JP2012164577A - Thin-walled resin reflecting mirror with high luminance and low gaseous property - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thin-walled resin reflecting mirror with high luminance and a low gaseous property which can restrain generation of a silver color and cloudiness at the time of molding of components having a thin-walled sections and is excellent in appearance before and after thermal aging, specially maintenance of surface reflectance after applying metal deposition, for example, aluminum deposition and is also excellent in rigidity and heat resistance.SOLUTION: In the thin-walled resin reflecting mirror with high luminance and a low gaseous property made of a resin composition, metal deposition is applied to the reflecting mirror, thickness of the metal-deposited section of a mold is 2 mm on average, initial surface reflectance of the metal-deposited section (vapor deposited surface) is 90% or more, surface roughness of the metal-deposited section is 12 nm or below, and a haze value of a glass plate after completing a fogging test on the resin composition is 1.0 or below.

Description

  The present invention relates to a high-intensity, low-gas thin resin reflector.

  Conventionally, thermosetting resins such as unsaturated polyester (BMC) have been widely used as materials for resin parts that reflect light (reflecting mirrors; reflectors, mainly automobile lamp parts). Although such a thermosetting resin is lighter than aluminum, the specific gravity exceeds 2.0, and therefore further weight reduction is required. In addition, the thermosetting resin has problems such as complicated post-processing of the molded product and contamination of the working environment due to dust and the like. Therefore, as a material for a reflecting mirror, conversion from a thermosetting resin to a thermoplastic resin such as polyetherimide is proceeding.

  In addition, high-heat-resistant polycarbonate and primers (undercoat) for metal deposition are required as materials for parts that require metallic luster (extension reflectors for automobiles) among reflectors. A glass reinforced material of polyethylene terephthalate (PET) / polybutylene terephthalate (PBT) is used. Furthermore, a technique using a polyphenylene ether resin having excellent heat resistance and hydrolysis resistance as an automobile lamp part is disclosed (for example, see Patent Document 1).

  In addition, as a technique for increasing the surface gloss of the reflecting mirror, a technique for directly depositing aluminum on a molded product obtained using a mirror-finished mold (see, for example, Patent Document 2), a mold temperature, A technique (for example, see Patent Document 3) of setting and molding in a range from a temperature about 40 ° C. lower than the temperature to a heating deformation temperature is disclosed.

Japanese Patent Laid-Open No. 5-320495 Japanese Patent Laid-Open No. 11-60935 JP 11-116793 A

  In automotive lamp parts, which is the main use of resin reflectors, there is an increasing demand for further weight reduction of molded products. For example, there is a case where 50% or more weight reduction of conventional molded products is required. Therefore, it is necessary to significantly reduce the thickness of the molded product. In order to obtain a thin-walled molded product, generally high shear conditions are required. Generally, the molded product is deteriorated in appearance (silver, cloudiness, peeling, etc.) and the resin is not sufficiently filled in the thin-walled part. There is a tendency for appearance to deteriorate. In addition, the use environment temperature has been increased due to the recent improvement in the engine room temperature, and even under such an environment, it is required that the appearance of the molded product does not deteriorate during use.

  Regarding the characteristics in such a thin portion, none of the above-mentioned documents solves the above-mentioned literature. The technique described in Patent Document 1 has a problem that the fluidity of thin-walled parts cannot be satisfied, and the appearance of the base material and the appearance of metal deposition are poor. Similarly, the technique disclosed in Patent Document 2 does not solve the problem of deterioration of the appearance of the molded product in the thin portion. In addition, the technique disclosed in Patent Document 3 is not studied for the appearance of the molded product in the thin-walled portion, and in order to obtain a desired effect, the molding conditions must be extremely limited. Since a molded article usually has a complicated shape, it is difficult to control the molding conditions to be limited such that the mold temperature cannot be kept uniform during molding.

  Therefore, the present invention provides a high-intensity, low-gas thin-walled resin reflector that is excellent in maintaining the appearance before and after thermal aging, particularly the surface reflectance, in a thin-walled portion that has been subjected to metal deposition, for example, aluminum deposition.

  The inventors of the present invention have made extensive studies to achieve the above-mentioned problems. As a result, the surface appearance before and after thermal aging, particularly the surface reflectance, can be obtained even if the molding condition has a thin portion where the molding conditions are high temperature and high shear. The present inventors have found a reflecting mirror excellent in holding and have completed the present invention.

  That is, the present invention is as follows.

[1]
A high-intensity, low-gas thin resin reflector made of a resin composition,
The reflecting mirror is metal-deposited,
The molded product thickness of the metal-deposited portion is an average of 2 mm or less,
The initial surface reflectance of the metal-deposited part (deposition surface) is 90% or more,
The surface roughness of the metal-deposited portion is 12 nm or less, and the haze value of the glass plate after performing the following fogging test on the resin composition is 1.0 or less. Low gas thin resin reflector.

<Foging test>
Put 50 g (± 1 g) of the resin composition in a glass sample bottle, leave it on a glass plate that can cover all the mouths of the glass sample bottle, cover it, and place it at 150 ° C. (± 5 ° C.) The glass plate is fogged by being heated for 24 hours underneath.

[2]
The high brightness and low gas thin resin reflector according to [1], wherein a heating temperature in the fogging test is 170 ° C.

[3]
The high-luminance, low-gas thin-walled resin reflector according to [1] or [2], wherein the thickness of the molded product on the metal-deposited portion is 1.5 mm or less on average.

[4]
After the thermal aging treatment for 24 hours in a 150 ° C. environment (± 5 ° C.) with respect to the initial surface reflectance, the reflectance of the surface reflectance of the reflecting mirror is 50% or more [1] to [3] The high-luminance and low-gas thin resin reflector according to any one of [3].

[5]
After the thermal aging treatment for 24 hours in a 150 ° C. environment (± 5 ° C.) with respect to the initial surface reflectance, the reflectance of the surface reflectance of the reflecting mirror is 70% or more [1] to [4] The high-luminance, low-gas thin resin reflector according to any one of [4].

[6]
After the thermal aging treatment for 24 hours in a 150 ° C. environment (± 5 ° C.) with respect to the initial surface reflectance, the surface reflectance retention of the reflecting mirror is 90% or more [1] to [5] The high-luminance, low-gas thin resin reflector according to any one of [5].

[7]
The high-luminance, low-gas thin resin reflector according to any one of [1] to [6], wherein the metal deposition is performed by a direct deposition method that does not require a primer.

[8]
The resin composition is
(A) polyphenylene ether resin (PPE);
(B) polystyrene resin;
(C) rubber polymer, and the ratio of each is (A) + (B) + (C) = 100% by weight,
(A) 59 to 98% by weight of polyphenylene ether resin (PPE),
(B) 1 to 40% by weight of polystyrene resin,
(C) 1-40% by weight of rubber polymer
And
The (C) rubber polymer is
(C-1) a hydrogenated block copolymer having a weight average molecular weight of 200,000 to 500,000,
(C-2) The high-luminance and low-gas according to any one of [1] to [7], comprising a hydrogenated block copolymer having a weight average molecular weight of 10,000 to 150,000. Thin-walled resin reflector.

[9]
The (C-1) is a hydrogenated block copolymer containing 10% by mass or more and less than 40% by mass of a monomer derived from a vinyl aromatic hydrocarbon,
The high brightness according to [8], wherein (C-2) is a hydrogenated block copolymer containing 40% by mass or more and 90% by mass or less of a monomer derived from a vinyl aromatic hydrocarbon.・ Low gas thin resin reflector.

[10]
The mass ratio ((C-1) / (C-2)) between the (C-1) and the (C-2) is in the range of 5/95 to 95/5 [8. ] The high-luminance and low-gas thin-walled resin reflector according to [9].

[11]
The (B) polystyrene resin is
(B-1) a polystyrene resin not reinforced with rubber;
(B-2) The high-brightness, low-gas thin-walled resin reflector according to any one of [8] to [10], comprising a polystyrene-based resin containing an acrylonitrile component.

[12]
The mass ratio ((B-1) / (B-2)) between the (B-1) and the (B-2) is in the range of 5/95 to 95/5 [11. ] The high-intensity, low-gas thin-walled resin reflecting mirror described in the above.

[13]
The melt flow rate (MFR) (test standard ISO 1133 pellet 200 ° C./5 kgf) of (B-1) is 1 g / 10 min or more, [11] or [12] Low gas thin resin reflector.

[14]
Any of [8] to [13], wherein the reduced viscosity of the (A) polyphenylene ether resin (0.5 g / dL solution of chloroform at 30 ° C.) is in the range of 0.2 to 0.6. High-intensity, low-gas thin-walled resin reflector as described in 1.

[15]
The reflecting mirror is obtained by a manufacturing method including a step of injecting the resin composition melted in a mold from a gate to a cavity,
The high brightness and low gas according to any one of [1] to [14], wherein the gate has a thickness of 2.0 mm or less, and a silver phenomenon does not occur in a molded product formed in the cavity. Thin-walled resin reflector.

[16]
The high brightness and low gas thin resin reflector according to [15], wherein the gate has a thickness of 1.0 mm or less.

