JP2022051350A - Light reflection member - Google Patents

Abstract

To provide a light reflection member capable of exhibiting a good appearance under a high-temperature and high-humidity environment even in a complicated shape.SOLUTION: The light reflection member includes three layers, i.e., a resin substrate, a metal layer, and a coating layer in this order. The resin substrate contains a resin composition containing a modified polyphenylene ether. The ratio (metal layer/resin substrate) of the linear expansion coefficient of the metal layer to that of the resin substrate is 0.24-1.0. The contact angle of the coating layer with water is 90-180°.SELECTED DRAWING: None

Description

The present invention relates to a light reflecting member.

Conventionally, in order to improve the efficiency of the brightness of lighting, a light reflecting member whose surface is a mirror surface is used together with a light emitting source for the lighting equipment.
In recent years, it has been actively used not only indoors but also outdoors, and the number of highly designed items has increased. The demand for weight reduction is increasing, and the raw materials are changing from metal to resin. There is a need for light-reflecting members that have a complex shape, have a good appearance, and can withstand the outdoor environment.

As one of the light reflecting members having a good appearance, a reflector (see Patent Documents 1 and 2) using polyphenylene sulfide (hereinafter, also referred to as “PPS”), which is a resin having high smoothness, is known.
Further, a light reflecting member (see Patent Documents 3 to 5) using a modified polyphenylene ether (hereinafter, also referred to as “mPPE”), which can obtain a molded product having similarly high smoothness and lighter weight, is known.
Further, as one of the means for solving the surface appearance defect in a high temperature and high humidity environment, a method of forming a multi-layer structure of the surface treatment of the light reflecting member is known (Patent Document 6).

Patent Document 1: Japanese Patent Application Laid-Open No. 3528208 Patent Document 2: Japanese Patent Application Laid-Open No. 7-53865 Patent Document 3: Japanese Patent Application Laid-Open No. 6010403 Patent Document 4: Japanese Patent Application Laid-Open No. 2018-058274 Japanese Patent Application Laid-Open No. 2002-361795 Japanese Patent Application Laid-Open No. 2002-361795

However, although the techniques described in Patent Documents 1 and 2 can obtain a light-reflecting member having a smooth surface and a good appearance, they may cause appearance defects such as peeling after exposure to an outdoor high-temperature and high-humidity environment. In some cases, it could not withstand the harsh environment.
Further, in the techniques described in Patent Documents 3 to 5, deterioration of the resin member can be prevented in a high temperature environment and a good appearance can be maintained, but in a high humidity environment, the surface vapor deposition layer is oxidized. , Surface peeling may occur, and it may not be possible to withstand the high temperature and high humidity outdoor environment.
Although the technique described in Patent Document 6 can also prevent surface peeling, it gradually occurs on the surface in an environment where the temperature changes drastically, such as outdoors, due to the difference in expansion rate from the substrate constituting the multilayer structure. Moisture entered from the minute cracks and oxidation was promoted, which could cause a poor appearance, so that it was insufficient for outdoor use.
As described above, the light-reflecting member of the lighting fixture having a highly designed and complicated shape as described above has insufficient resistance in a high-temperature and high-humidity environment such as outdoor use, and is on the surface of the light-reflecting member. Poor appearance such as peeling and cracking may occur.

Therefore, an object of the present invention is to provide a light reflecting member capable of exhibiting a good appearance even in a complicated shape in a high temperature and high humidity environment.

As a result of diligent studies to solve the above problems, the present inventors have assumed that the resin substrate has three layers of a resin substrate, a metal layer, and a coating layer in this order, and the resin substrate contains a modified polyphenylene ether. We have found that the above problems can be solved by setting the ratio of the linear expansion coefficient between the resin and the metal layer and the contact angle of the coating layer with water within a specific range, and have completed the present invention.

That is, the present invention is as follows.
[1] It has three layers, a resin substrate, a metal layer, and a coating layer, in this order.
The resin substrate contains a resin composition containing a modified polyphenylene ether and contains.
The ratio of the coefficient of linear expansion of the metal layer to the resin substrate (metal layer / resin substrate) is 0.24 to 1.0.
A light reflecting member having a contact angle of the coating layer with respect to water of 90 to 180 °.
[2] The light reflecting member according to [1], wherein the melt flow rate (based on ISO1133) of the resin composition is 5 to 40 g / 10 min.
[3] The light reflecting member according to [1] or [2], wherein the modified polyphenylene ether contains polyphenylene ether and polystyrene.
[4] The light reflecting member according to any one of [1] to [3], wherein the modified polyphenylene ether contains polyphenylene ether and polyphenylene sulfide.
[5] The light reflecting member according to any one of [1] to [4], wherein the metal layer is made of aluminum or an aluminum alloy.
[6] The light reflecting member according to any one of [1] to [5], which has a spherical recess in the thickness direction.
[7] The light reflecting member according to any one of [1] to [6], which has a convex portion in the thickness direction.
[8] The light reflecting member according to any one of [1] to [7], which has portions having different thicknesses of 1 mm or more.
[9] The light reflecting member according to any one of [1] to [8], wherein the resin substrate has a weld line.

According to the present invention, it is possible to provide a light reflecting member capable of exhibiting a good appearance even in a complicated shape in a high temperature and high humidity environment.

It is a perspective view which shows the light reflection member produced in an Example. It is a perspective view which shows the light reflection member produced in an Example and a comparative example.

