 ℃.The first exhaust portion is decided to be atmospheric pressure, and the second exhaust portion is decided to be under the decompression of 2.7Kpa, removes volatile ingredient, with its granulating, obtains maleimide based copolymerized resin (x-3) with granulator.(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 (PBT) (a-1) of 76.2 mass parts of thermoplastic resin (A) in fusion, commodity are called " タ Off ペ Star ト N1100 ", reduced viscosity η sp/C=1.14, acid value=62meq/kg), the PETG of 19 mass parts (a-2) (make by Mitsubishi's レ イ ヨ Application (strain), commodity are called " ダ イ ヤ Na イ ト MA580D ", inherent 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 (refreshing island chemical industry (strain) is made with surface-treated (the adhesion amount 2.2 quality %) winnofil (B1-1) of stearic acid, trade name " カ Le シ-ズ ", average grain diameter 0.15 μ m), as the montanic acid of 0.19 mass parts carbon number 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 name " Licolub WE4 "), and (change firmly that カ ラ-(strain) make as the carbon black of 0.25 mass parts of pigment, trade name " Block ラ Star Network BPM-8E756 "), mixed 5 minutes with the V-type blender, make it mix homogenization, under 260 ℃ of temperature cylinders, drop into the two axle extruders with 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, at the upper injection molding forming of the square flat board metal pattern of 100mm (metal pattern surface #14000 polishing granularity polishing), the linear shrinkage ratio that obtains formed products (100mm * 100mm, thick 3mm) formed products is 1.40%.
Below, direct AM aluminum metallization by the following method on the formed products that obtains.
At first, import inert gas and oxygen in the evaporation coating device under vacuum state, indoor is plasmoid, makes the plasma activation of formed products surface activation.Then, AM aluminum metallization in the evaporation coating device under vacuum state.By make the electrifying electrodes of carrying object in evaporation coating device, produce plasma indoor by induction discharge, ion in plasma makes the object splash, makes the splash particle that flies out from object, is that aluminum particulate is attached on the formed products surface, forms the aluminium-vapour deposition film comprehensively.The thickness of aluminium-vapour deposition film is 80nm.Then, as the diaphragm of the metal steam surfacing such as aluminium, carry out plasma polymerization and process.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 directly forming the light reflector of light reflective metal layer on the thermoplastic polyester resin formed products.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 after determination test is 1.9%, and is good.
Embodiment 2～10
Except thermoplastic resin composition's the composition that consists of table 1, the method that other is used similarly to Example 1 obtains particle, formed products, light reflector.Evaluation result is as shown in table 1.
Comparative example 1～6
Except thermoplastic resin composition's the composition that consists of table 2, the method that other is used similarly to Example 1 obtains particle, formed products, light reflector.Evaluation result is as shown in table 2.
Table 2
Figure G2008102148262D00231
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) winnofil: use stearic acid effects on surface is processed (2.2 quality %) winnofil excessively, and (refreshing island chemical industry (strain) is made, trade name " カ Le シ-ズ P "), average grain diameter=0.15 μ m (infiltration type electron microscope method);
(B1-2) china clay: process the moisture china clay that (0.5 quality %) cross (ENGELHARD society make, trade name " ASP101 "), average grain diameter (median)=0.4 μ m (measured value of laser diffractometry) with the stearic acid effects on surface;
(b1-3) talcum: surperficial untreated talcum (woods changes into the manufacturing of (strain) society, trade name " #5000S "), average grain diameter (median)=5.3 μ m (measured value of laser diffractometry);
(b1-4) powdered whiting: surperficial untreated powdered whiting (Japan's Off ア イ Application ケ ミ カ Le (strain) is made, trade name " ホ ワ イ ト Application P-70 "), average grain diameter=2.31 μ m (BET specific area scaled value);
(b1-5) winnofil: surperficial untreated winnofil (white lapicide's industry (strain) is made, trade name " Brilliant-1500 "), average grain diameter=0.2 μ m (BET specific 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 name " CHC-13S-05E "), average grain diameter (median)=5.3 μ m (measured value of laser diffractometry);
The montanate paraffin of carbon number 24～34: Network ラ リ カ Application ト ジ ヤ パ Application (strain) is made, trade name " LicolubWE4 ";
Fatty mono glyceride: reason grinds that PVC タ ミ Application (strain) makes, trade name " リ ケ マ-Le S100A ";
The montanic acid sodium salt of carbon number 24～34; Network ラ リ カ Application ト ジ ヤ パ Application (strain) is made, trade name " LicomontNaV101 ".