[17]
[1] to [16], wherein the reflecting mirror is obtained by a production method including a step of molding the resin composition under conditions of a cylinder temperature of 300C to 340C and a mold temperature of 90C to 150C. ] The high-intensity and low-gas thin-walled resin reflector according to any one of the above.

[18]
The reflecting mirror is obtained by a manufacturing method including a step of molding the resin composition using a molding machine having a pressure reducing mechanism in a pellet feeder, [1] to [17] High brightness and low gas thin-walled resin reflector.

[19]
The high brightness and low gas thin resin reflector according to any one of [1] to [18], wherein the metal deposition is aluminum deposition.

[20]
The high brightness and low gas thin resin reflector according to any one of [1] to [19], which is used as a reflector attached to a moving body.

[21]
The high brightness and low gas thin resin reflector according to [20], wherein the moving body is powered by an internal combustion engine or a motor.

[22]
The high brightness and low gas thin resin reflector according to [20] or [21], wherein the moving body is a flying body, a land traveling body, a sea traveling body or an underwater traveling body.

[23]
The high brightness and low gas thin resin reflector according to any one of [20] to [22], wherein the moving body has wheels.

[24]
The high brightness and low gas thin resin reflector according to any one of [1] to [23], which is used as a reflector of a light source.

[25]
The high-brightness, low-gas thin resin reflector according to [24], wherein the light source is a halogen lamp, a discharge lamp, or an LED lamp.

[26]
The high-luminance, low-gas thin resin reflector according to any one of [19] to [25], which is an extension reflector, a reflector, other lamp parts, or a mirror.

[27]
(A) polyphenylene ether resin (PPE);
(B) polystyrene resin;
(C) rubber polymer, and the ratio of each is (A) + (B) + (C) = 100% by weight,
(A) 59 to 98% by weight of polyphenylene ether resin (PPE),
(B) 1 to 40% by weight of polystyrene resin,
(C) 1-40% by weight of rubber polymer
And
The (C) rubber polymer is
(C-1) a hydrogenated block copolymer having a weight average molecular weight of 200,000 to 500,000,
(C-2) A high-brightness, low-gas thin-walled resin reflector comprising a resin composition comprising a hydrogenated block copolymer having a weight average molecular weight of 10,000 to 150,000.

  The high-luminance, low-gas thin-walled resin reflector of the present invention has a good surface roughness of the metal-deposited portion even if the molded product thickness of the metal-deposited portion is as thin as 2 mm or less on average. It is a high-brightness, low-gas thin-walled resin reflector that has excellent appearance, has a haze value of 1.0 or less after the fogging test, and suppresses gas generation even in a high-temperature environment. . Such a high-brightness, low-gas thin-walled resin reflecting mirror of the present invention is excellent in surface reflectance retention, heat resistance and mechanical properties, and therefore can be effectively used particularly as an automobile lamp extension.

  Hereinafter, modes for carrying out the present invention (hereinafter referred to as the present embodiment) will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.

≪High brightness, low gas thin resin reflector≫
The high-brightness and low-gas thin resin reflector of the present embodiment is a high-brightness and low-gas thin-walled reflector made of a resin composition, wherein the reflector is metal-deposited, and the metal-deposited The average thickness of the molded product in the part is 2 mm or less, the initial surface reflectance of the metal-deposited part (deposition surface) is 90% or more, and the surface roughness of the metal-deposited part is 12 nm or less. And the haze value of the glass plate after performing the following fogging test about the said resin composition (a reflective mirror or a pellet) is 1.0 or less.

[Foging test;
Put 50 g (± 1 g) of the resin composition in a glass sample bottle, leave it on a glass plate that can cover all the mouths of the glass sample bottle, cover it, and place it at 150 ° C. (± 5 ° C.) The glass plate is fogged by being heated for 24 hours underneath. ]
In the high-brightness / low-gas thin-walled resin reflector according to this embodiment, the thickness of the molded product at the portion where the metal is deposited as described above is thinner (2 mm or less) than the conventional one. The weight reduction of a molded product becomes stronger every year, and the goal is to reduce the weight of a conventional molded product by 50% or more. Therefore, there is a demand in the market for the thickness of the molded product that must be reduced by 30% or more than the conventional one. Similarly, reduction of the thickness of the molded product is required for the portion where metal is deposited. The high-brightness, low-gas thin-walled resin reflector according to this embodiment has an appearance of a molded product even when the thickness of the molded product in which the metal is deposited as described above is thinner (2 mm or less) than the conventional one. (Having no peeling or clouding) and excellent haze value after the fogging test.

  The average thickness of the molded part of the metal-deposited portion is preferably 1.5 mm or less, more preferably 1 mm or less.

  Further, the surface roughness of the metal-deposited portion is preferably 12 nm or less, and more preferably 10 nm or less. When the surface roughness of the metal-deposited portion is within the above range, the appearance and other characteristics tend to be excellent. In the present embodiment, the surface roughness of the metal-deposited portion is a value measured by the method described in the examples described later. In order to make the surface roughness of the metal-deposited portion 12 nm or less, it is important to improve the mold transferability, for example, setting an appropriate molding temperature or mold temperature as described later, or This can be achieved by improving the fluidity of the resin composition.

  Furthermore, in the high-luminance and low-gas thin resin reflector of this embodiment, the initial surface reflectance of the metal-deposited portion (deposition surface) is 90% or more. A reflecting mirror having an initial surface reflectance within the above range is excellent in reflecting performance. In this embodiment, the initial surface reflectance of the metal-deposited portion (deposition surface) is a value measured by the method described in the examples described later. In order to make the initial surface reflectance of the metal-deposited portion 90% or more, it is important to improve the mold transferability and suppress the surface peeling that is likely to occur in a thin molded product. For example, as described later, an appropriate molding temperature and mold temperature are set, or the fluidity of the resin composition is improved, and the morphology of the resin composition is appropriately designed (for example, a phase of a continuous phase and a dispersed phase). It can be achieved by increasing the solubility).

  The high brightness and low gas thin resin reflector of this embodiment has a haze value of 1.0 or less after the fogging test. When the haze value of the glass plate is within the above range, the reflecting mirror made of the resin composition can suppress the generation of gas components even in a high temperature environment. Therefore, a part including the reflecting mirror (for example, a lamp part) has less precipitation of gas components such as cloudiness, and can maintain the reflection performance for a long time.

  In the present embodiment, the fogging property refers to a property that fogging occurs in a portion to which a gas component (outgas) generated when the resin composition is heated is attached. It means that the smaller the haze value of the glass plate after the fogging test is, the better the fogging property and the better the performance of the reflecting mirror made of the resin composition.

  In recent years, when a reflecting mirror is used as a part attached to a moving body, particularly a part attached to an automobile, there is an increasing demand for the haze value of the glass plate after the fogging test. For example, an extension reflector is required to have a haze value of 1.0 or less after performing the fogging test under the condition of heating in a 150 ° C. (± 5 ° C.) environment for 24 hours. .

  In the high-brightness / low-gas thin resin reflector according to the present embodiment, it is further preferable that the haze value of the glass plate is within the above range when the heating temperature in the fogging test is 170 ° C. In general, the higher the heating temperature in the fogging test, the more fogging of the glass plate and the higher the haze value.

  In order to set the haze value of the glass plate after the fogging test to 1.0 or less, it is necessary to use a resin composition having high heat resistance and low content of volatile components, and further to the glass plate after volatilization. This can be achieved, for example, by using a resin composition with a low content of adhering components.

  As described above, the high-intensity, low-gas thin resin reflector of this embodiment is excellent in the surface roughness of a thin metal-deposited component (deposition surface) and excellent in the initial surface reflectance of the metal-deposited portion. In addition, it has a feature of excellent fogging properties. For the first time by satisfying the above requirements, even if the metal vapor deposition surface has a thinner wall thickness than before, the appearance after metal vapor deposition is excellent and the retention rate of the surface reflectance of the reflector after heat aging treatment The effect that it is excellent in can be acquired.

  Regarding the retention rate of the surface reflectance of the reflector after the heat aging treatment, after the heat aging treatment for 24 hours in the environment of 150 ° C. (± 5 ° C.) with respect to the initial surface reflectance of the metal-deposited portion (deposition surface). The surface reflectance retention of the reflecting mirror is preferably 50% or more, more preferably 70% or more, and even more preferably 90% or more. Furthermore, the retention ratio of the surface reflectance of the reflector after heat aging treatment for 24 hours under a 170 ° C. environment (± 5 ° C.) is preferably 50% or more, more preferably 70% or more, More preferably, it is 90% or more. A reflecting mirror having a retention rate of the surface reflectance within the above range can maintain the reflection performance for a long period of time, and can be preferably used particularly as an automobile extension reflector.

  In the present embodiment, the retention rate of the surface reflectance is a value measured by the method described in Examples described later.

<Resin composition>
Since the high-brightness and low-gas thin-walled resin reflector of this embodiment is usually manufactured by injection molding, a thermoplastic resin is used as a material. It does not specifically limit as a thermoplastic resin, A well-known thing can be used. Examples of the thermoplastic resin include polyphenylene ether resin, polycarbonate resin, polymer alloy containing polycarbonate resin and ABS, polybutylene terephthalate resin, polyethylene terephthalate resin, and polyphenylene sulfide resin. In particular, since it is often used in the vicinity of a high-temperature light source, the resin composition used for the high-brightness, low-gas thin-walled resin reflector of this embodiment may contain a thermoplastic resin with high heat resistance. preferable. As the thermoplastic resin having high heat resistance, a resin having a glass transition temperature of 100 ° C. or higher is particularly preferable, and polyphenylene ether resin or high heat-resistant polycarbonate resin can be suitably used. Of these, polyphenylene ether resins are preferred.