Hereinafter, embodiments for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. The following embodiments are examples for explaining the present invention, and the present invention is not limited to the following embodiments. Further, the present invention can be appropriately modified and carried out within the scope of the gist thereof.

[Light reflecting member]
The light reflecting member of the present embodiment has three layers of a resin substrate, a metal layer, and a coating layer in this order, and the resin substrate contains a resin composition containing a modified polyphenylene ether, and the metal layer with respect to the resin substrate. The ratio of the linear expansion coefficient (metal layer / resin substrate) is 0.24 to 1.0, and the contact angle of the coating layer is 90 ° to 180 °.

Further, the light reflecting member of the present embodiment is used for a lighting fixture having a device that emits light, and from the viewpoint of being used as a member used for the purpose of increasing the luminous efficiency, the metal layer is surface-treated so as to have at least a metallic luster. Furthermore, it is preferable that the coating layer transmits visible light (transparent) so as to maintain metallic luster.

<Resin substrate>
The light reflecting member of this embodiment has a resin substrate. The resin substrate of the present embodiment contains a resin composition containing a modified polyphenylene ether, and preferably comprises only a resin composition containing a modified polyphenylene ether.
Hereinafter, the resin composition of the present embodiment will be described.

<< Resin composition >>
The resin composition of the present embodiment contains a modified polyphenylene ether.

(Modified polyphenylene ether)
The modified polyphenylene ether is a polymer alloy of polyphenylene ether (hereinafter, also referred to as “PPE”) and another resin.
Examples of the modified polyphenylene ether contained in the resin composition of the present embodiment include polyphenylene ether / polystyrene alloy, polyphenylene ether / high impact-polystyrene alloy, polyphenylene ether / polystyrene / high impact-polystyrene alloy, and polyphenylene ether / polyphenylene sulfide alloy. , Polyphenylene ether / Polyamide alloy and the like.
The modified polyphenylene ether may be used alone or in combination of two or more.

The polyphenylene ether in the modified polyphenylene ether is preferably a homopolymer and / or a copolymer having a repeating unit (structural unit) represented by the following formula (1).

・・・（１）
（式（１）中、Ｒ_１、Ｒ_２、Ｒ_３及びＲ_４は、それぞれ独立して、水素原子、ハロゲン原子、炭素数１～７の第一級又は第二級低級アルキル基、フェニル基、ハロアルキル基、アミノアルキル基、炭化水素オキシ基、及び少なくとも２個の炭素原子がハロゲン原子と酸素原子とを隔てているハロ炭化水素オキシ基からなる群から選択される一価の基であり、互いに同一であっても異なっていてもよい。また、ｎは１以上の整数である。）

... (1)
In formula (1), R ₁ , R ₂ , R ₃ and R ₄ are independently hydrogen atoms, halogen atoms, primary or secondary lower alkyl groups having 1 to 7 carbon atoms, and phenyl groups, respectively. , A haloalkyl group, an aminoalkyl group, a hydrocarbon oxy group, and a monovalent group selected from the group consisting of a halohydrocarbon oxy group in which at least two carbon atoms separate a halogen atom and an oxygen atom. They may be the same or different from each other, and n is an integer of 1 or more.)

Specific examples of the above PPE are not limited to the following, but for example, poly (2,6-dimethyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1, Homopolymers such as 4-phenylene ether), poly (2-methyl-6-phenyl-1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether), and the like, and 2 more. , 6-Dimethylphenol and other phenols (eg, 2,3,6-trimethylphenol and 2-methyl-6-butylphenol) and other copolymers and the like.
The polyphenylene ether copolymer is a copolymer having a repeating unit represented by the above formula (2) as a main repeating unit.
Of these, poly (2,6-dimethyl-1,4-phenylene ether), a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol is preferable, and poly (2,6-dimethyl-1,4, 4-Phenylene ether) is more preferable.

The PPE can be produced by a known method. The method for producing PPE is not particularly limited, and for example, a complex of ferrous salt and amine according to Hay described in US Pat. No. 3,306,874 is used as a catalyst, and for example, 2,6-xylenol can be used. It can be easily produced by oxidative polymerization, and in addition, US Pat. No. 3,306,875, US Pat. No. 3,257,357, US Pat. No. 3,257,358, Japanese Patent Application Laid-Open No. 52-17880, Japanese Patent Application Laid-Open No. 50- Examples thereof include the methods described in Japanese Patent Application Laid-Open No. 51197 and Japanese Patent Application Laid-Open No. 63-152628.

When the modified polyphenylene ether is a polymer alloy as described above, the content of PPE is preferably 10 to 99% by mass, more preferably 10 to 90% by mass, still more preferably 10% by mass, based on 100% by mass of the polymer alloy. It is 20 to 80% by mass.

As the polystyrene-based resin that can be used for the modified polyphenylene ether, a homopolymer of a styrene-based compound, a copolymer of two or more kinds of styrene-based compounds, and a rubber-like weight in a matrix composed of a polymer of the styrene-based compound. Examples thereof include rubber-modified polystyrene (high-impact-polystyrene) in which the coalescence is dispersed in the form of particles. Examples of the styrene-based compound that brings about these polymers include styrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, α-methylstyrene, ethylstyrene, α-methyl-p-methylstyrene, and 2,4-. Examples thereof include dimethylstyrene, monochlorostyrene, p-tert-butylstyrene and the like.

