JP5417374B2 - Method for producing molded article for light reflector and light reflector - Google Patents

Description

  The present invention relates to a method for manufacturing a molded article for a light reflector used for a light reflector such as a housing, reflector, extension, and lighting fixture for an automobile lamp, and the light reflector.

  Conventionally, a bulk molding compound (hereinafter abbreviated as BMC), which is a thermosetting resin, has been used as a material for light reflectors such as reflectors and extensions used in automobile lamps. Although BMC is excellent in heat resistance and dimensional stability, it has a problem that it has a long molding cycle, takes time for processing such as burrs during molding, and has low productivity. As means for solving such problems, studies using thermoplastic resins have been conducted.

  Examples of using thermoplastic resins include materials in which various reinforcing materials are blended into crystalline resins such as polybutylene terephthalate and polyethylene resins such as polyethylene terephthalate, and amorphous resins such as polycarbonate resins. Is used.

  For example, a method has been proposed in which a polyethylene terephthalate resin is used as a thermoplastic resin and a composition in which glass fiber and talc are blended as a reinforcing material is used (see Patent Document 1).

  However, in this method, since the smoothness of the surface of the molded product is insufficient due to the embossing of the filler and the mold release failure, an undercoat treatment is performed before forming the light reflecting metal layer on the molded product, Must be smoothed. Without this undercoat treatment, even if a light reflecting metal layer was formed, a mirror surface was not produced, and a satisfactory light reflector could not be obtained. Such an undercoat treatment requires an extra process, the problem of processing the solvent used in the undercoat material, and further the drying of the paint. There was a problem that the load to give was large.

  In recent years, a direct vapor deposition (direct vapor deposition) method has been proposed as a method that does not require such an undercoat treatment. In this direct vapor deposition method, a metal is directly deposited on a molded product, or a metal film is deposited after a plasma activation process is performed on the molded product, so that the surface of the molded product is not subjected to an undercoat process, and light reflection is performed. In this method, the metal layer is directly formed.

  On the other hand, recently, there is a tendency to use a high-power lamp in order to increase the brightness, the temperature inside the headlamp rises, and a heat resistant temperature of 160 to 180 ° C. is required as a base material for the reflector. It is coming. However, in the light reflector manufactured by the direct vapor deposition method, the problem that the light reflection layer becomes cloudy (heating cloudiness) is particularly noticeable when held for a long time in a high temperature environment.

  There are several types of this heat fogging phenomenon. For example, (1) Phenomenon in which the base resin and the metal layer are peeled off due to thermal deformation of the base resin (decrease in surface smoothness) ), (2) Phenomenon in which the base resin and the metal layer are peeled or deformed by the thermal decomposition gas of the base resin (whitening), (3) Exudation of components such as additives in the base resin, There is a phenomenon (whitening) in which the material resin and the metal layer peel or deform.

  Various attempts have been made to solve the problem of heat fogging. For example, a resin composition in which a polybutylene terephthalate resin is blended with an inorganic filler, an antioxidant, and an internal lubricant (see Patent Document 2). In addition, a resin composition (see Patent Document 3) in which an inorganic reinforcing material and a wax are blended with a resin composed of a polybutylene terephthalate resin and a polyalkylene naphthalate resin has been proposed.

  The resin composition described in Patent Document 2 suppresses generation of pyrolysis gas (the phenomenon of (2) above) of the polyester resin as the base resin by setting the terminal carboxyl group amount to a specific amount or less. This suppresses heating clouding (whitening). However, the resin composition described in the same document has no problem when molding a small and simple molded product such as a 50 mm square flat plate, but does not include a release agent component, so that it is a reflector. When molding a large and complex three-dimensional molded product such as an extension, there is a problem of molding defects (surface smoothness of the molded product, mold release mark, etc.) due to mold release failure.

  The resin composition described in Patent Document 3 increases the heat resistance of the substrate by using a polyalkylene naphthalate resin, and suppresses a decrease in surface smoothness of the substrate due to heating (the phenomenon of (1) above). This suppresses heating clouding (skin skin defects). However, since the resin composition described in the same document uses calcium montanate (Hostalb CaV102) or pentaerythritol tetraester montanate (Hostalub WE40) as a release agent wax, A release mark problem occurs. Although the resin composition using calcium montanate has good releasability, heat build-up (whitening) occurs because calcium montanate begins to bleed out in a high temperature environment, and pentaerythritol tetraester montanate When is used, although heat fogging (whitening) is small, the release effect is small, and a release mark or the like due to a release failure occurs.