As a resin composition containing a polyphenylene ether resin,
(A) polyphenylene ether resin (PPE);
(B) polystyrene resin;
(C) It is preferable to contain a specific rubber polymer.

  Hereinafter, the components (A) to (C) will be described in detail.

[Polyphenylene ether resin (A)]
<(A) component>
The (A) polyphenylene ether resin used in the present embodiment is not particularly limited, and a known one can be used, which may be a homopolymer or a copolymer.

  Polyphenylene ether homopolymers include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl-1,4-phenylene) ether, and poly (2,6-diethyl). -1,4-phenylene) ether, poly (2-ethyl-6-n-propyl-1,4-phenylene) ether poly (2,6-di-n-propyl-1,4-phenylene) ether, poly ( 2-methyl-6-n-butyl-1,4-phenylene) ether, poly (2-ethyl-6-isopropyl-1,4-phenylene) ether, poly (2-methyl-6-chloroethyl-1,4-phenylene) Phenylene) ether, poly (2-methyl-6-hydroxyethyl-1,4-phenylene) ether, poly (2-methyl-6-chloroethyl-1,4-phenylene) ether Etc. The.

  Among them, poly (2,6-dimethyl-1,4-phenylene) ether is preferable from the viewpoint of practical use as a raw material, and 2- (dialkylaminomethyl) -6-methylphenylene ether unit or 2- (N A polyphenylene ether containing a partial structure such as -alkyl-N-phenylaminomethyl) -6-methylphenylene ether unit is preferred.

  The poly (2,6-dimethyl-1,4-phenylene) ether preferably has an intrinsic viscosity of 0.3 to 0.7 as measured with a chloroform solution at 30 ° C. from a practical viewpoint as a raw material. More preferably, it is 0.35-0.6. By using two or more kinds of poly (2,6-dimethyl-1,4-phenylene) ether having different intrinsic viscosities, it is possible to widen the molecular weight distribution.

  As the copolymer of polyphenylene ether, a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, a copolymer of 2,6-dimethylphenol and o-cresol, Examples thereof include a copolymer of dimethylphenol, 2,3,6-trimethylphenol and o-cresol.

  The above-mentioned (A) polyphenylene ether resin may be used alone or in combination of two or more.

  The reduced viscosity of the (A) polyphenylene ether resin used in this embodiment (chloroform 0.5 g / dL solution at 30 ° C.) is preferably in the range of 0.2 to 0.6, preferably 0.25 to 0.55. More preferably, it is the range.

  In this embodiment, the reduced viscosity of (A) polyphenylene ether resin is the reduced viscosity (ηsp /) measured at 30 ° C. using an Ubbelohde viscometer tube with (A) polyphenylene ether as a 0.5 g / dL chloroform solution. c). The unit of reduced viscosity is dL / g.

  The weight average molecular weight of the (A) polyphenylene ether resin used in the present embodiment is not particularly limited, and the lower limit is preferably 30,000 or more, more preferably 35,000 or more, from the viewpoint of toughness and chemical resistance. Yes, more preferably 40,000 or more. The upper limit is 100,000 or less from the viewpoint of molding processability.

  The weight average molecular weight of the component (A) used in this embodiment was measured by gel permeation chromatography (GPC), tetrahydrofuran was used as the mobile phase, and a calibration curve prepared using the peak molecular weight of standard polystyrene. Is the weight average molecular weight determined using

  The hydroxyl group concentration of the component (A) used in the present embodiment is not particularly limited, and is preferably 0.8 or more per 100 units of monomer, more preferably 1.0 or more, and still more preferably 1.5 or more. The thermal stability at the time of shaping | molding can be improved by making the said hydroxyl group concentration into this range.

  The measurement of the hydroxyl group concentration can be performed in accordance with the method described in Journal of Applied Polymer Science: Applied Polymer Symposium 34, 103-117 (1978). The unit is the number of hydroxyl groups per 100 units of monomer (2,6-xylenol). For measurement, a U3310 spectrophotometer manufactured by Hitachi High-Technology Corporation can be used.

  In this embodiment, the hydroxyl group concentration of the polyphenylene ether used as the component (A) varies depending on the conditions for polymerizing the phenolic compound and the conditions for the quinone reaction after termination of polymerization. As an example of the polymerization, poly (2,6-dimethyl-1,4-phenylene) ether is described in JP-A Nos. 2000-281767 and 2000-281778, and 2,6-dimethyl is used at the time of polymerization. The amount of quinone compound produced varies depending on the amount of phenol added and time. In general, the larger the amount to be added, the greater the amount of quinone compound produced, the shorter the addition time. In the quinone reaction after the termination of polymerization, the terminal hydroxyl group concentration varies depending on the temperature and time. The higher the temperature and the longer the time, the higher the hydroxyl group concentration.

  In this regard, the thermal stability during molding can be improved by setting the hydroxyl group concentration of the component (A) used in the present embodiment to 0.8 or more per 100 units of monomer.

  In this embodiment, a polyphenylene ether resin modified with an unsaturated carboxylic acid or a derivative thereof can be used as a part of the polyphenylene ether used as the component (A). The modified polyphenylene ether is not particularly limited, and known ones can be used. For example, modified polyphenylene ether resins are described in JP-A-2-276823, JP-A-63-108059, JP-A-59-59724, and the like.

  The production method of the modified polyphenylene ether resin is not particularly limited and can be obtained by a known method. For example, it can be produced by melting and kneading an unsaturated carboxylic acid or derivative thereof with polyphenylene ether in the presence or absence of a radical initiator. Or it can manufacture by dissolving polyphenylene ether, unsaturated carboxylic acid, and its derivative (s) in the organic solvent in the presence or absence of a radical initiator, and making it react under a solution.

  It does not specifically limit as unsaturated carboxylic acid or its derivative (s), A well-known thing can be used. For example, maleic acid, fumaric acid, itaconic acid, halogenated maleic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, endo-cis-bicyclo [2.2.1] -5-heptene-2,3- Dicarboxylic acids and the like, acid anhydrides, esters, amides, and imides of these dicarboxylic acids; acrylic acid, methacrylic acid, and the like, and esters and amides of these monocarboxylic acids.

  In addition, a compound which is a saturated carboxylic acid but can itself be thermally decomposed into a derivative at the reaction temperature when producing the modified polyphenylene ether can also be used. Specific examples include malic acid and citric acid. These may be used alone or in combination of two or more.

  The blending amount of the (A) polyphenylene ether resin is preferably 59 to 98% by weight and preferably 60 to 98% by weight with respect to (A) + (B) + (C) = 100% by weight. More preferred is 70 to 95% by weight. By setting it as such a compounding quantity, the haze value of the glass plate after performing the said fogging test can be 1.0 or less, and generation | occurrence | production of gas can be suppressed also in a high temperature environment.

  About the compounding quantity of (B) polystyrene resin and (C) rubber-like polymer mentioned later, it is preferable that it is 1 to 40 weight%, respectively, it is more preferable that it is 1 to 20 weight%, and 1-15. More preferably, it is% by weight.

  The resin composition having the above blending amount is excellent in properties such as molding fluidity and fogging property. Therefore, the reflecting mirror made of the resin composition is excellent in surface appearance because the metal-deposited portion has a good surface roughness even if the thickness of the molded product is as thin as 2 mm or less on average. In addition, the haze value of the glass plate after the fogging test is 1.0 or less, and the generation of gas can be suppressed even in a high temperature environment. Furthermore, the reflecting mirror made of the resin composition tends to be excellent in surface reflectance and retention, and excellent in heat resistance and mechanical properties.

<(B) component>
In this embodiment, the (B) polystyrene resin used in combination with the (A) polyphenylene ether resin is not particularly limited, and a known one can be used, such as a homopolymer of a styrene compound, a styrene compound, And a polymer obtained by polymerizing a compound copolymerizable with a styrenic compound in the presence or absence of a rubbery polymer.

  The styrene compound is not particularly limited, and examples thereof include styrene, α-methylstyrene, 2,4-dimethylstyrene, monochlorostyrene, p-methylstyrene, p-tert-butylstyrene, and ethylstyrene. Among these, styrene is preferable from the viewpoint of practicality of raw materials.

  Examples of the compound copolymerizable with the styrene compound include methacrylic acid esters such as methyl methacrylate and ethyl methacrylate; unsaturated nitrile compounds such as acrylonitrile and methacrylonitrile; and acid anhydrides such as maleic anhydride. And used with styrenic compounds. Examples of rubbery polymers include conjugated diene rubbers, copolymers of conjugated dienes and aromatic vinyl compounds, hydrogenated products thereof, or ethylene-propylene copolymer rubbers.

In the present embodiment, particularly preferred (B) polystyrene resin is
(B-1) a polystyrene resin not reinforced with rubber;
(B-2) A polystyrene resin containing an acrylonitrile component.