When the above-mentioned polymer alloy is used as the modified polyphenylene ether, the polystyrene-based resin contained in PPE may be a copolymer obtained by using two or more kinds of styrene-based compounds in combination or high-impact-polystyrene. Of these, polystyrene obtained by polymerizing using styrene alone is preferable. As the polystyrene contained in the modified polyphenylene ether, polystyrene having a three-dimensional ordered structure such as atactic polystyrene and syndiotactic polystyrene can be effectively used.

(Molecular weight of polyphenylene ether)
The molecular weight of the polyphenylene ether contained in the modified polyphenylene ether is preferably 0.16 to 0.36 dL / g as the ultimate viscosity (measured in chloroform at 30 ° C. using a Ubbelohde viscometer), more preferably. It is 0.20 to 0.34 dL / g. By setting the ultimate viscosity within this range, the balance between mechanical properties, fluidity, and releasability can be improved.

(Content of modified polyphenylene ether)
The content of the modified polyphenylene ether in the resin composition is preferably 10 to 99% by mass, more preferably 10 to 90% by mass, and 20 to 80% by mass with respect to 100% by mass of the resin composition. Is more preferable. When the content of the modified polyphenylene ether is in the above range, the surface appearance, heat resistance, fluidity during molding, and strength tend to be appropriately designed.

(Inorganic filler)
The resin composition of the present embodiment may contain an inorganic filler, if mechanical strength is required.
Examples of the inorganic filler include, but are not limited to, glass fiber, glass flakes, carbon fiber, wollastonite, talc, mica, kaolin, zonotrite, titanium oxide, potassium titanate, calcium carbonate, zinc oxide and the like.
The content of the inorganic filler in the resin composition is preferably 0 to 50% by mass, more preferably 0 to 40% by mass, based on 100% by mass of the resin composition. When the content of the inorganic filler is in the above range, a good appearance as a light reflecting member tends to be obtained. The resin composition may not contain an inorganic filler from the viewpoint of improving the appearance.

(Flame retardants)
The resin composition of the present embodiment may contain a flame retardant in order to improve the flame retardancy. As the flame retardant, a flame retardant added to a normal thermoplastic resin can be used, but it is preferable to add an organic phosphorus-based flame retardant containing no halogen.
The flame retardant may be used alone or in combination of two or more.

Examples of the organic phosphorus-based flame retardant include a phosphate ester-based compound and a phosphazene-based compound.

The phosphoric acid ester compound is added to improve the flame retardancy of the resin composition, and any organic phosphoric acid ester compound generally used as a flame retardant can be used.

Specific examples of the phosphate ester compound include triphenyl phosphate, trisnonylphenyl phosphate, resorcinol bis (diphenyl phosphate), resorcinol bis [di (2,6-dimethylphenyl) phosphate], 2,2-bis {4-. Examples thereof include [bis (phenoxy) phosphoryloxy] phenyl} propane, 2,2-bis {4- [bis (methylphenoxy) phosphoryloxy] phenyl} propane, and the like, but the present invention is not limited thereto. Further, examples of the phosphorus-based flame retardant other than the above include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, tricresyl phosphate, cresylphenyl phosphate, octyldiphenyl phosphate, diisopropylphenyl phosphate and the like. Phenylic acid ester flame retardant, diphenyl-4-hydroxy-2,3,5,6-tetrabromobenzylphosphonate, dimethyl-4-hydroxy-3,5-dibromobenzylphosphonate, diphenyl-4-hydroxy- 3,5-dibromobenzyl phosphate, tris (chloroethyl) phosphate, tris (dichloropropyl) phosphate, tris (chloropropyl) phosphate, bis (2,3-dibromopropyl) -2,3-dichloropropyl phosphate, tris ( Monophosphate ester compounds such as 2,3-dibromopropyl) phosphate and bis (chloropropyl) monooctyl phosphate hydroquinonyl diphenyl phosphate, phenylnonylphenylhydroquinonyl phosphate, phenyldinonylphenyl phosphate, and aromatic condensed phosphates. Examples include ester compounds.
Among these, aromatic condensed phosphoric acid ester compounds are preferably used because they generate less gas during processing and are excellent in thermal stability and the like.

As the aromatic condensed phosphoric acid ester compound that can be used in the present embodiment, the aromatic condensed phosphoric acid ester compound represented by the following general formula (I) or the following general formula (II) is preferable. Particularly preferred is an aromatic condensed phosphoric acid ester compound represented by the following general formula (I).

・・・（Ｉ）

・・・（ＩＩ）
（一般式（Ｉ）及び（ＩＩ）中、Ｑ１、Ｑ２、Ｑ３及びＱ４は、各々置換基であって各々独立に炭素数１から６のアルキル基を表し、Ｒ１１及びＲ１２は各々メチル基を表し、Ｒ１３及びＲ１４は各々独立に水素原子又はメチル基を表し、ｎは１以上の整数であり、ｎ１及びｎ２は各々独立に０から２の整数を示し、ｍ１、ｍ２、ｍ３及びｍ４は各々独立に０から３の整数を示す。）
上記一般式（Ｉ）又は（ＩＩ）で示される縮合リン酸エステル化合物は、それぞれの分子において、ｎは、好ましくは１から３の整数である。

... (I)

... (II)
(In the general formulas (I) and (II), Q1, Q2, Q3 and Q4 are substituents and each independently represents an alkyl group having 1 to 6 carbon atoms, and R11 and R12 each represent a methyl group. , R13 and R14 each independently represent a hydrogen atom or a methyl group, n is an integer of 1 or more, n1 and n2 each independently represent an integer of 0 to 2, and m1, m2, m3 and m4 are independent of each other. Indicates an integer from 0 to 3.)
In the condensed phosphate ester compound represented by the general formula (I) or (II), n is preferably an integer of 1 to 3 in each molecule.