  Thus, there has not been a thermoplastic resin composition that satisfies both the problem of heat fogging and the problem of releasability at the same time.

  On the other hand, automobile headlamps that use reflectors and extensions have a structure in which a light source device, reflector, extension, etc. are incorporated in a container sealed with a case (housing) that houses lenses and components. There is also a problem that volatile matter is generated from the resin exposed to high temperature when the light source is turned on, and it adheres to the lens portion and the lens surface becomes cloudy. This fogging of the lens surface is called fogging, and improving it is also an important technical problem for resin reflectors and extension materials. Studies have been made to improve fogging properties by adding an epoxy-containing substance to a thermoplastic polyester resin (see Patent Document 4). However, the resin composition described in Patent Document 4 also has the problem of fogging (heating clouding) of the light reflecting metal layer.

In addition, even if the above problems can be solved in terms of materials, a problem that did not become a problem when forming a light-reflecting metal layer after performing a conventional undercoat treatment will newly occur depending on the type of material. It became clear. When using a mold that has the same surface condition (surface roughness) as the mold used when molding a light reflector of the type that undercoats, depending on the type of molding material, the surface of the molded product In other words, the surface roughness (unevenness) of the mold is transferred to the surface, resulting in poor image clarity. Since the unevenness of the mold transferred to the molded product is very slight, when an undercoat is applied to this, the unevenness is smoothed, and there has been no particular problem in the past. However, when the light-reflecting metal layer is formed directly on the molded article for light reflector without applying an undercoat, the unevenness transferred to the molded article affects the reflection characteristics of the light reflector, resulting in image sharpness. Only a light reflector having an appearance that is inferior to the image quality could be obtained.
JP-A-6-203613 JP 2000-35509 A JP 2002-179895 A JP 2001-316573 A

  An object of the present invention is to provide a method for producing a light reflector having an appearance excellent in molding appearance, particularly image sharpness, when producing a light reflector from a thermoplastic resin composition containing a polyester resin. It is in.

The present invention uses a thermoplastic resin composition containing a polyester resin, molded with a mold having an arithmetic average surface roughness Ra of 0.075 μm or less, and a light reflector having an image sharpness of 90% or more. the method of manufacturing the light reflecting-body moldings, characterized in Rukoto give use moldings, using the thermoplastic resin composition containing a polyester resin, and a mold having polished the surface with polishing grit # 5000 or , using a thermoplastic resin composition containing a light reflection-body method of producing moldings or polyester resin, the image sharpness is characterized Rukoto obtain a light reflection-body moldings is 90% or more, molded chrome plated mold, the image sharpness is related to a method of manufacturing an optical reflection-body moldings, characterized in Rukoto obtain a light reflection-body moldings is 90% or more.

Polyester by molding with a mold having an arithmetic average surface roughness Ra of 0.075 μm or less, by molding with a mold polished with a polishing count of 5000 or more, or with a mold subjected to chrome plating surface treatment Even when a thermoplastic resin composition containing a resin is used, a light reflector in which a light-reflecting metal layer having a good reflective appearance is directly formed can be obtained.

  The present invention will be described below.

  Examples of the polyester resin used in the present invention include polyesters obtained by polycondensation of aromatic or alicyclic dicarboxylic acids or their derivatives and polyols. Examples of the dicarboxylic acid include terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, cyclohexanedicarboxylic acid and the like. Examples of the polyol include alkylene diols such as ethylene glycol, diethylene glycol, propane diol, and butane diol having 2 to 6 methylene chains, adducts of bisphenol A polyethylene glycol and / or polypropylene glycol, and the like.

  (A) Specific examples of the polyester resin include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate and the like, and these may be used alone or polyester resins having different compositions and / or molecular weights. You may use the mixture which used together.