  The (B-2) is preferably a styrene-acrylonitrile copolymer resin containing 5 to 15% by mass of an acrylonitrile component.

  The resin composition containing (B-1) and (B-2) is excellent in properties such as molding fluidity and fogging property. Therefore, the reflecting mirror made of the resin composition has a good surface roughness of the metal-deposited portion and excellent fluidity even if the thickness of the molded product with the metal-deposited portion is as thin as 2 mm or less on average. In addition, the haze value of the glass plate after the fogging test is 1.0 or less, and the generation of gas can be suppressed even in a high temperature environment. Furthermore, the reflecting mirror made of the resin composition tends to be excellent in surface reflectance and retention, and excellent in heat resistance and mechanical properties.

  The melt flow rate (MFR) of (B-1) used in this embodiment is not particularly limited, but is preferably 0.5 g / 10 min or more, more preferably 1 g / 10 min or more, and further preferably 2 g / 10. More than a minute.

  The melt flow rate (MFR) of the component (B-1) used in the present embodiment is a value obtained by measuring the pellet of the component (B-1) under the condition of 200 ° C./5 kgf according to the test standard ISO 1133.

  The styrene-acrylonitrile copolymer resin that is the component (B-2) used in this embodiment is preferably an acrylonitrile component, preferably 5 to 15% by mass, more preferably 7 to 11% by mass, and still more preferably 8 to 10% by mass. %, Particularly preferably 8.5 to 9.5% by mass.

  In the styrene-acrylonitrile copolymer, the content of the acrylonitrile component is preferably 5% by mass or more from the viewpoint of improving the balance between fluidity and heat resistance. Further, from the viewpoint of improving compatibility and mechanical properties, the content of the acrylonitrile component is preferably 15% by mass or less.

  The styrene-acrylonitrile copolymer preferably has a melt flow rate of 5 to 100 g / 10 minutes, more preferably 10 to 90 g / 10 minutes, and still more preferably 20 to 80 g / 10 minutes. The higher the melt flow rate of the styrene-acrylonitrile copolymer, the better the fluidity of the composition, but it is preferably 100 g / 10 min or less from the viewpoint of maintaining sufficient mechanical properties.

  The melt flow rate (MFR) of the component (B-2) used in the present embodiment is a value measured at 220 ° C. under a load of 10 kg in accordance with ASTM D-1238.

  In the present embodiment, the mass ratio of the component (B-1) and the component (B-2) is not particularly limited, and can be selected in an arbitrary range in consideration of desired fogging properties. In particular, in the present embodiment, when the haze value of the glass plate in the fogging test is 1.0 or less, the mass ratio of the component (B-1) to the component (B-2) from the standpoint of practical use. Is preferably (B-1) / (B-2) = 5/95 to 95/5, more preferably 20/80 to 80/20, still more preferably 30/70 to 70/30. is there.

<(C) component>
The (C) rubber polymer used in this embodiment is a hydrogenated block copolymer. The hydrogenated block copolymer is a hydrogenated product of a block copolymer containing a polymer block mainly composed of vinyl aromatic hydrocarbon and a polymer block mainly composed of a diene compound.

  In this embodiment, “mainly” means that the monomer is contained in the block in an amount of 50% by mass or more. Preferably, the monomer is contained in the block at 55% by mass or more, and more preferably 60% by mass or more.

  The vinyl aromatic hydrocarbon used in the present embodiment is not particularly limited, and a known one can be used. Examples thereof include alkyl styrene such as styrene, α-methyl styrene, p-methyl styrene, and p-tert-butyl styrene, paramethoxy styrene, vinyl naphthalene, and the like. Among these, styrene is preferable from the viewpoint of practicality of raw materials. These can be used as monomers derived from vinyl aromatic hydrocarbons.

  The content of the vinyl aromatic hydrocarbon-derived monomer unit in the polymer block mainly composed of vinyl aromatic hydrocarbons may be 50% by mass or more, preferably 55% by mass or more, more preferably 60% by mass or more. By setting it as this content, peeling resistance can be improved.

  The diene compound used in the present embodiment is not particularly limited, and a known compound can be used. For example, 1,3-butadiene, 2-methyl-1,3-butadiene (ie, isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene may be mentioned, and not only one type but also two or more types may be used. Among these, 1,3-butadiene and isoprene are preferable from the viewpoint of improving toughness. These can be used as monomer units derived from butadiene compounds.

  The content of the monomer unit derived from the butadiene compound in the polymer block mainly composed of the diene compound may be 50% by mass or more, preferably 55% by mass or more, and more preferably 60% by mass or more. . Toughness can be improved by setting it as this content.

  Examples of the method for producing the block copolymer before hydrogenation of the hydrogenated block copolymer (C) used in the present embodiment include Japanese Patent Publication No. 36-19286, Japanese Patent Publication No. 43-171979, The methods described in JP-B-46-32415, JP-B-49-36957, JP-B-56-28925, JP-A-59-166518 and the like can be mentioned.

  The block copolymer obtained by these methods is represented by the following general formulas (1) to (7), for example.

(Ab) _n (1)
a- (b-a) _n (2)
b- (ab) _n (3)
(In the formula, a represents a polymer block mainly composed of vinyl aromatic hydrocarbons, and b represents a polymer composed mainly of a diene compound. The boundary between the a block and the b block must always be clearly distinguished. N is an integer of 1 or more, preferably an integer of 1 to 5.)
[(B−a) _n ] _{(m + 1)} −X (4)
[(A−b) _n ] _{(m + 1)} −X (5)
[(B−a) _n −b] _{(m + 1)} −X (6)
[(A−b) _n −a] _{(m + 1)} −X (7)
(Wherein a, b and n are the same definitions as in formulas (1) to (3), and X is, for example, silicon tetrachloride, tin tetrachloride, epoxidized soybean oil, or a bifunctional to hexafunctional epoxy group-containing compound. Represents a residue of a coupling agent of a polyvinyl compound such as polyhalogenated hydrocarbon, carboxylic acid ester and divinylbenzene, or a residue of an initiator such as a polyfunctional organolithium compound, where m is an integer of 1 or more. Yes, preferably an integer from 1 to 10.)
The monomer units derived from the vinyl aromatic hydrocarbon in the copolymer block may be uniformly distributed or may be distributed in a tapered shape. The copolymer portion may contain a plurality of portions in which monomer units derived from vinyl aromatic hydrocarbons are uniformly distributed and a portion in which the monomer units are distributed in a tapered shape.

  As the hydrogenated block copolymer that can be used in the present embodiment, for example, hydrogenated products of the block copolymers represented by the above general formulas (1) to (7) can be used in an arbitrary ratio.

The (C) hydrogenated block copolymer used in this embodiment is obtained by hydrogenating the above block copolymer (hydrogenation reaction). It does not specifically limit as a catalyst used for hydrogenation reaction, A well-known thing can be used. In particular,
(I) a supported heterogeneous catalyst in which a metal such as Ni, Pt, Pd, or Ru is supported on carbon, silica, alumina, diatomaceous earth, or the like;
(Ii) a so-called Ziegler-type catalyst using an organic acid salt such as Ni, Co, Fe, Cr or a transition metal salt such as acetylacetone salt and a reducing agent such as organic aluminum;
(Iii) Uniform catalysts such as so-called organometallic complexes such as organometallic compounds such as Ti, Ru, Rh, and Zr can be mentioned.

  The method of the hydrogenation reaction is not particularly limited and can be performed by a known method. For example, Japanese Patent Publication No. 42-8704, Japanese Patent Publication No. 43-6636, Japanese Patent Publication No. 63-4841, Japanese Patent Publication No. 1-337970, Japanese Patent Publication No. 1-35381, and Japanese Patent Publication No. 2-9041 The methods described can be mentioned and can be hydrogenated in a hydrocarbon solvent in the presence of a hydrogenation catalyst to obtain a hydrogenated product. At that time, the hydrogenation rate of the block copolymer can be controlled by adjusting the reaction temperature, reaction time, hydrogen supply amount, catalyst amount and the like.

  In the hydrogenated block copolymer as the component (C) used in the present embodiment, the total hydrogenation rate of unsaturated double bonds based on the diene compound is not particularly limited, but is preferably 90% or more, more preferably 95. % Or more, more preferably 99% or more. By setting the total hydrogenation rate within such a range, the thermal stability during molding, chemical resistance, and fluidity are excellent, and a good reflecting mirror can be obtained.

  Here, the total hydrogenation rate of the unsaturated double bond based on the diene compound is the hydrogenation relative to the content of the unsaturated double bond based on the diene compound incorporated in the block copolymer before hydrogenation. The percentage of unsaturated double bonds formed.

  In the present embodiment, the hydrogenation rate of the aromatic double bond based on the vinyl aromatic hydrocarbon in the block copolymer is not particularly limited, but is preferably 50% or less, more preferably 30% or less, and still more preferably. 20% or less. By setting the hydrogenation rate within such a range, the thermal stability during molding can be improved.

  In the present embodiment, the hydrogenation rate can be measured by a nuclear magnetic resonance apparatus (NMR).

  In the present embodiment, (C) a hydrogenated block copolymer used in the present embodiment can be obtained by removing the solvent from the hydrogenated block copolymer solution by a known method. If necessary, a step of deashing metals can be employed. Moreover, you may use reaction terminator, antioxidant, neutralizing agent, surfactant, etc. as needed.