The condensed phosphoric acid ester compound represented by the general formula (I) or (II) is preferably the condensed phosphoric acid ester compound represented by the general formula (I), and is m1, m2, m3, m4 in the formula (I). , N1 and n2 are zero and R13 and R14 are methyl groups, or Q1, Q2, Q3, Q4, R13 and R14 in the formula (I) are methyl groups, and n1 and n2. Is zero, m1, m2, m3 and m4 are integers from 1 to 3, and n is an integer from 1 to 3 (particularly preferably n is 1). Those contained in the acid ester-based compound in an amount of 50% by mass or more are preferable.

These aromatic condensed phosphoric acid ester compounds are generally commercially available, and for example, CR741, CR733S, PX200 manufactured by Daihachi Chemical Industry Co., Ltd., FP600, FP700, FP800 manufactured by ADEKA Corporation, and the like are known. There is.

Particularly preferred among these aromatic condensed phosphoric acid ester compounds are aromatic condensed phosphoric acid ester compounds having an acid value (value obtained in accordance with JIS K2501) of 0.1 or less from the viewpoint of thermal stability. be.

Further, as the phosphazene compound, phenoxyphosphazene and a crosslinked product thereof are preferable, and phenoxy having an acid value (value obtained according to JIS K2501) of 0.1 or less is particularly preferable from the viewpoint of thermal stability. It is a phosphazene compound.

The content of the flame retardant varies depending on the required flame retardant level, but is preferably in the range of 1 to 30% by mass, more preferably in the range of 5 to 25% by mass in 100% by mass of the resin composition. .. When the content of the flame retardant is 1% by mass or more, the fluidity and flame retardancy of the resin composition are improved, and when it is 30% by mass or less, the flame retardancy of the resin composition is sufficient and the flow. The balance between sex, releasability, and burr suppression is improved.

(Other additives)
In addition to the various materials described above, the resin composition of the present embodiment is stable with various additives added to ordinary thermoplastic resins, such as heat stabilizers, antioxidants, and UV absorbers, as needed. Agents, conductivity-imparting agents, antistatic agents, colorants such as pigments and dyes, and mold release agents can also be appropriately contained.
The content of the other additives is preferably 0 to 5% by mass, more preferably 0.001 to 4% by mass, and 0.1 to 3% by mass with respect to 100% by mass of the resin composition. % Is more preferable.

(Fluidity of resin composition)
The resin composition of the present embodiment preferably has appropriate fluidity. The melt flow rate (MFR) is mentioned as a numerical value that defines the fluidity. According to ISO1133, the MFR measured under the condition of 280 ° C. (300 ° C. in the case of PPS / PPE alloy) and 5 kgf load is preferably 5 to 40 g / 10 min. When the MFR is 5g / 10min or more, even when injection molding a light reflecting member with a complicated shape, molding defects such as short shots and hot water wrinkles in the part far from the gate are prevented and the appearance is good. There is a tendency to be able to do it. On the other hand, when the MFR is 40 g / 10 min or less under the above conditions, it tends to prevent the resin from overflowing from the parting line of the mold during injection molding and generate burrs, and the appearance can be improved. The MFR is more preferably 10 to 30 g / 10 min under the above conditions.

(Manufacturing method of resin composition)
The resin composition of the present embodiment is not particularly limited and can be produced by using various melt kneaders, kneading extruders and the like.
The melt kneader and the kneading extruder are not particularly limited, and a known kneader can be used. For example, an extruder such as a multi-screw extruder such as a single-screw extruder or a twin-screw extruder; a roll, a kneader. , Brabender plast graph, heat-melt kneader such as Banbury mixer and the like. Of these, a twin-screw extruder is preferable.

When an extruder is used, the type and specifications thereof are not particularly limited, and a known extruder can be appropriately used. The L / D ratio (barrel effective length (L) / barrel inner diameter (D)) of the extruder is preferably 20 to 75, and more preferably 30 to 60.
As an extruder, a first raw material supply port is provided on the upstream side in the flow direction of the raw material, a first vacuum vent is provided downstream of the first raw material supply port, a second raw material supply port is provided downstream of the first vacuum vent, and further downstream thereof. It is preferable that a die raw material supply port is provided and a second vacuum vent is provided further downstream thereof. The extruder may be further provided with a third raw material supply port, a third vacuum vent, or the like downstream of these. The total number of raw material supply ports of the extruder and their arrangement can be appropriately set in consideration of the number of types of materials of the resin composition and the like.

The method of supplying the raw material to the second raw material supply port is not particularly limited, but the forced side feeder is provided from the extruder side opening port rather than the simple addition supply from the opening ports of the second and third raw material supply ports of the extruder. The method of adding and supplying using is preferable because it is more stable.

The melt-kneading temperature and the screw rotation speed are not particularly limited, but it is usually preferable that the melt-kneading temperature is 280 ° C. or higher and the screw rotation speed is 100 to 1200 rpm.