  In particular, it is preferable to use (a-1) polybutylene terephthalate and (a-2) polyethylene terephthalate in combination from the viewpoints of moldability, appearance, and economy. Although the mixing ratio in the case of using these together is not restrict | limited, In (a) polyester resin whole quantity, (a-1) Polybutylene terephthalate 55-95 mass%, (a-2) Polyethylene terephthalate 5-45 mass% Preferably there is. (A-1) When the mixing ratio of polybutylene terephthalate is 55% by mass or more, the molding cycle time tends to be short and the productivity tends to be good, and when it is 95% by mass or less, the surface smoothness of the molded product is It tends to be good. Further, when the mixing ratio of (a-2) polyethylene terephthalate is 5% by mass or more, the surface smoothness of the molded product tends to be good, and when it is 45% by mass or less, the molding cycle time is shortened. Productivity tends to be good. The lower limit value of the mixing ratio of the component (a-1) is more preferably 60% by mass or more, and particularly preferably 70% by mass or more. (A-1) 90 mass% or less is more preferable, and, as for the upper limit of the mixing ratio of a component, 85 mass% or less is especially preferable. Moreover, 10 mass% or more is more preferable, and, as for the lower limit of the mixing ratio of (a-2) component, 15 mass% or more is especially preferable. (A-2) As for the upper limit of the mixing ratio of a component, 40 mass% or less is more preferable, and 37 mass% or less is especially preferable.

  (A-1) The polybutylene terephthalate is not particularly limited, and may be a homopolymer of a butylene terephthalate unit or a copolymer containing 70% by mass or more of a butylene terephthalate unit in a repeating unit. . Monomers to be copolymerized include dibasic acid components other than terephthalic acid and lower alcohol esters thereof, and aromatic or aliphatic polyvalents such as isophthalic acid, naphthalenedicarboxylic acid, adipic acid, sebacic acid, trimellitic acid, and succinic acid. Examples thereof include basic acids or esters thereof. Examples of glycol components other than 1,4-butanediol include alkylenes such as ethylene glycol, diethylene glycol, propylene glycol, trimethylene glycol, hexamethylene glycol, neoventyl glycol, cyclohexanedimethanol, and 1,3-octanediol. Glycol; Aromatic alcohols such as bisphenol A and 4,4′-dihydroxybiphenyl; Alkylene oxide adducts such as ethylene oxide 2-mole adduct of bisphenol A, propylene oxide 3-mole adduct of bisphenol A; Glycerin, pentaerythritol, etc. These polyhydroxy compounds or their ester-forming derivatives.

  The molecular weight of (a-1) polybutylene terephthalate is not particularly limited, but the reduced viscosity (ηsp / C) at 25 ° C. as an index of molecular weight is preferably 0.7 to 2.0. When the reduced viscosity is 0.7 or more, the strength tends to be good, and when it is 2.0 or less, the fluidity and appearance tend to be good. The lower limit of the reduced viscosity is more preferably 0.8 or more, and particularly preferably 0.9 or more. Further, the upper limit of the reduced viscosity is more preferably 1.7 or less, and particularly preferably 1.5 or less.

  (A-2) The polyethylene terephthalate is not particularly limited, and may be a homopolymer of ethylene terephthalate units or a copolymer containing 70% by mass or more of ethylene terephthalate units in the repeating unit. Monomers to be copolymerized include dibasic acid components other than terephthalic acid and lower alcohol esters thereof, and aromatic or aliphatic polyvalents such as isophthalic acid, naphthalenedicarboxylic acid, adipic acid, sebacic acid, trimellitic acid, and succinic acid. Examples thereof include basic acids or esters thereof. Examples of the glycol component other than ethylene glycol include alkylene glycols such as diethylene glycol, propylene glycol, butylene glycol, trimethylene glycol, hexamethylene glycol, neopentyl glycol, cyclohexane dimethanol, and 1,3-octanediol; bisphenol A, 4, Aromatic alcohols such as 4'-dihydroxybiphenyl, alkylene oxide adduct alcohols such as ethylene oxide 2 mol adducts of bisphenol A, propylene oxide 3 mol adducts of bisphenol A; polyhydroxy compounds such as glycerin and pentaerythritol or the like Examples include ester-forming derivatives.

  (A-2) The molecular weight of polyethylene terephthalate is not particularly limited, but the intrinsic viscosity ([η]) as an index of molecular weight is preferably 0.4 to 1.0. When the intrinsic viscosity is 0.4 or more, the strength tends to be good, and when it is 1.0 or less, the fluidity and appearance tend to be good. The lower limit of the intrinsic viscosity is more preferably 0.45 or more, and particularly preferably 0.5 or more. Further, the upper limit of the intrinsic viscosity is more preferably 0.9 or less, and particularly preferably 0.8 or less.