  In the hydrogenated block copolymer (C) used in this embodiment, a polar group-containing functional group containing at least one selected from the group consisting of nitrogen, oxygen, silicon, phosphorus, sulfur and tin is bonded to the polymer. A modified block copolymer obtained by modifying a modified polymer or a hydrogenated block copolymer with a modifying agent such as maleic anhydride is also included.

  The (C) hydrogenated block copolymer used in the present embodiment can be blended with known naphthenic and paraffinic process oils and mixed oils thereof as softeners or processing aids.

The rubber polymer (C) used in this embodiment is
(C-1) a hydrogenated block copolymer having a weight average molecular weight of 200,000 to 500,000,
(C-2) It is preferable to include a hydrogenated block copolymer having a weight average molecular weight of 10,000 to 150,000.

  The resin composition containing the rubber polymer containing (C-1) and (C-2) is excellent in properties such as molding fluidity and fogging property. Therefore, the reflecting mirror made of the resin composition is excellent in surface appearance because the metal-deposited portion has a good surface roughness even if the thickness of the molded product is as thin as 2 mm or less on average. In addition, the haze value of the glass plate after the fogging test is 1.0 or less, and the generation of gas can be suppressed even in a high temperature environment. Furthermore, the reflecting mirror made of the resin composition tends to be excellent in surface reflectance and retention, and excellent in heat resistance and mechanical properties.

  Furthermore, in the component (C) used in this embodiment, the content of the monomer derived from the vinyl aromatic hydrocarbon in the (C-1) hydrogenated block copolymer is 10% by mass or more and less than 40% by mass. And the weight average molecular weight is preferably 200,000 to 500,000, and the (C-2) hydrogenated block copolymer has a content of a monomer derived from a vinyl aromatic hydrocarbon of 40 mass. % To 90% by mass, and the weight average molecular weight is preferably 10,000 to 150,000. By containing the components (C-1) and (C-2), not only the toughness is excellent, but also the morphology of the component (C) can be stabilized and the peel resistance can be improved.

  Adjustment of the content of the monomer derived from the vinyl aromatic hydrocarbon is carried out by using ether compounds such as dimethyl ether, diethyl ether, diphenyl ether, tetrahydrofuran, diethylene glycol dimethyl ether and diethylene glycol dibutyl ether as vinylating agents, trimethylamine, triethylamine, N, N, N A tertiary amine such as', N'-tetramethylethylenediamine and diazabicyclo [2.2.2] octane can be added during the production of the block copolymer. The content of the monomer derived from vinyl aromatic hydrocarbon can be measured by a nuclear magnetic resonance apparatus (NMR).

  (C-1) The content of the vinyl aromatic hydrocarbon-derived monomer in the block copolymer is preferably 10% by mass or more and less than 40% by mass, more preferably 15% by mass or more and less than 40% by mass. More preferably, it is 20 mass% or more and 35 mass% or less. The weight average molecular weight of the (C-1) hydrogenated block copolymer is 200,000 to 500,000 in terms of standard polystyrene, preferably 200,000 to 400,000, more preferably, as measured by GPC. Is 250,000-300,000.

  (C-2) The content of the vinyl aromatic hydrocarbon-derived monomer in the block copolymer is preferably 40% by mass to 90% by mass, and more preferably 45% by mass to 85% by mass. More preferably, it is 50 mass% or more and 80 mass% or less. The weight average molecular weight of the (C-2) hydrogenated block copolymer is 10,000 to 150,000, preferably 20,000 to 150,000, more preferably 30 in terms of standard polystyrene as measured by GPC. , 150,000 to 150,000.

  The weight average molecular weight of the component (C) used in this embodiment is a calibration curve prepared by measuring by gel permeation chromatography (GPC), using chloroform as the mobile phase, and using the peak molecular weight of standard polystyrene. Is the weight average molecular weight determined using

  In the present embodiment, the mass ratio of the component (C-1), the component (C-2), and the component is not particularly limited, and can be selected within an arbitrary range in consideration of desired fogging property, peeling resistance, and the like. it can. From the viewpoint of setting the haze value of the glass plate in the fogging test to 1.0 or less, the mass ratio of the component (C-1) to the component (C-2) is preferably (C-1) / (C-2). = 5/95 to 95/5, more preferably 5/95 to 80/20, and even more preferably 5/95 to 50/50.

  Furthermore, from the viewpoint of improving impact properties and toughness, other elastomer components can be used in combination as long as the required performance of the high-brightness, low-gas thin resin reflector of this embodiment is satisfied.

<Other additives>
Other known additives may be added to the resin composition used in the present embodiment as necessary, as long as the effects of the present invention are not impaired. One or more conventional additives such as stabilizers and inhibitors against heat and UV degradation, lubricants and mold release agents, colorants including dyes and pigments, nucleating agents, blowing agents, plasticizers, inorganic There are fillers and antistatic agents. As a specific example, it is preferable to add a heat stabilizer (antioxidant) for the purpose of improving the stability of the composition. It does not specifically limit as a heat stabilizer, A well-known thing can be used. For example, a hindered phenol-based antioxidant, a sulfur-based antioxidant, a phosphorus-based antioxidant, and the like may be used, and these may be used alone or in combination of two or more. For the purpose of improving thermal stability, it is also effective to add inorganic compounds such as zinc oxide, magnesium oxide and zinc sulfide.

  For the purpose of improving light resistance, it is preferable to add a stabilizer such as an ultraviolet absorber or a light stabilizer. It does not specifically limit as a ultraviolet absorber and a light stabilizer, A well-known thing can be used. For example, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-t-butylphenyl) benzotriazole, 2- (2′-hydroxy-3) Benzotriazole ultraviolet absorbers such as', 5'-di-t-butylphenyl) -5-chlorobenzotriazole; benzophenone ultraviolet absorbers such as 2-hydroxy-4-methoxybenzophenone; hindered amine light stabilizers, etc. Can be mentioned.

  It is preferable to add a polyolefin homopolymer or copolymer as a releasability improver from the mold during injection molding. In particular, polyethylene, an ethylene-propylene copolymer, an ethylene-butene copolymer, an ethylene-octene copolymer, and the like are more preferable from the viewpoint of having better releasability.

  Flame retardants such as phosphate esters; flame retardant aids such as antimony trioxide; char promoters; red phosphorus, various organic and inorganic phosphorus compounds other than the above; cyclic nitrogen such as melamine and melon Compounds and derivatives thereof; phosphazene compounds, halogen compounds, hydroxides such as magnesium hydroxide and aluminum hydroxide; metal oxides such as zinc borate compounds, zinc stannate compounds, antimony trioxide, iron oxide; silica, silica alumina Inorganic silicon compounds such as tetrafluoroethylene polymers, silicone compounds, phenol compounds and phenol resins, polyhydric alcohols, saccharides and the like may be added.

  Furthermore, in this embodiment, colorants such as various organic or inorganic dyes and pigments, waxes such as paraffin wax, microcristan wax, and low molecular weight polyethylene wax as a lubricant, higher fatty acids, metal salts or esters thereof, higher alcohols Various antistatic agents, conductive carbon, plasticizers and the like can be added.

<< Method for Producing Resin Composition >>
Examples of the method for producing the resin composition used in the present embodiment include a method of melt-kneading the components described above. As for the melt-kneading conditions for the respective components for producing the resin composition, a twin-screw extruder was used from the viewpoint of obtaining a resin composition that can sufficiently exhibit the desired effect in the present embodiment. In this case, it is preferable to perform melt kneading under conditions of a cylinder temperature of 290 to 350 ° C., a screw rotation speed of 50 to 500 rpm, and a vent vacuum of 100 Torr or less.

  In the method for producing a resin composition used in the present embodiment, a resin composition can be prepared in a large amount and stably by using a twin screw extruder.

≪Method for manufacturing high-intensity, low-gas thin resin reflector≫
The high-brightness and low-gas thin-walled resin reflector of the present embodiment can be manufactured, for example, by molding the above resin composition. The molding method is not limited, but injection molding, extrusion molding, vacuum molding, pressure molding, and the like are preferable. Furthermore, when the injection molding system and the pellet supply unit described in Japanese Patent No. 3786972 are used as a special prescription at the time of molding, a molded product can be obtained stably even with a gate where higher shear is applied. In particular, when the gate thickness is 0.5 mm or less, the effect of obtaining a molded product stably as compared with the conventional case is remarkable. Furthermore, in the case of a gate having a thickness of 2.0 mm or less, it is effective in reducing silver and a molded product having an excellent appearance can be obtained.

  In the present embodiment, the “gate” refers to a gate in which molten resin is injected into a cavity in a mold.

  Usually, when a molded product is obtained from a resin composition, the thickness of the molded product or the thickness of the gate tends to be reduced, so that heat tends to be generated by shearing. The degree of influence varies depending on the type of resin composition used and the type of molded product. In general, an alloy of polyphenylene ether (PPE) generates heat due to shearing, so that the compounding agent becomes unstable and silver is generated in a molded product. The high-brightness, low-gas thin-walled resin reflecting mirror of this embodiment can effectively suppress the above-described problems particularly when the gate is thin or the molded product is thin. Specifically, the peeling phenomenon can be reduced even if the thickness of the gate is 2 mm or less. In addition, even if the gate thickness is 1.5 mm or less, 1.0 mm or less, or 0.5 mm or less, the molded product in the cavity is hardly peeled off, and the molded product formed in the cavity. There is a tendency that the silver phenomenon does not occur, and a stable molded product tends to be obtained.