<Linear expansion coefficient of resin substrate>
The coefficient of linear expansion of the resin substrate depends on the resin composition used for the resin substrate. The coefficient of linear expansion of the resin substrate is not particularly limited as long as the ratio of the coefficient of linear expansion of the metal layer to the resin substrate (metal layer / resin substrate) described later is 0.24 to 1.0, but the ratio of the coefficient of linear expansion is not particularly limited. From the viewpoint of satisfying the conditions, the value is preferably 2.4 to 10, more preferably 3 to 9, and even more preferably 3 to 7.5.
The coefficient of linear expansion of the resin substrate can be controlled by changing the type and amount of the inorganic filler added in the resin composition used. In addition to glass fibers and carbon fibers being used to control the expansion of the resin composition in the flow direction during molding, other inorganic fillers are also preferably used, and the coefficient of linear expansion should be reduced by increasing the amount added. Can be done. In addition, it can be controlled by blending a crystalline alloy and an amorphous alloy. When a crystalline alloy is used, there is generally shrinkage and expansion during crystallization, so the coefficient of linear expansion tends to be large. On the contrary, by using an amorphous alloy, the coefficient of linear expansion tends to be reduced.
The coefficient of linear expansion of the resin substrate is a value measured in accordance with ISO11359-2, and specifically, it can be measured by the method described in Examples described later.

<Weld line of resin substrate>
The resin substrate often has a complicated shape in order to give the light-reflecting member a design, and the resin flowing from multiple directions may meet during molding, and the welding line (weld line). May exist. When such a weld line is present, minute irregularities are present on the surface of the resin substrate and thus the light reflecting member, and the difference in irregularities makes it easy for components that cause deterioration such as moisture and oxygen to invade, resulting in high temperature. It may cause deterioration of the mirror surface in a high humidity environment. The light reflecting member of the present embodiment can maintain an excellent appearance even when there are one or more weld lines.

The thickness of the resin substrate is preferably 0.2 to 6 mm, more preferably 0.5 to 5 mm, and further preferably 0.5 to 5 mm from the viewpoint of poor appearance such as voids on the surface of the molded product and poor filling of the flow end (from the viewpoint of preventing short shots). It is preferably 1 to 3 mm.

<Manufacturing method of resin substrate>
The resin substrate of the present embodiment uses the above-mentioned resin composition and is used in conventionally known methods such as injection molding, metal inmold molding, outsert molding, hollow molding, extrusion molding, sheet molding, film molding, and hot pressing. It can be molded by a known method such as molding, rotary molding, and laminated molding. Above all, injection molding, which can freely produce a highly designed form, is preferable.
The mold temperature for molding by injection molding is preferably 100 ° C. or lower. By molding at a mold temperature of 100 ° C or less, the adhesion between the resin substrate and the metal of the mold can be appropriately controlled, and the resin on the surface can be prevented from remaining finely on the mold. Is thought to be possible. This tends to maintain the smoothness of the surface and improve the appearance.

<Metal layer>
The light reflecting member of this embodiment has a metal layer. The metal layer may cover at least a part of the surface of the resin substrate, may directly cover the surface of the resin substrate, or may be covered with an additional layer sandwiched between them. From the viewpoint of increasing the efficiency with which the light reflecting member reflects light and preventing deterioration of the resin substrate due to the influence of oxygen, moisture, light, etc., it is preferable to directly cover the entire surface of the resin substrate.

(Metal constituting the metal layer)
The metal constituting the metal layer is not particularly limited, but is preferably made of aluminum or an aluminum alloy from the viewpoint of being able to be satisfactorily formed (deposited) by vapor deposition or sputtering. Particularly preferably, it is a metal species obtained by doping aluminum with a small amount of copper, and since the cost of film formation can be suppressed and the resistance to oxidation can be increased, a metal layer having a metallic luster appearance can be easily formed. Can be done.

<Linear expansion coefficient of metal layer>
The coefficient of linear expansion of the metal layer depends on the metal constituting the metal layer. The coefficient of linear expansion of the metal layer is not particularly limited as long as the ratio of the coefficient of linear expansion of the metal layer to the resin substrate (metal layer / resin substrate) described later is 0.24 to 1.0, but the ratio of the coefficient of linear expansion is not particularly limited. From the viewpoint of satisfying the above conditions, it is preferably 1 to 4, and more preferably 2 to 3.
The coefficient of linear expansion of the metal layer is a value measured in accordance with ISO11359-2.

<Thickness of metal layer>
The thickness of the metal layer is preferably 10 to 500 nm, more preferably 20 to 400 nm, still more preferably 40 to 100 nm, from the viewpoint of appropriately controlling the adhesion strength, the reflectance of light, the design, and the like.

<Method of forming a metal layer>
The method for forming the metal layer of the present embodiment is not particularly limited as long as it is a method for forming the metal layer so as to cover at least a part of the surface of the resin substrate, and is sputtering, chemical vapor deposition (CVD). And vapor deposition such as physical vapor deposition (PVD) is exemplified.

<Coating layer>
The light reflecting member of this embodiment has a coating layer. The coating layer may cover at least a part of the surface of the metal layer, may directly cover the surface of the metal layer, or may cover an additional layer in between. From the viewpoint of protecting the metal layer, it is preferable to directly cover the entire surface of the metal layer.