  In the present invention, the method for producing the thermoplastic resin composition is not particularly limited, and for example, it can be produced by a melt kneading method. The apparatus used for melt kneading is not particularly limited, and a known apparatus can be used. For example, an extruder, a Banbury mixer, a roller, a kneader, or the like can be used.

  In the present invention, when a thermoplastic resin composition containing a polyester resin is used as the thermoplastic resin composition, a molded article for a light reflector is manufactured with a mold having an arithmetic average surface roughness Ra of 0.075 μm or less. To do. Here, the arithmetic average surface roughness Ra is defined by JIS B0601, using a non-contact three-dimensional measuring device NH-3 manufactured by Mitaka Kogyo, an evaluation length of 2 mm, and a cutoff value of 0.8 mm. The mold surface was measured at an evaluation speed of 0.3 mm / sec.

  In the case of a molded article for a light reflector, particularly a molded article for a light reflector for directly forming a light-reflecting metal layer, a thermoplastic resin composition is used and the type of the thermoplastic resin composition is molded. The mold combination for this is particularly important.

  When molding a thermoplastic resin composition containing a polyester resin, the surface state (surface roughness) of the mold particularly affects the surface state of the molded article for light reflector. This is due to the flow characteristics of the polyester resin. Since the polyester resin has good fluidity, the resin also flows between minute irregularities on the mold surface. As a result, the molded product becomes a mold. There is a tendency to transfer the surface state of the film as it is.

  This tendency tends to appear when the content of the polyester resin is 10% by mass or more in the thermoplastic resin constituting the thermoplastic resin composition, and becomes more prominent at 30% by mass or more, and 50% by mass. The above becomes more prominent, particularly prominent at 80% by mass or more, and most prominent in the case of 100% by mass of the polyester resin.

  Therefore, it is preferable to appropriately select the arithmetic average surface roughness Ra of the mold in accordance with the content of the polyester resin. For example, when the content of the polyester resin is 10% by mass or more, the arithmetic surface roughness Ra of the mold is preferably 0.07 μm or less, and when 30% by mass or more, Ra is preferably 0.065 μm or less, In the case of 50% by mass or more, Ra is preferably 0.06 μm or less, in the case of 80% by mass or more, 0.055 μm or less is preferable, and in the case of 100% by mass, 0.05 μm or less is preferable.

  A method for bringing the surface of the mold into such an arithmetic average surface roughness Ra is not particularly limited, and an ultrasonic polishing machine using a diamond file, a grindstone, a ceramic grindstone, a ruby grindstone, a GC grindstone, or the like. Alternatively, the desired arithmetic surface roughness Ra can be adjusted by polishing the mold surface manually. For example, in order to reduce the arithmetic surface roughness Ra of the mold to 0.07 μm or less, it is preferable to polish the mold surface at a polishing count of 4000 or more, and to set the arithmetic surface roughness Ra of the mold to 0.06 μm or less. Therefore, it is preferable to polish the mold surface with a polishing count of 5000 or more, and in order to reduce the arithmetic surface roughness Ra of the mold to 0.05 μm or less, it is preferable to polish the mold surface with a polishing count of 6000 or more. In order to reduce the arithmetic surface roughness Ra of the mold to 0.04 μm or less, it is preferable to polish the mold surface at a polishing count of 8000 or more, and to reduce the arithmetic surface roughness Ra of the mold to 0.03 μm or less. For this, it is preferable to polish the mold surface with a polishing count of 14000 or higher.

  In the present invention, when a thermoplastic resin composition containing a polyester resin is used as the thermoplastic resin composition, a chromium plated mold may be used instead of the mold polished as described above. Moreover, you may further chrome-plat on the metal mold | die polished as mentioned above. Of course, the mold polished as described above may be used as it is.

  And it exists in the tendency which can make the image clarity of the molded article for light reflectors favorable by manufacturing the molded article for light reflectors by such a method. Here, the image clarity of the molded article for the light reflector was measured with an optical comb width of 0.5 mm using Suga Test Instruments Co., Ltd. image clarity measuring instrument ICM-1DP in accordance with JIS H 8686. Is. The image clarity of the molded article for light reflector is preferably 90% or more, more preferably 93% or more, further preferably 95% or more, particularly preferably 96% or more, and most preferably 97% or more.