  Moreover, it is preferable that the high-intensity and low-gas thin resin reflector of this embodiment is obtained by a manufacturing method including a step of molding the resin composition using a molding machine having a pressure reducing mechanism in a pellet feeder.

  The pressure during the molding is preferably 300 Torr or less, and more preferably 100 Torr or less.

  Furthermore, the technique of the injection molding method using carbon dioxide (Japanese Patent Laid-Open No. 2002-79540) can be used in combination. In the injection molding method, the filling pressure of carbon dioxide can be up to 20 MPa, but is practically preferably about 10 to 15 MPa. Further, the amount of carbon dioxide absorbed into the resin is preferably 5% by mass or less, and more preferably 2 to 3% by mass practically. The injection molding method is an effective means for thin-walled flow because the fluidity is improved by 20% or more as the injection pressure is reduced by 20% or more.

  The high-brightness, low-gas thin-walled resin reflector according to the present embodiment includes a step of molding the resin composition under conditions of a cylinder temperature of a molding machine of 300 ° C. to 340 ° C. and a mold temperature of 90 ° C. to 150 ° C. It is preferably obtained by a method. By this manufacturing method, it is possible to obtain a reflecting mirror in which the surface roughness of the metal-deposited portion and the initial surface reflectance of the metal-deposited portion (deposition surface) are within the above-described range. The conditions in the production method are more preferably a cylinder temperature of 310 ° C. to 340 ° C., a mold temperature of 100 ° C. to 150 ° C., further preferably a cylinder temperature of 320 ° C. to 340 ° C., and a mold temperature of 110 ° C. to 150 ° C. .

  The reflecting mirror obtained by the above-described manufacturing method has a good surface roughness of the metal-deposited part, even if the thickness of the molded part of the metal-deposited part is as thin as an average of 2 mm or less. Moreover, the haze value of the glass plate after performing the said fogging test is 1.0 or less, and generation | occurrence | production of gas can be suppressed also in a high temperature environment. Furthermore, the reflecting mirror obtained by the manufacturing method described above tends to have excellent surface reflectivity and retention, and excellent heat resistance and mechanical properties.

  The high-brightness, low-gas thin-walled resin reflector according to this embodiment is a metal-deposited metal mirror. The metal vapor deposition method is not limited but is preferably a direct vapor deposition method that does not require a primer. The metal deposition is preferably aluminum deposition.

  Hereinafter, the vapor deposition method by the presence or absence of a primer is demonstrated taking a lamp reflector as an example.

  Generally, as a method of metal vapor deposition, there is “dry plating” (so-called dry metal plating method), specifically, vacuum vapor deposition method, ion plating method (ion plating method) or an intermediate technique thereof. A sputtering method can be exemplified.

The specific manufacturing method is shown below by taking vacuum deposition as an example.
(I) Degreasing the injection-molded reflecting mirror in a solvent such as isopropyl alcohol (Dipping), and drying at 60 to 120 ° C. if necessary.
(II) If necessary, apply and cure a primer (undercoat) on the surface of the molded product after degreasing.
(III) The molded product is attached to a supporting jig, inserted into a vacuum vessel, evacuated, and evaporation of evaporated metal such as metallic aluminum evaporated under a predetermined pressure is started. At this time, if necessary, the attached jig is rotated and revolved above the evaporation source. The thickness of the metal film is 0.05 to 0.1 μm.
(IV) After vapor deposition, if necessary, a top coating is applied to protect the vapor deposition surface.

  The primer is used for the purpose of (a) improving the surface smoothness of the reflecting surface, (b) improving the adhesion between the metal film and the surface of the molded product. The film thickness is about 10 to 50 μm. As the primer paint, for example, melamine alkyd type, urethane type and acrylic type are generally used. The acrylic type is mainly UV curable type, and the others are mainly heat curable type. As the primer coating used in the high-brightness, low-gas thin-walled resin reflector of this embodiment, a urethane system that can provide a cured film having excellent heat resistance is preferable. In particular, those obtained by a reaction between a long-chain diol having a main chain of polybutadiene and a blocking isocyanate blocked with phenol or the like (curing and baking conditions are 150 ° C. or higher, preferably 180 ° C. or higher and heated for 1 hour or longer). preferable.

  In addition, the high-brightness, low-gas thin-walled resin reflecting mirror of this embodiment can be vapor-deposited without using a primer. When a primer is not used, it is preferable to employ an ion plating method (ion plating method) that is excellent in adhesion to the substrate.

≪Usage≫
The high-luminance and low-gas thin resin reflector of this embodiment can be used as a reflector attached to a moving body. The moving body is preferably powered by an internal combustion engine or a motor. Examples of the moving body include a flying body, a land traveling body, an ocean traveling body, and an underwater traveling body. Furthermore, it is more preferable that the moving body has wheels.

  The high-intensity, low-gas thin resin reflector of this embodiment can be used as a light source reflector. The type of the light source is not particularly limited, and examples thereof include a fluorescent lamp, a mercury lamp, a halogen lamp, a discharge lamp, and an LED lamp. The light source is preferably a halogen lamp, a discharge lamp or an LED lamp.

  The high-brightness / low-gas thin resin reflector of this embodiment is preferably an extension reflector, a reflector, other lamp parts, or a mirror. In particular, the high-brightness, low-gas thin resin reflector of this embodiment is preferably used for a vehicle with wheels. For example, it is used as a vehicle extension reflector, a vehicle reflector, a vehicle lamp, or a vehicle mirror. be able to.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated concretely, this invention is not limited to these Examples.

  The resin compositions obtained in Examples and Comparative Examples, methods for measuring the physical properties of the molded products, and raw materials are shown below.

  Each measured value in Examples and Comparative Examples was determined by the following method.

(1) Deflection temperature under load (HDT) (DTUL: High load 1.82 MPa)
It was measured by a method based on ISO 75.

(2) Molding fluidity (SSP)
Injection molding machine manufactured by TOSHIBA MACHINE Co., Ltd .: Short shot pressure (SSP) of a 0.16 cm thick tanzaku (both-end gate) test piece prepared from the resin compositions obtained in Examples and Comparative Examples using IS-80C Was measured by gauge pressure. The lower the gauge pressure, the better the molding fluidity.

(3) Surface reflectivity For the vapor-deposited products created in the examples and comparative examples, the surface reflectivity of the aluminum-deposited portion (deposition surface) was measured using a reflectometer TR-1100AD / S manufactured by Tokyo Denshoku Co., Ltd. Measured with As the measurement points on the vapor deposition surface, three portions having a flat shape and no protrusions were selected. The said measurement was performed at normal temperature, and made the average value of the measurement result of the said 3 places the surface reflectance.

  Moreover, the said measurement was similarly implemented about the vapor deposition goods after carrying out the heat aging process using oven in the conditions of 150 degreeC * 24 hours and 170 degreeC * 24 hours.

  The retention ratio of the surface reflectance was defined as “surface reflectance after thermal aging treatment / surface reflectance before thermal aging treatment × 100”.

(4) Tensile strength test and tensile elongation test The tensile strength test and the tensile elongation test were performed in a 23 ° C environment by a method based on the measurement method of ISO 527-1.

(5) Flexural strength test and flexural modulus test The flexural strength test and flexural modulus test were performed in a 23 ° C environment by a method based on ISO 178.

(6) Charpy impact strength test The Charpy impact strength test was performed in a 23 ° C environment by a method based on ISO 179.

(7) Silver / cloudiness determination About the molded article (before metal vapor deposition) and vapor deposition article created by the Example and the comparative example, the degree of generation | occurrence | production of silver and cloudiness was determined visually. A case where no silver or cloudiness occurred and no problem was observed in the appearance was rated as ◯, and a case where silver or cloudiness occurred significantly and there was a problem in the appearance was judged as x.

  Moreover, the said evaluation was similarly implemented about the vapor deposition goods after carrying out the heat aging process using oven on the conditions of 150 degreeC * 24 hours and 170 degreeC * 24 hours.

(8) Fogging property (haze value)
Put 50 g (± 1 g) of the resin composition pellets obtained in the examples and comparative examples in a glass sample bottle, place the slide glass so as to completely cover the mouth of the sample bottle, and cover it. It was allowed to stand for 24 hours in a oven set at 150 ° C. (± 5 ° C.) or 170 ° C. (± 5 ° C.) (manufactured by Toyo Seiki Seisakusho Co., Ltd., with no damper opening) and heated. After the heating, the haze (haze value) of the portion of the slide glass that covered the mouth of the sample bottle was measured using a haze meter NDH2000 type manufactured by Nippon Denshoku Industries Co., Ltd.

(9) Surface roughness About the vapor deposition goods created in the Example and the comparative example, the surface roughness of the metal vapor-deposited part (deposition surface) was measured with the surface shape measuring instrument "DEKTAK 8" by ULVAC, Inc. . In addition, the average value (surface average roughness Ra) of arbitrary three places (N = 3) of the vapor deposition surface center part was described as a numerical value of the measurement result.