Embodiment 14
(Mitsubishi's レ イ ヨ Application (strain) is made as the polybutylene terephthalate (PBT) (a-1) of 76.2 mass parts of thermoplastic resin (A) in fusion, commodity are called " タ Off ペ Star ト N1100 ", reduced viscosity η sp/C=1.14, acid value=62meq/kg), the PETG of 19 mass parts (a-2) (make by Mitsubishi's レ イ ヨ Application (strain), commodity are called " ダ イ ヤ Na イ ト MA580D ", inherent 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, blanc fixe (B2-1) (boundary's chemical industry (strain) is made, trade name " B-30NC ", average grain diameter 0.3 μ m, refractive index 1.64) as 4.8 mass parts of inorganic filler, as the montanic acid of the carbon number 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 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 name " Block ラ Star Network BPM-8E756 "), made it mix homogenization in 5 minutes with the V-type blender, under 260 ℃ of temperature cylinders, drop into the two axle extruders with 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 (metal pattern is surperficial with the polishing of #14000 polishing grain size number), the linear shrinkage ratio that obtains formed products (100mm * 100mm, thick 3mm) formed products is 1.4%.
Below, direct AM aluminum metallization by the following method on the formed products that obtains.
At first, import inert gas and oxygen in the evaporation coating device under vacuum state, indoor is plasmoid, makes the plasma activation of formed products surface activation.Then, AM aluminum metallization in the evaporation coating device under vacuum state.By make the electrifying electrodes of carrying object in evaporation coating device, produce plasma indoor by induction discharge, ion in plasma makes the object splash, makes the splash particle that flies out from object, is that aluminum particulate is attached on the formed products surface, forms the aluminium-vapour deposition film comprehensively.The thickness of aluminium-vapour deposition film is 80nm.Then, as the diaphragm of the metal steam surfacing such as aluminium, carry out plasma polymerization and process.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 directly forming the light reflector of light reflective metal layer on the thermoplastic polyester resin formed products.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 after determination test is 1.9% and good.
Embodiment 2～10
Except thermoplastic resin composition's the composition that consists of table 3, the method that other is used similarly to Example 14 obtains particle, formed products, light reflector.Evaluation result is as shown in table 3.
Comparative example 1～6
Except thermoplastic resin composition's the composition that consists of table 4, the method that other is used similarly to Example 14 obtains particle, formed products, light reflector.Evaluation result is as shown in table 4.
Figure G2008102148262D00261
Table 4
Figure G2008102148262D00271
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) blanc fixe: boundary's chemical industry (strain) is made, trade name " B-30NC "), average grain diameter=0.3 μ m (infiltration type electron microscope method) refractive index 1.64;
(B2-2) blanc fixe: boundary's chemical industry (strain) is made, trade name " SS-50 "), average grain diameter=0.1 μ m (infiltration type electron microscope method) refractive index 1.64;
(b2-3) talcum: surperficial untreated talcum (woods changes into the manufacturing of (strain) society, trade name " #5000S "), average grain diameter (median)=5.3 μ m (measured value of laser diffractometry) refractive index 1.56;
The montanate paraffin Network ラ リ カ Application ト ジ ヤ パ Application (strain) of carbon number 24～34 is made, trade name " LicolubWE4 ";
The montanic acid sodium salt of carbon number 24～34; Network ラ リ カ Application ト ジ ヤ パ Application (strain) is made, trade name " LicomontNaV101 ".
Fatty mono glyceride: reason grinds that PVC タ ミ Application (strain) makes, trade name " リ ケ マ-Le S100A ";
Embodiment 27
(Mitsubishi's レ イ ヨ Application (strain) is made as the polybutylene terephthalate (PBT) (a-1) of 80 mass parts of thermoplastic resin (A) in fusion, commodity are called " タ Off ペ Star ト N1100 ", reduced viscosity η sp/C=1.14, acid value=62meq/kg), the PETG of 20 mass parts (a-2) (make by Mitsubishi's レ イ ヨ Application (strain), commodity are called " ダ イ ヤ Na イ ト MA580D ", inherent 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 name " Licolub WE4 ") as 0.2 mass parts of (C1) composition, (C2-1) stearic acid triglycerides (reason is ground PVC タ ミ Application (strain) manufacturing, trade 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 name " #SG200 "), and (change firmly that カ ラ-(strain) make as the carbon black of 0.24 mass parts of pigment, trade name " Block ラ Star Network BPM-8E756 "), mixing with the V-type blender made it mix homogenization in 5 minutes, under 260 ℃ of temperature cylinders, drop into the two axle extruders with 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, in (the metal pattern surface #14000 polishing granularity polishing of the square flat board metal pattern of 100mm, arithmetic mean surface roughness Ra=0.03 μ m) upper injection molding forming, obtain formed products (100mm * 100mm, thick 3mm).The plate forming product that obtain be 98.2% as clarity.
Then, after the square plate forming product of the 100mm that obtains were estimated mist formation, the value of mist was 27%.
Below, direct AM aluminum metallization by the following method on the formed products that obtains.