  The light reflector of the present invention has a light-reflecting metal layer directly formed on at least a part of the surface of a molded article made of the thermoplastic resin composition. When the diffuse reflectance after the initial stage or after the heat test is 3% or less, it is preferable because it performs a good function as a light reflector. The image clarity of the light reflector is preferably 90% or more, more preferably 93% or more, still more preferably 95% or more, particularly preferably 96% or more, and most preferably 97% or more.

  The method for directly forming the light reflecting metal layer on the molded product is not particularly limited, and can be formed by a known method such as vapor deposition. For example, the following method is mentioned.

  (1) First, the molded product is placed in a vacuum deposition apparatus, and an inert gas such as argon and oxygen are introduced to subject the molded product surface to plasma activation treatment. (2) Next, by energizing the electrode carrying the target in the vapor deposition apparatus, sputtered particles (aluminum particles or the like) sputtered by the plasma subjected to induction discharge in the chamber are adhered to the compact. (3) Furthermore, plasma polymerization treatment is performed on a gas containing silicon as a protective film for a metal vapor deposition film such as aluminum, or silicon oxide is deposited on the surface of the aluminum vapor deposition film by an ion plating method.

EXAMPLES Next, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited to these.
[Evaluation method of mold surface roughness]
The surface of the mold is measured with a non-contact three-dimensional measuring device NH-3 manufactured by Mitaka Kogyo at an evaluation length of 2 mm, a cutoff value of 0.8 mm, and an evaluation speed of 0.3 mm / sec. In accordance with JIS B0601 Then, the arithmetic average surface roughness Ra was determined.
[Evaluation method of resin]
(1) Reduced viscosity (ηsp / C)
50 ml of a 1: 1 (mass ratio) mixed solvent of phenol and tetrachloroethane (trade name “PTM11”, manufactured by Kanto Chemical Co., Ltd.) is added to 0.25 g of polybutylene terephthalate resin, and the mixture is added at 140 ° C. for 10 to 30 minutes. Dissolved to obtain a solution. After adjusting the temperature for 3 minutes in a constant temperature water bath at 25 ° C., the time taken to pass between the marked lines was measured with an Ubbelohde viscometer to determine the reduced viscosity ηsp / C.

ηsp / C = (ηrel-1) / C = (T / T0-1) / C
T: Sample solution passage time (second)
T0: transit time between capillary gauge lines of mixed solvent only (seconds)
C: Sample concentration (g / dl)
(2) Intrinsic viscosity ([η])
Using a 1: 1 (mass ratio) mixed solvent of phenol and tetrachloroethane, polyethylene terephthalate resin solutions having concentrations of 0.2, 0.3, and 0.4 g / dl were prepared. The viscosity of the solution of each concentration was measured at a temperature of 25 ° C. using an Ubbelohde automatic viscometer (manufactured by SAN DENSHI Co., Ltd., AVL-2C), and the obtained value was measured with a Huggins plot at a concentration of 0 g / dl. And the intrinsic viscosity [η] was determined.
(3) Acid value Polybutylene terephthalate was dissolved in benzyl alcohol and titrated with a 1 / 50N NaOH benzyl alcohol solution.
[Method for evaluating molded products]
(1) Releasability After drying the melt-kneaded pellets of each composition, cylinder temperature 260 ° C., mold temperature 80 ° C., cooling time 20 seconds, cycle 35 seconds using an injection molding machine (SANJECT 3601 60T manufactured by Yamashiro Seimitsu Co., Ltd.) Under these conditions, a cylinder-formed product having a length of 50 mm, an inner diameter of 45 mm, and a wall thickness of 3 mm to 4 mm was molded, and the protruding force (release force) at the time of release was measured with a pressure sensor. The smaller the release force, the better the mold release properties.