<Coating agent that constitutes the coating layer>
The coating agent constituting the coating layer is preferably a UV curable resin from the viewpoint of enhancing the gloss of the surface of the light reflecting member and preventing deterioration of the resin substrate due to the influence of oxygen, moisture, light, etc., and specifically, a UV curable resin. , Epoxy ester resin, epoxy acrylate resin, urethane acrylate resin, polymer type acrylate resin and the like.

<Thickness of coating layer>
The thickness of the coating layer is preferably 1 to 1000 μm, more preferably 10 to 1000 μm from the viewpoint of increasing the gloss of the surface of the light reflecting member and preventing deterioration of the resin substrate due to the influence of oxygen, moisture, light and the like. It is 500 μm, more preferably 20 to 100 μm.

<Contact angle of coating layer with water>
The contact angle (static contact angle) of the coating layer with water is 90 to 180 °, preferably 90 to 160 °, and more preferably 92 to 135 °. It is considered that when the contact angle is within this range, it has appropriate hydrophobicity, and it is possible to prevent fine organic substances from adhering to the surface due to the action of static electricity and the like, and scratches starting from the deposits. As a result, it is possible to suitably prevent oxygen and water from coming into contact with the metal layer, and there is a tendency that the metallic luster can be maintained.
The contact angle of the coating layer with water is the angle formed by the tangent line of the contour curve of the water droplet and the surface of the coating layer at the intersection of the contour curve of the water droplet and the surface of the coating layer. The contact angle can be measured by the static sessile drop method using a contact angle meter, and specifically, can be measured by the method described in Examples described later.

<Method of forming the coating layer>
The method for forming the coating layer of the present embodiment is not particularly limited as long as the coating layer is formed so as to cover at least a part of the surface of the metal layer, and the coating agent is applied to the surface and dried. After that, a method of irradiating with UV to cure the metal is exemplified.

<Ratio of linear expansion coefficient of metal layer to resin substrate>
The light reflecting member of the present embodiment has a three-layer structure of a resin substrate containing a modified polyphenylene ether, a metal layer, and a coating layer, and the ratio of the linear expansion coefficient of the metal layer to the resin substrate (metal layer / resin substrate) is It is 0.24 to 1.0. The ratio is preferably 0.25 to 0.9, more preferably 0.7 to 0.8. When the ratio of the coefficient of linear expansion is 0.24 or more, it tends to prevent the formation of cracks in the coating layer that protects the metal layer, and when it is 1.0 or less, the metal layer expands too much even in a high temperature environment. However, there is a tendency that it can be prevented from peeling off from the resin substrate. In either case, it is considered that the decrease in glossiness due to the oxidation of the metal layer is prevented from occurring in a fine range, and the appearance tends to be good.

<Shape of light reflecting member>
The shape of the light-reflecting member of the present embodiment is not particularly limited, and various shapes such as concave portions, convex portions, through holes, etc. may be formed depending on the shape of the fixture, lighting, etc. in which the light-reflecting member of the present embodiment is used. You may have. From the viewpoint of design, the shape of the light reflecting member of the present embodiment preferably has a spherical concave portion in the thickness direction, preferably has a convex portion in the thickness direction, and has a portion having a thickness different by 1 mm or more. It is preferable to have. It is more preferable that the light reflecting member of the present embodiment has all the spherical concave portions, convex portions, and portions having different thicknesses.

The spherical recess is a portion having a surface curved in a spherical shape in the thickness direction. The spherical recess has a larger surface area per unit volume than the flat surface, and is a metal (target material) when forming a metal layer (deposited metal) or forming a coating layer (forming a film). Since the distance from the spray source of the coating agent (coating resin) is not constant, it becomes difficult to form a uniform layer (coating) as compared with the flat surface portion. The light-reflecting member of the present embodiment can maintain an excellent appearance of the light-reflecting member even when it has such a spherical recess.
The size of the spherical recess may be determined according to the shape and size of the fixture, lighting, etc. in which the light reflecting member of the present embodiment is used.

Further, at the time of molding, the slide core structure of the mold can be used to provide a convex portion (for example, an arch shape, a hook shape, etc.) protruding in the thickness direction of the light reflecting member. , The distance from the spray source of the metal (target material) and coating agent (coating resin) is not constant, and the metal (target material) and coating agent (coating resin) do not adhere sufficiently. In comparison, it becomes difficult to form a uniform layer (coating). The light-reflecting member of the present embodiment can maintain an excellent appearance of the light-reflecting member even when it has such a convex portion.
The size of the spherical recess may be determined according to the shape and size of the fixture, lighting, etc. in which the light reflecting member of the present embodiment is used.

Furthermore, even if the shape has a portion with a thickness difference of 1 mm or more, such as an inclination in thickness or the presence of a groove, there is a portion where the metal (target material) or coating agent (resin coating) does not sufficiently adhere, which is compared with the flat surface portion. This makes it difficult to form a uniform layer (coating). The light-reflecting member of the present embodiment can maintain an excellent appearance of the light-reflecting member even when the thickness differs by 1 mm or more.
The difference in thickness may be determined according to the shape and size of the fixture, lighting, etc. in which the light reflecting member of the present embodiment is used.
Further, the thickness of the light reflecting member is preferably 0.2 to 6 mm, more preferably 0., from the viewpoint of preventing poor appearance such as voids on the surface of the light reflecting member and poor filling of the flow end (short shot). It is 5 to 5 mm, more preferably 1 to 3 mm.