  As in the case of the surface reflectance, the measurement was also performed on the vapor-deposited product after heat aging treatment using an oven under conditions of 150 ° C./24 hours and 170 ° C./24 hours.

[Raw material 1]
Polyphenylene ether resin (A)
(A-1) Reduced viscosity (ηsp / c value): 0.42, poly (2,6-dimethyl-1,4-phenylene) ether having a residual volatile content of 1.0% by mass.

  (A-2) Poly (2,6-dimethyl-1,4-phenylene) ether having a reduced viscosity (ηsp / c value) of 0.54 and a residual volatile content of 0.6% by mass.

  (A-3) Poly (2,6-dimethyl-1,4-phenylene) ether having a reduced viscosity (ηsp / c value) of 0.31 and a residual volatile content of 0.8% by mass.

  In this example, the reduced viscosity (ηsp / c) of (A) polyphenylene ether resin was measured at 30 ° C. using an Ubbelohde viscometer tube with (A) polyphenylene ether as a 0.5 g / dL chloroform solution. The unit of reduced viscosity is dL / g.

  In this example, the residual volatile content in the (A) polyphenylene ether resin was calculated as a mass reduction ratio (a mass ratio reduced with respect to the original mass) after drying at 180 ° C. for 3 hours in a vacuum dryer.

[Raw material 2]
Polystyrene resin (B)
(B-1) General purpose polystyrene (polystyrene not containing a rubber component. Trade name: PSJ-polystyrene 685, manufactured by PS Japan). The melt flow rate (MFR) (test standard ISO 1133 pellet 200 ° C./5 kgf) of (B-1) was 2.1 g / 10 min.

(B-2) Styrene-acrylonitrile resin A styrene-acrylonitrile resin (B-2) was produced as follows.

  A mixed solution consisting of 4.7 parts by mass of acrylonitrile, 73.3 parts by mass of styrene, 22 parts by mass of ethylbenzene, and 0.02 parts by mass of t-butylperoxy-isopropyl carbonate as a polymerization initiator at a flow rate of 2.5 liters per hour. The polymer was continuously fed to a fully mixed reactor having a capacity of 5 liters and polymerization was carried out at 142 ° C. The obtained polymerization liquid was continuously introduced into an extruder equipped with a vent, and unreacted monomers and a solvent were removed under conditions of 260 ° C. and 40 Torr to obtain a polymer. The obtained polymer was continuously cooled and solidified and chopped to obtain particulate styrene-acrylonitrile resin (B-2). This copolymer resin (B-2) was analyzed by infrared absorption spectroscopy. As a result, the copolymer resin (B-2) was 9% by mass of acrylonitrile units and 91% by mass of styrene units, and melt flow rate (according to ASTM D-1238, 220 ° C.). 78 g / 10 min measured with a 10 kg load).

[Raw material 3]
Rubber polymer (C)
(C-1) Production of hydrogenated block copolymer (SEBS) of a block copolymer of a vinyl aromatic hydrocarbon and a conjugated diene compound Washing, drying, and nitrogen of a 100 liter autoclave with a stirrer and a jacket The cyclohexane solution containing 15 parts by mass of styrene that had been substituted and purified in advance was added to the autoclave. Next, after adding n-butyllithium and tetramethylethylenediamine and polymerizing at 70 ° C. for 1 hour, a cyclohexane solution containing 70 parts by mass of pre-purified butadiene was added for 1 hour, and a cyclohexane solution containing 15 parts by mass of styrene was further added. In addition, polymerization was carried out for 1 hour to obtain a block copolymer solution.

  A part of the obtained block copolymer solution was sampled, and octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate was added to 100 parts by mass of the block copolymer. 0.3 parts by mass was added, and then the solvent was removed by heating. Next, using the remaining block copolymer solution, hydrogenation was performed at a temperature of 70 ° C. using di-p-trisbis (1-cyclopentagenyl) titanium and n-butyllithium as a hydrogenation catalyst. An added block copolymer (C-1) was obtained. The hydrogenation rate was controlled by measuring the amount of hydrogen gas supplied with a flow meter and stopping the gas supply when the target hydrogenation rate was achieved. The physical properties of the hydrogenated block copolymer (C-1) were as follows.

  (C-1): Hydrogenated block copolymer having a polystyrene-hydrogenated polybutadiene-polystyrene structure, 30% by mass of bound styrene, a weight average molecular weight of 250,000, and a hydrogenation rate of the polybutadiene part of 99%. .

In this example, the weight average molecular weight of the hydrogenated block copolymer was measured using a gel permeation chromatography measuring device [GPC SYSTEM21: manufactured by Showa Denko KK] and an ultraviolet spectroscopic detector [UV-41: Showa. Manufactured by Denko Co., Ltd.] and converted to standard polystyrene with a known molecular weight. The measurement conditions were as follows.
[Solvent: chloroform, temperature: 40 ° C., column: sample side (KG, K-800RL, K-800R), reference side (K-805L × 2), flow rate 10 mL / min, measurement wavelength: 254 nm, pressure 15-17 kg / cm < ² >].

  Further, the hydrogenation rate of the hydrogenated block copolymer was measured by a nuclear magnetic resonance apparatus (NMR).

(C-2) Production of Hydrogenated Block Copolymer (SEBS) of Block Copolymer of Vinyl Aromatic Hydrocarbon and Conjugated Diene Compound Styrene / butadiene mass ratio, n-butyllithium and tetramethylethylenediamine A hydrogenated block copolymer (C-2) was prepared in the same manner as (C-1) except that the addition amount and the hydrogenation rate were controlled. The physical properties of the hydrogenated block copolymer (C-2) were as follows.

  (C-2): a hydrogenated block copolymer having a structure of polystyrene-hydrogenated polybutadiene-polystyrene, 60% by mass of bound styrene, a weight average molecular weight of 100,000, and a hydrogenation rate of the polybutadiene part of 99%. .

[Example 1]
80 parts by mass of polyphenylene ether (A-1), 5 parts by mass of polystyrene resin (B-1), 5 parts by mass of polystyrene resin (B-2), 5 parts by mass of rubber polymer (C-1), and rubber polymer ( C-2) 5 parts by mass of ZSK25 twin-screw extruder (manufactured by Werner & Pfleiderer, Germany, 10 barrels, screw diameter 25 mm (kneading disk L: 2, kneading disk R: 6, kneading disk N: The resin composition (pellet) was obtained by melting and kneading at the cylinder temperature of 320 ° C., screw rotation speed of 250 rpm, and vent vacuum degree of 60 Torr. The measurements (2) and (8) were carried out using the obtained resin composition. The measurement results are shown in Table 1.

  Next, the obtained resin composition (pellet) was dried in a hot air dryer at 120 ° C. for 3 hours. The resin composition (pellet) after drying was subjected to molding conditions shown in Table 1 (cylinder temperature 330 ° C., mold temperature 135 ° C., gate thickness 2 mm, molded body thickness) using FE120, an injection molding machine manufactured by Nissei Plastic Industry Co., Ltd. 2 mm) to form a molded product. The molded product was obtained by injecting the resin composition melted in a mold from a gate to a cavity. A flat plate test piece (100 mm × 100 mm, thickness: 2 mm) was prepared using the obtained molded product, and the appearance of the test piece was evaluated as described in (7) above. The evaluation results are shown in Table 1.

  Moreover, the vapor deposition surface of aluminum was formed in the surface of the obtained molded article by the direct vapor deposition method which does not require a primer, and the vapor deposition product was obtained. Using the obtained vapor-deposited product, a flat plate test piece (100 mm × 100 mm, thickness: 2 mm) was prepared, and the appearance, surface reflectance and surface roughness of the test piece were the above (3), (7) and (9 ) Was evaluated and measured as follows. The results are shown in Table 1.

  In addition, the resin composition (pellet) obtained above was molded by Toshiba Machine Co., Ltd. injection molding machine: IS-80C under the molding conditions (cylinder temperature and mold temperature) shown in Table 1. Test pieces for measuring mechanical strength and the like (various ISO test pieces) were prepared. About the said ISO test piece, the measurement of said (1), (4)-(6) was implemented. The measurement results are shown in Table 1.

[Examples 2-7, Comparative Examples 1-4]
A resin composition (pellet), a molded product, and a vapor-deposited product were prepared in the same manner as in Example 1 except that the blending ratio was changed as shown in Table 1, and the above measurements were performed. The measurement results are shown in Table 1.

As shown in Table 1, when a resin composition in which two or more types of (B) polystyrene resin and (C) rubber polymer are used is used, the effect of the obtained molded product is increased, and reflection is achieved. It became clear that it has utility as a mirror.

[Examples 8 to 11, Comparative Examples 5 to 8]
Resin composition (pellet) in the same manner as in Example 1 except that the molding conditions (cylinder temperature and mold temperature) when molding a molded product from the resin composition (pellet) were changed as shown in Table 2. Then, a molded product and a vapor-deposited product were prepared, and the above measurements were performed. The measurement results are shown in Table 2.

As shown in Table 2, it has been found that there is an appropriate range for improving the properties of the obtained molded product with respect to the molding conditions of the molded product.