In addition, when this mold release force is 500 N or less, when it molds as a component of various lamps, it has favorable mold release property. When the release force exceeds 500 N, there is a difficulty in releasability, resulting in a decrease in productivity or a problem when molding a large molded product or a molded product having a complicated shape.
(2) Fogging property To a fogging tester (fogging tester WSF-2 improved type manufactured by Suga Test Instruments Co., Ltd.) in which a small piece of about 20 mm x 10 mm is cut from the molded product, 6 g is put into a test tube (φ30 x 200 mm), and the temperature is adjusted to 160 ° C I set it. Furthermore, after covering the test tube with a heat-resistant glass (Tempax glass 55 × 55 × 3 mmt), an aluminum block in which cooling water whose temperature was adjusted to 25 ° C. was passed, and heat treatment was performed at 160 ° C. for 20 hours. Carried out. As a result of this heat treatment, deposits due to decomposition products sublimated from the resin composition were deposited on the inner wall of the glass plate. The haze (light transmittance) in these glass plates was measured using a reflection / transmittance meter (HR-100, manufactured by Murakami Color Research Laboratory).

In addition, when the glass plate haze after heating at 160 ° C. for 20 hours exceeds 45%, there is a practical problem as various lamp parts. When the haze of the glass plate is 45% or less, it functions as a component of various lamps and is preferable, and the case of 20% or less is particularly preferable.
(3) Image clarity In accordance with JIS H 8686, the image clarity of the molded article for light reflectors with an optical comb width of 0.5 mm is obtained by using the image measuring instrument ICM-1DP manufactured by Suga Test Instruments Co., Ltd. It was measured.
[Evaluation method of light reflector]
(1) Visual appearance evaluation The visual appearance of the light reflecting metal layer of the light reflector was evaluated by visual inspection before and after the heat resistance test for defects (defects due to a release mark, flaw skin-like defects, whitening).
1) Release mark A: There is no white pattern due to transfer of mold surface unevenness due to poor resin releasability (mold uneven transfer) and fluffy unevenness due to resin shrinkage (flow mark shape).

  ◯: A white pattern due to mold uneven transfer or a white pattern in the form of a flow mark is slightly recognized depending on the viewing angle, but at a level that does not cause any problem in practice.

  (Triangle | delta): The white pattern by type | mold uneven | corrugated transfer or the white pattern of a flow mark shape exists in the surface.

X: The white pattern by the uneven | corrugated transcription | transfer and the white pattern of a flow mark shape are conspicuous conspicuously.
2) Scratch-like defects A: There is no rough surface (roughness, rough feeling).

  ○: Roughness of the surface (roughness, rough feeling) is slightly recognized depending on the visual angle, but it is a level with no practical problem.

  (Triangle | delta): There exists a rough surface (roughness, a rough feeling).

X: The surface roughness (roughness, rough feeling) is remarkably conspicuous.
3) Whitening (before heat test)
(Double-circle): There is no whitening of the non-uniform | heterogenous shape (spotted shape etc.) resulting from the additive oozing out to the molded article surface at the time of shaping | molding.

  A: Whitening of a non-uniform shape (such as a spotted shape) resulting from the exudation of the additive to the surface of the molded product at the time of molding is slightly observed depending on the visual angle, but at a level causing no practical problem.

  (Triangle | delta): Whitening of the non-uniform | heterogenous shape (spotted shape etc.) resulting from the additive oozing out to the molded article surface at the time of shaping | molding is recognized.

X: Whitening of a non-uniform shape (spotted shape, etc.) due to the additive oozing out to the surface of the molded product during molding is remarkably recognized.
4) Whitening (after heat test)
A: Whitening of a non-uniform shape (spotted shape, etc.) resulting from the exudation of the additive to the surface of the molded product during molding, or non-uniformity resulting from the exudation of the additive to the surface of the molded product during the heat test. There is no whitening of the shape (spots etc.).

  ○: Whitening of a non-uniform shape (spotted shape, etc.) due to the additive oozing out to the surface of the molded product during molding, or non-uniformity due to the additive oozing out to the surface of the molded product during the heat test. Whitening of the shape (spots, etc.) is slightly observed depending on the viewing angle, but at a level that is not a problem for practical use.

  Δ: Whitening of a non-uniform shape (spotted shape, etc.) resulting from the exudation of the additive to the surface of the molded product during molding, or non-uniformity resulting from the exudation of the additive to the surface of the molded product during the heat test. Whitening (such as spots) is observed.

X: Whitening of a non-uniform shape (spotted shape, etc.) resulting from the exudation of the additive to the surface of the molded product during molding, or non-uniformity resulting from the exudation of the additive to the surface of the molded product during the heat test Whitening of various shapes (such as spots) is noticeable.
(2) Diffuse reflectance The diffuse reflectance of the light reflector before and after the heat resistance test was measured using a reflection / transmittance meter HR-100, Murakami Color Research Laboratory.