As described above, it is usually difficult to form a uniform metal layer and a coating layer with a light-reflecting member having a complicated shape having spherical concave portions, convex portions, and portions having different thicknesses in order to have a design. Therefore, it is difficult to maintain the appearance under high temperature and high humidity conditions, but by adopting the configuration of this embodiment, even a light reflecting member having such a complicated structure is excellent in high temperature and high humidity conditions. The effect of maintaining the appearance can be exhibited.

[Use of light reflecting member]
The light reflecting member of the present embodiment is not particularly limited, but can be used for the following appliances, lighting, and the like, for example, for indoor lighting fixtures, outdoor lighting fixtures, mobile medium lighting, and electronic devices such as office machines. It can be used for lighting, housing members for office machines, and the like. Further, the light reflecting member of the present embodiment can be used in a high temperature and high humidity environment, and is a closed container containing a heat source or in a state where the heat source is present in the vicinity, a member directly irradiated with sunlight, and the like. The member can also be used in a sealed container.

Hereinafter, the present invention will be described with reference to specific examples and comparative examples, but the present invention is not limited thereto.
The measurement methods and raw materials used in Examples and Comparative Examples are shown below.

<Measurement / evaluation method of physical properties>
(Measurement method of coefficient of linear expansion)
After the resin composition is dried at 100 ° C. for 3 hours, the ISO-A dumbbell is used in an EC75SX molding machine (manufactured by Toshiba Machine Co., Ltd.) under predetermined conditions, with an injection time of 20 seconds and a cooling time of 20 seconds. A dumbbell test piece was molded. The obtained test pieces are 10 mm × 5 mm × 4 mmt, respectively, from the central portion in the flow direction (MD direction) and the direction perpendicular to the flow direction (TD direction) of the resin composition at the time of injection molding. I cut it out. The coefficient of linear expansion of the cut out test piece was measured according to ISO11359-2. Specifically, the cut out test piece was held at 130 ° C. for 3 minutes using TMA-7 (manufactured by PerkinElmer), annealed at a temperature lowering rate = 5 ° C./min, and then heated. The coefficient of linear expansion at −30 to 65 ° C. was measured at a speed of 5 ° C./min and a load of 10 mN. The measurement was performed using three different test pieces in each direction (MD direction, TD direction), and the arithmetic mean value was taken as the linear expansion coefficient of the resin substrate.

(Measurement method of contact angle)
The static contact angle when water droplets were dropped on the light reflecting members obtained in Examples and Comparative Examples was measured. Using DMo-901 (manufactured by Kyowa Interface Science Co., Ltd.), water droplets were dropped on the surface of the coating layer of the light reflecting member, and then the water droplets were photographed from the side with a camera. From the image, the angle formed by the tangent line of the contour curve of the water droplet and the surface of the coating layer at the intersection of the contour curve of the water droplet and the surface of the coating layer was obtained. 10 drops of water were measured, and the average value was taken as the contact angle (degrees).

(Appearance evaluation)
After the light-reflecting members obtained in Examples and Comparative Examples were placed in a constant temperature and humidity chamber at 85 ° C. and 85% for 7 days, the surface of the light-reflecting members was visually observed, and the appearance was poor. , The presence or absence of peeling, cracking, and cloudiness of the metal layer and the coating layer was confirmed. The evaluation criteria for passing are shown below. If even one item was rejected, the comprehensive judgment was rejected, and if all the items were passed, the comprehensive judgment was judged to be acceptable. [Evaluation criteria]
(1) Peeling:
The vapor deposition mirror surface is not distorted, and the metal layer and coating layer are not peeled off at the vapor deposition mirror surface and edges: 4 points (pass)
The vapor deposition mirror surface is not distorted, but the metal layer and coating layer are peeled off at the vapor deposition mirror surface and / or the edge: 3 points (pass)
The vapor deposition mirror surface is distorted, but the metal layer and coating layer are not peeled off at the vapor deposition mirror surface and edges: 2 points (failure)
The vapor deposition mirror surface is distorted, and the metal layer and coating layer are peeled off at the vapor deposition mirror surface and / or the edge: 1 point (failure)
(2) Cracks:
No cracks in the coating layer and no cracks in the metal layer: 3 points (pass)
Small cracks less than 1 mm are seen in the coating layer, but no cracks in the metal layer: 2 points (pass)
The coating layer has cracks of 1 mm or more, or the coating layer has minute cracks of less than 1 mm, and the metal layer also has cracks: 1 point (failure)
(3) Cloudy:
No fogging on the coating layer: 3 points (pass)
Fogging with a diameter of less than 1 mm is present in the coating layer: 2 points (pass)
Cloudiness with a diameter of 1 mm or more exists in the coating layer: 1 point (failure)