[Examples 12-14, 18]
A resin composition (pellet), molded product, and vapor-deposited product were prepared in the same manner as in Example 1 except that the gate thickness and molded body thickness in the mold when molding the molded product were changed as shown in Table 3. Then, each of the above measurements was performed. The measurement results are shown in Table 3.

[Example 15, Example 19]
When molding a molded product, a pressure reducing mechanism device is attached to the upper part of the pellet hopper of the molding machine, the sealability of other parts is increased, the pressure of the hopper is reduced to 100 Torr or less, the gate thickness in the mold and the molded body A resin composition (pellet), a molded product, and a vapor-deposited product were prepared in the same manner as in Example 1 except that the thickness was changed as shown in Table 3, and the above measurements were performed. The measurement results are shown in Table 3.

[Example 16, Example 20]
When molding a molded product, attach a carbon dioxide supply device to the cylinder part of the molding machine, change the filling pressure of carbon dioxide to 12 MPa, and change the gate thickness and molded body thickness in the mold as shown in Table 3. A resin composition (pellet), a molded product, and a vapor-deposited product were prepared in the same manner as in Example 1 except that the above measurements were performed. The measurement results are shown in Table 3.

[Example 17, Example 21]
When molding a molded product, attach a pressure reducing mechanism to the upper part of the pellet hopper of the molding machine, improve the sealability of other parts, reduce the pressure of the hopper part to 100 Torr or less, and add it to the cylinder part of the molding machine. A carbon dioxide supply device was attached, the carbon dioxide filling pressure was set to 12 MPa, and the gate thickness and the molded body thickness in the mold were changed as shown in Table 3 to perform molding in the same manner as in Example 1. Then, a resin composition (pellet), a molded product, and a vapor-deposited product were prepared, and the above measurements were performed. The measurement results are shown in Table 3.

As shown in Table 3, even if the thickness of the molded product and the gate thickness are shifted to the more difficult one (thin wall), if the blending ratio of the resin composition described in the present embodiment and the molding conditions are used, it can be obtained. The molded product thus obtained was found to have the performance represented by Example 1. Furthermore, it has been clarified that the quality of the obtained molded product is further improved by producing the molded product under reduced pressure using a reduced pressure supply facility and / or filling with carbon dioxide. .

  The reflecting mirror of the present invention is excellent in surface appearance and surface gloss, and is excellent in physical properties such as heat resistance and rigidity, so that it can be effectively used for vehicle lamp parts, particularly vehicle lamp extension reflectors and vehicle reflectors. Is possible.

Claims (27)

A high-intensity, low-gas thin resin reflector made of a resin composition,
The reflecting mirror is metal-deposited,
The molded product thickness of the metal-deposited portion is an average of 2 mm or less,
The initial surface reflectance of the metal-deposited part (deposition surface) is 90% or more,
The surface roughness of the metal-deposited portion is 12 nm or less, and the haze value of the glass plate after performing the following fogging test on the resin composition is 1.0 or less. Low gas thin resin reflector.
<Foging test>
Put 50 g (± 1 g) of the resin composition in a glass sample bottle, leave it on a glass plate that can cover all the mouths of the glass sample bottle, cover it, and place it at 150 ° C. (± 5 ° C.) The glass plate is fogged by being heated for 24 hours underneath.   The high-luminance and low-gas thin resin reflector according to claim 1, wherein a heating temperature in the fogging test is 170 ° C.   3. The high-luminance, low-gas thin resin reflector according to claim 1, wherein the thickness of the molded product on the metal-deposited portion is 1.5 mm or less on average.   The retention rate of the surface reflectance of the reflecting mirror is 50% or more after thermal aging treatment for 24 hours in a 150 ° C environment (± 5 ° C) with respect to the initial surface reflectance. The high-luminance, low-gas thin-walled resin reflector according to any one of 3 above.   The retention rate of the surface reflectance of the reflecting mirror is 70% or more after thermal aging treatment for 24 hours in a 150 ° C environment (± 5 ° C) with respect to the initial surface reflectance. 5. The high-luminance and low-gas thin resin reflector according to any one of 4 above.   The retention rate of the surface reflectance of the reflecting mirror is 90% or more after thermal aging treatment for 24 hours in a 150 ° C environment (± 5 ° C) with respect to the initial surface reflectance. The high-luminance, low-gas thin-walled resin reflecting mirror according to any one of 5.   The high-luminance / low-gas thin resin reflector according to claim 1, wherein the metal deposition is performed by a direct deposition method that does not require a primer. The resin composition is
(A) polyphenylene ether resin (PPE);
(B) polystyrene resin;
(C) rubber polymer, and the ratio of each is (A) + (B) + (C) = 100% by weight,
(A) 59 to 98% by weight of polyphenylene ether resin (PPE),
(B) 1 to 40% by weight of polystyrene resin,
(C) 1-40% by weight of rubber polymer
And
The (C) rubber polymer is
(C-1) a hydrogenated block copolymer having a weight average molecular weight of 200,000 to 500,000,
(C-2) A hydrogenated block copolymer having a weight average molecular weight of 10,000 to 150,000 and high brightness and low gas according to any one of claims 1 to 7 Thin-walled resin reflector. The (C-1) is a hydrogenated block copolymer containing 10% by mass or more and less than 40% by mass of a monomer derived from a vinyl aromatic hydrocarbon,
The high brightness according to claim 8, wherein (C-2) is a hydrogenated block copolymer containing 40% by mass or more and 90% by mass or less of a monomer derived from a vinyl aromatic hydrocarbon.・ Low gas thin resin reflector.   The mass ratio ((C-1) / (C-2)) between the (C-1) and the (C-2) is in the range of 5/95 to 95/5. The high-intensity and low-gas thin resin reflector according to 8 or 9. The (B) polystyrene resin is
(B-1) a polystyrene resin not reinforced with rubber;
(B-2) The high-brightness and low-gas thin-walled resin reflector according to any one of claims 8 to 10, comprising a polystyrene-based resin containing an acrylonitrile component.   The mass ratio ((B-1) / (B-2)) between the (B-1) and the (B-2) is in the range of 5/95 to 95/5. 11. A high-intensity, low-gas thin-walled resin reflector as described in item 11.   The high-luminance and low-gas according to claim 11 or 12, wherein the melt flow rate (MFR) (test standard ISO 1133 pellet 200 ° C / 5kgf) of (B-1) is 1 g / 10 min or more. Thin-walled resin reflector.   14. The reduced viscosity (30 g of chloroform 0.5 g / dL solution) of the (A) polyphenylene ether resin is in the range of 0.2 to 0.6. 14. High-intensity, low-gas thin-walled resin reflector as described in 1. The reflecting mirror is obtained by a manufacturing method including a step of injecting the resin composition melted in a mold from a gate to a cavity,
The high brightness and low gas according to any one of claims 1 to 14, wherein the gate has a thickness of 2.0 mm or less, and a silver phenomenon does not occur in a molded product formed in the cavity. Thin-walled resin reflector.   The high brightness and low gas thin resin reflector according to claim 15, wherein the gate has a thickness of 1.0 mm or less.   The said reflecting mirror is obtained by the manufacturing method including the process of shape | molding the said resin composition on conditions with a cylinder temperature of 300 to 340 degreeC, and mold temperature of 90 to 150 degreeC. The high-intensity and low-gas thin resin reflector according to any one of the above.   The said reflecting mirror is obtained by the manufacturing method including the process of shape | molding the said resin composition using the molding machine which has a pressure reduction mechanism in a pellet supply machine, The Claim 1 characterized by the above-mentioned. High brightness and low gas thin-walled resin reflector.   The high-luminance / low-gas thin resin reflector according to claim 1, wherein the metal deposition is aluminum deposition.   The high-luminance / low-gas thin resin reflector according to claim 1, wherein the reflector is used as a reflector attached to a moving body.   The high brightness and low gas thin resin reflector according to claim 20, wherein the moving body is powered by an internal combustion engine or a motor.   The high brightness and low gas thin resin reflector according to claim 20 or 21, wherein the moving body is a flying body, a land traveling body, a sea traveling body or an underwater traveling body.   The high-luminance / low-gas thin resin reflector according to any one of claims 20 to 22, wherein the moving body has wheels.   24. The high-luminance / low-gas thin resin reflector according to any one of claims 1 to 23, wherein the reflector is used as a reflector of a light source.   The high-intensity, low-gas thin resin reflector according to claim 24, wherein the light source is a halogen lamp, a discharge lamp, or an LED lamp.   It is an extension reflector, a reflector, other lamp components, or a mirror, The high-intensity and low-gas thin resin reflector according to any one of claims 19 to 25. (A) polyphenylene ether resin (PPE);
(B) polystyrene resin;
(C) rubber polymer, and the ratio of each is (A) + (B) + (C) = 100% by weight,
(A) 59 to 98% by weight of polyphenylene ether resin (PPE),
(B) 1 to 40% by weight of polystyrene resin,
(C) 1-40% by weight of rubber polymer
And
The (C) rubber polymer is
(C-1) a hydrogenated block copolymer having a weight average molecular weight of 200,000 to 500,000,
(C-2) A high-brightness, low-gas thin-walled resin reflector comprising a resin composition comprising a hydrogenated block copolymer having a weight average molecular weight of 10,000 to 150,000.