In addition, when the diffuse reflectance after the initial stage or after the heat test is 3% or less, it functions as a light reflector and is good. When the diffuse reflectance exceeds 3%, there is a practical problem as a light reflector.
(3) Image clarity Based on JIS H 8686, the image clarity of the light reflector was measured with an optical comb width of 0.5 mm using a image clarity measuring device ICM-1DP manufactured by Suga Test Instruments Co., Ltd.
(4) Metal film adhesive strength The initial strength of the light reflector and the metal layer adhesive strength after the heat resistance test were evaluated by a cross-cut peel test. For the cross-cut peel test, a cellophane tape (product number: CT-24) manufactured by Nichiban was used, and a cross-cut peel test with 100 cross cuts at 1 mm intervals was performed. The evaluation was expressed as a percentage (%) of the number of grids remaining on the surface of the molded product with respect to the total number of grids. Those that are 100% at the initial stage and 80% or more after the heat resistance test function as a light reflector and are good.

The initial cross-cut peel test of the light reflector was performed after aluminum deposition was performed on the light reflector molded article and left at room temperature for 24 hours or more. Further, the cross-cut peeling test after the heat test was performed after the light reflector was left at room temperature for 24 hours or more after the heat test.
(5) Heat resistance test Using a gear oven GPH (H) -100 manufactured by Tabeisbek Co., Ltd., the light reflector was left in hot air at 160 ° C. for 24 hours for heat treatment.
Example 1
As component (A), (a-1) polybutylene terephthalate resin (manufactured by Mitsubishi Rayon Co., Ltd., trade name “Toughpet N1300”, reduced viscosity ηsp / C = 1.01, acid value = 42 meq / kg) 80 parts by mass And (a-2) polyethylene terephthalate resin (Mitsubishi Rayon Co., Ltd., trade name “Dianite MA521H-D”, intrinsic viscosity [η] = 0.780) 20 parts by mass, (B) as component (B- 1) Montanic acid glycerin triester (manufactured by Clariant Japan Co., Ltd., trade name “Licolube WE4”) 0.2 parts by mass, (E) as reinforcing material (E-1) talc (manufactured by Hayashi Kasei Co., Ltd., trade name) “# SG200”, an average particle diameter of 4.4 μm) surface-treated with γ-glyoxydoxypropyltrimetraxin (0.5% by mass), 1 part by mass, and carbon black as a pigment (Commercially available from Sumika Color Co., Ltd., trade name “Black BPM-8E756”) 0.24 parts by mass, mixed and homogenized with a V-type blender for 5 minutes, vented with a cylinder temperature of 260 ° C. and a diameter of 30 mm The mixture was put into a twin screw extruder to obtain pellets.

  It was 406 N when the mold release force was measured using the obtained pellet.

  Separately, using a molding machine (IS80FPB manufactured by Toshiba Corporation), pellets were molded at a cylinder temperature of 260 ° C. and a mold temperature of 80 ° C. (100 mm square plate mold (with a mold surface of # 14000). Polished, arithmetic average surface roughness Ra = 0.03 μm) was injection molded to obtain a flat molded product (100 mm × 100 mm) for a light reflector. The image clarity of the obtained flat plate molded product was 98.2%.

  Next, when the fogging property was evaluated using the obtained 100 mm square flat plate molded product, the haze value was 27%.

  Moreover, aluminum was directly vapor-deposited on the obtained 100 mm square flat plate molded article by the following method. First, an inert gas and oxygen were introduced into a vapor deposition apparatus under a vacuum state, and the inside of the chamber was brought into a plasma state to perform a plasma activation process for activating the surface of the molded product. Next, aluminum was vapor-deposited with the vapor deposition apparatus under a vacuum state. By energizing the electrode carrying the target in the vapor deposition system, plasma is generated by induction discharge in the chamber, the ions in the plasma sputter the target, and the sputtered particles, that is, the aluminum particles jumped out of the target, are on the surface of the molded product An aluminum vapor deposition film was formed on the entire surface. The film thickness of the aluminum vapor deposition film was 80 nm. Further, a plasma polymerization treatment was performed as a protective film on the aluminum deposition surface. As the plasma polymerized film, hexamethylenedisiloxane was introduced under a vacuum plasma state to form a silicon dioxide polymerized film. The film thickness of the silicon dioxide polymer film was 50 nm.