At first, import inert gas and oxygen in the evaporation coating device under vacuum state, indoor is plasmoid, makes the plasma activation of formed products surface activation.Then, AM aluminum metallization in the evaporation coating device under vacuum state.By make the electrifying electrodes of carrying object in evaporation coating device, produce plasma indoor by induction discharge, ion in plasma makes the object splash, makes the splash particle that flies out from object, is that aluminum particulate is attached on the formed products surface, forms the aluminium-vapour deposition film comprehensively.The thickness of aluminium-vapour deposition film is 80nm.Then, as the diaphragm of the metal steam surfacing such as aluminium, carry out plasma polymerization and process.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 directly forming the light reflector of light reflective metal layer on the thermoplastic polyester resin formed products.The evaluation result of the light reflector that obtains is shown in table 5 and table 7.
Then, carry out the heat-resistant experiment of resulting light reflector, the evaluation result of light reflector after experiment is shown in table 5.
Embodiment 28～31
Except thermoplastic resin composition's the composition that consists of table 5, the method that other is used similarly to Example 27 obtains particle, formed products, light reflector.Evaluation result is as shown in table 5.
Comparative example 10～20
Except thermoplastic resin composition's the composition that consists of table 6, the method that other is used similarly to Example 27 obtains particle, formed products, light reflector.Evaluation result is as shown in table 6.
Table 5
Figure G2008102148262D00301
Figure G2008102148262D00311
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 triglycerides: Network ラ リ カ Application ト ジ ヤ パ Application (strain) is made, trade name " Licolub WE4 ";
(C2-1) stearic acid monoglyceride: reason grinds that PVC タ ミ Application (strain) makes, trade 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 name " Licomont NaV ";
(c-4) montanic acid calcium: Network ラ リ カ Application ト ジ ヤ パ Application (strain) is made, trade name " Licomont CaV102 ";
(c-5) montanic acid pentaerythrite four esters: Network ラ リ カ Application ト ジ ヤ パ Application (strain) is made, trade name " LicolubWE40 ";
(c-6) montanic acid ethylene glycol diester: Network ラ リ カ Application ト ジ ヤ パ Application (strain) is made, trade name " Licowax E ";
(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 name " Licowax OP ";
Talcum (average grain diameter 4.4 μ m): woods changes into (strain) and makes, trade name " #SG2000 ") carry out the talcum that γ-surface treatment (0.5 quality %) is crossed;
Talcum (average grain diameter 0.9 μ m): woods changes into (strain) and makes, to trade 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 with stearic acid the moisture china clay that surface treatment (0.5 quality %) is crossed, ENGELHARD makes, trade 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, in (the metal pattern surface #8000 polishing granularity polishing of the square flat board metal pattern of 100mm, arithmetic mean surface roughness Ra=0.04 μ m) upper injection molding forming obtains the formed products (100mm * 100mm) of light-reflecting article.With similarly to Example 27 the direct AM aluminum metallization of method, obtain light reflector on the square plate forming product of the 100mm that obtains.The light reflector that obtains is shown in table 7 as clarity.
Embodiment 33
Use metal pattern except conduct is dull and stereotyped, outside the metal pattern (arithmetic average roughness Ra=0.06 μ m) of metal pattern surface with the #5000 polishing, 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
Use metal pattern except conduct is dull and stereotyped, outside the metal pattern (arithmetic average roughness Ra=0.08 μ m) of metal pattern surface with the #3000 polishing, 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
Use metal pattern except conduct is dull and stereotyped, outside the metal pattern (arithmetic average roughness Ra=0.13 μ m) of metal pattern surface with the #800 polishing, 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
Figure G2008102148262D00331
The possibility of utilizing on 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 heat under 160 ℃ of conditions, heating ambiguity (tangerine peel is planar, whiting) occurs few on the light reflective metal layer that forms by direct vapour deposition method; Light reflector of the present invention has feature good aspect mist formation; The reflection appearance of light reflector of the present invention is clear, good appearance; The picture clarity of light emitter of the present invention is good; Light emitter of the present invention is good with the liftability of formed products; 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 can use suitably as the light reflector of cover, speculum, prolongation or the household electrical appliances illuminator lamp case etc. of automobile etc.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 advantages of the free degree increase the when free degree of design of light reflector and metal pattern are made.

Claims (4)

1. the manufacture method of a light reflector, it is characterized in that, use contains the thermoplastic resin composition of the above mylar of 50 quality %, with the metal pattern shaping formed article for light reflector of arithmetic mean surface roughness Ra less than or equal to 0.07 μ m, directly form the light reflective metal layer on the surface of described formed article for light reflector at least a portion.
2. the manufacture method of light reflector as claimed in claim 1, is characterized in that, the arithmetic mean surface roughness Ra of metal pattern is less than or equal to 0.06 μ m.
3. the manufacture method of light reflector as claimed in claim 1, is characterized in that, the arithmetic mean surface roughness Ra of metal pattern is less than or equal to 0.04 μ m.
4. the manufacture method of light reflector as claimed in claim 1, is characterized in that, the arithmetic mean surface roughness Ra of metal pattern is less than or equal to 0.03 μ m.
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