<Raw materials>
(Resin composition)
-PA / PPE: Alloy with a mass ratio of polyamide 6 and polyphenylene ether of 1: 2 (MFR (280 ° C.) is 30 g / 10 min)
-PS / PPE1: Alloy with a mass ratio of polystyrene and polyphenylene ether of 1: 1 (MFR (280 ° C.) is 20 g / 10 min)
PS / PPE2: Alloy with a mass ratio of polystyrene and polyphenylene ether of 1: 1 and 20% by mass of glass fiber as an inorganic filler with respect to 100% by mass of the resin composition (MFR (280 ° C.) is 36 g / 10 min. )
-PPS / PPE: Alloy with a mass ratio of polyphenylene sulfide and polyphenylene ether of 6: 4 (MFR (300 ° C) is 16 g / 10 min)
LDPE: Low density polyethylene (MFR (280 ° C) is 43 g / 10 min)
A semi-automelt indexer (2A manufactured by Toyo Seiki Seisakusho Co., Ltd.) was used for measuring the MFR of each resin composition. After setting the barrel temperature to 280 ° C. (300 ° C. in the case of PPS / PPE array) and setting a load of 5 kgf, the resin composition pellets obtained in Examples and Comparative Examples were filled and the resin composition flowed. After confirming that the resin composition had been discharged, the mass of the strand-shaped resin composition discharged in 10 seconds was measured 5 times. The measured value was converted into the mass discharged in 10 minutes, and the average value was taken as the MFR value (g / 10 min).

(metal)
-Aluminum (coefficient of linear expansion: 2.4)
-Aluminum-Cu (coefficient of linear expansion: 2.4)

(Coating agent)
・ Epoxy ester resin ・ Epoxy acrylate resin

[Example 1]
(Manufacturing of resin substrate)
Using PA / PPE as the resin composition and an injection molding machine EC60SX (manufactured by Toshiba Machinery Co., Ltd.) as the molding device, the resin temperature is 260 to 320 ° C, the mold temperature is 90 ° C, the injection pressure (gauge pressure) is 150 MPa, and the injection speed. A resin substrate having a shape shown in FIG. 1A and having a shape of 120 mm × 80 mm × thickness of 1 to 3 mm was molded at 50 mm / sec (panel set value).
The thickness of the resin composition at the time of injection molding was inclined with the upstream side (gate side) end in the flow direction as 3 mm and the downstream end (end side) in the flow direction as 1 mm. Further, as shown in FIGS. 1A and 1A, one spherical concave portion having R = 300 mm and an arch-shaped convex portion that draws an arch in the thickness direction are formed in order from the upstream side in the flow direction of the resin composition. The shape has one and one weld line exists in the convex portion. The arrows in the figure indicate the flow direction (gate direction) of the resin composition during injection molding.
(Formation of metal layer (mirror surface treatment))
A metal layer having a thickness of 40 nm was formed on the entire surface of the resin substrate obtained above by a PVD method (physical vapor deposition method) using aluminum (mirror surface treatment). Before the mirror surface treatment, a plasma treatment for giving an ion impact to the surface of the resin substrate was performed to improve the adhesion between the metal layer and the resin substrate.
(Formation of coating layer)
The epoxy ester resin and the epoxy acrylate resin are coated on the entire surface of the metal layer formed above so that the film thickness after solidification is 50 μm, and UV is irradiated to form a coating layer (coating treatment). As a result, a light reflecting member was produced.

[Examples 2 to 11]
A light reflecting member was produced in the same manner as in Example 1 except that the composition, molding conditions, shape, etc. shown in Table 1, FIG. 1 and FIG. 2 were used.
In addition, each of Examples 4 and 5 and Example 6 had a shape having through holes shown in FIGS. 1 (b) and 1 (c), respectively.

[Comparative Examples 1 to 5]
A light reflecting member was produced in the same manner as in Example 1 except that the composition, molding conditions, shape, etc. shown in Table 2 and FIG. 2 were used.
In Comparative Example 1, the thickness was not inclined and was set to a uniform thickness (2 mm).

Tables 1 and 2 show the evaluation results of the light reflecting members of Examples and Comparative Examples.

While the appearance evaluation results of all the molded products within the scope of the present invention were pass judgments, all of the molded bodies were rejected in the comparative examples, and the effectiveness of the present invention can be recognized.

Since the light reflecting member of the present invention can exhibit a good appearance in a high temperature and high humidity environment even if it has a complicated shape, it can be used for indoor lighting equipment, outdoor lighting equipment, mobile medium lighting, office machines, and the like. It can be suitably used for lighting for equipment, housing members for office machines, and the like.

1 Light reflecting member 2 Spherical concave part 3 Convex part 4 Weld 5 Through hole

Claims (9)

It has three layers, a resin substrate, a metal layer, and a coating layer, in this order.
The resin substrate contains a resin composition containing a modified polyphenylene ether and contains.
The ratio of the coefficient of linear expansion of the metal layer to the resin substrate (metal layer / resin substrate) is 0.24 to 1.0.
A light reflecting member having a contact angle of the coating layer with respect to water of 90 to 180 °. The light reflecting member according to claim 1, wherein the melt flow rate (based on ISO1133) of the resin composition is 5 to 40 g / 10 min. The light reflecting member according to claim 1 or 2, wherein the modified polyphenylene ether contains polyphenylene ether and polystyrene. The light reflecting member according to any one of claims 1 to 3, wherein the modified polyphenylene ether contains polyphenylene ether and polyphenylene sulfide. The light reflecting member according to any one of claims 1 to 4, wherein the metal layer is made of aluminum or an aluminum alloy. The light reflecting member according to any one of claims 1 to 5, which has a spherical recess in the thickness direction. The light reflecting member according to any one of claims 1 to 6, which has a convex portion in the thickness direction. The light reflecting member according to any one of claims 1 to 7, which has portions having different thicknesses of 1 mm or more. The light reflecting member according to any one of claims 1 to 8, wherein the resin substrate has a weld line.

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