  In this way, a light reflector in which a light-reflecting metal layer was directly formed on a thermoplastic polyester resin molded product was obtained. The evaluation results of the obtained light reflector are shown in Tables 1 and 3.

Next, a heat resistance test of the obtained light reflector was performed. The evaluation results of the light reflector after the test are shown in Table 1.
Examples 2-8
Pellets, molded articles, and light reflectors were obtained in the same manner as in Example 1 except that the composition of the thermoplastic resin composition was changed to the composition shown in Table 1. The evaluation results are shown in Table 1.
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Example 9
Using the pellets of Example 1, an injection molding machine (IS80FPB manufactured by Toshiba Corp.) was used, and a 100 mm square plate mold (with a mold surface of # 8000) under the conditions of a cylinder temperature of 260 ° C. and a mold temperature of 80 ° C. The product was polished into an arithmetic average surface roughness Ra = 0.04 μm) to obtain a flat molded product (100 mm × 100 mm) for a light reflector. Aluminum was directly vapor-deposited on the obtained 100 mm square flat plate molded article in the same manner as in Example 1 to obtain a light reflector. Table 2 shows the image clarity of the obtained light reflector.
Example 10
A light reflector was obtained in the same manner as in Example 9 except that a mold whose surface was polished with # 5000 (arithmetic average surface roughness Ra = 0.06 μm) was used as a mold for a flat plate. . Table 2 shows the image clarity of the obtained light reflector.
Comparative Example 1
A light reflector was obtained in the same manner as in Example 10 except that a mold whose surface was polished with # 3000 (arithmetic average surface roughness Ra = 0.08 μm) was used as the mold for a flat plate. . Table 2 shows the image clarity of the obtained light reflector.
Comparative Example 2
A light reflector was obtained in the same manner as in Example 10 except that a mold whose surface was polished with # 800 (arithmetic average surface roughness Ra = 0.13 μm) was used as the mold for the flat plate. . Table 2 shows the image clarity of the obtained light reflector.
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The materials listed in Table 1 were as follows.
(B-1) Montanic acid glycerin triester: manufactured by Clariant Japan Co., Ltd., trade name “Licolub WE4”
(B-2) Sodium montanate: manufactured by Clariant Japan Co., Ltd., trade name “Licomont NaV”
(B-3) Calcium montanate: manufactured by Clariant Japan Co., Ltd., trade name “Licomont CaV102”
(C-1) Fatty acid glycerol monoester: manufactured by Riken Vitamin Co., Ltd., trade name “Riquemar S100A”
(E-1) Talc (average particle size 4.4 μm): Hayashi Kasei Co., Ltd. product name “# SG200” surface-treated with γ-glyoxydoxypropyltrimetraxin (0.5% by mass) (E-2) Talc (average particle size 0.9 μm): manufactured by Hayashi Kasei Co., Ltd., trade name “# SG2000” and surface treatment with γ-glyoxydoxypropyltrimetraxin (epoxysilane) (0.5 mass) %) (E-3) Kaolin (0.4 μm): hydrous kaolin surface-treated with stearic acid (0.5% by mass), manufactured by ENGELHARD, trade name “ASP-101”
(Others) Sodium benzoate: Wako Pure Chemical Industries, Ltd.

Claims (4)

Using a thermoplastic resin composition containing a polyester resin, a molded article for a light reflector having an arithmetic average surface roughness Ra of 0.075 μm or less and an image sharpness of 90% or more is obtained. the method of manufacturing an optical reflection-body moldings, wherein obtain Rukoto. By using a thermoplastic resin composition containing a polyester resin, and a mold having polished the surface with polishing grit # 5000 or more, Rukoto obtain a light reflection-body moldings image sharpness is 90% or more A method for producing a molded article for a light reflector, characterized by comprising: By using a thermoplastic resin composition containing a polyester resin, molded in chrome plated mold, the light reflector image sharpness is characterized Rukoto obtain a light reflection-body moldings is 90% or more Method of manufacturing molded products.   The light reflection body by which the light reflection metal layer was directly formed in the surface of at least one part of the molded article for light reflectors obtained by the manufacturing method of Claims 1-3.