JPS62257101A - Optical element having metallic film - Google Patents

Abstract

PURPOSE:To improve the adhesiveness between a plastic substrate and metallic layer by compounding at least one kind of compd. among the group consisting of a specific compd., hydroxyphenyl benzotriazole and substitution product thereof and org. phosphate compd. with a resin component contg. a polymer to form a base material. CONSTITUTION:This optical element is constituted by forming the metallic film on the base material formed by compounding at least one kind of the compd. selected from the group consisting of the compd. expressed by the formula I, the hydroxyphenyl benzotriazole and substitution product thereof and the org. phosphite compd. with the resin component contg. the polymer obtd. by polymerizing 100-5wt% methacrylate or acrylate having an alicyclic hydrocarbon group of 5-22C in the ester part and 0-95wt% other copolymerizable unsatd. monomer. In the formula I, R<1> denotes hydrogen or alkyl group of 1-6C, R<2> denotes hydrogen or alkyl group of 1-6C, R<3> denotes alkylene group of 1-6C, R<4> denotes monovalent - tetravalent aliphat. or arom. group of 1-30, m is a repeating number of R<3> and is 0 or 1 and n is the number of substituent and is 1-4 integer.

Description

[Detailed description of the invention] (Industrial application field) The present invention relates to an optical element having a metal film.

(Prior Art) Conventionally, optical elements having a metal film include mirrors in which a metal layer of aluminum or the like is formed on a substrate by vapor deposition, etc.
A half-mirror 2 optical reading disc and the like are known.

Recently, as base materials for the above elements, compared to glass, it has been developed that it is lightweight, has good productivity, is easy to process, has excellent impact resistance, and is highly safe even if broken. Due to their advantages, plastic substrates are becoming widely used.

On the other hand, compared to glass, plastic substrates have poor adhesion with the metal layer and are highly hygroscopic, so if placed in a high temperature and humid environment, they will expand due to hygroscopic expansion, resulting in a decrease in flatness and require high precision. However, it has drawbacks such as difficulty in applying it to certain application fields. Particularly, in plastic base materials that still retain the distortion generated during molding or processing, reduction in flatness and deformation of shape are noticeable due to the relaxation of residual distortion due to moisture absorption.

The ninth method for solving the above-mentioned drawbacks of plastic substrates is to take measures that focus on the interface between the substrate and the metal layer, rather than modifying the plastic substrate itself. For example, a method has been proposed in which a hard polysiloxane resin containing fine silica particles and an epoxy resin is applied to the substrate, an adhesive layer is provided, and a metal layer is then provided on this (Japanese Patent Laid-Open No. 59-216101). .

In addition, in order to improve the drawbacks due to the hygroscopicity of the plastic substrate, a method has been proposed in which a moisture-proof film is formed using liquid silicone, molten paraffin, etc. on the outer surface or intermediate layer of the element (Patent Application No. 129824/1983). , JP-A-59-1
No. 29825).

Further, as a method for forming a moisture-proof film, a method of vacuum-depositing silicon oxide, polyparaxylene, polyethylene, etc. onto an element is also known.

It is also known to improve the hygroscopicity itself of plastic substrates.

(Problems to be Solved by the Invention) The above method of providing an adhesive layer not only has the disadvantage that a step of forming the adhesive layer is essential, but also has the disadvantage that it is difficult to maintain a constant thickness of the adhesive layer, and the device The disadvantage is that the surface accuracy of the surface is deteriorated.

Further, even if the hygroscopicity of the plastic substrate is improved, the adhesion of the metal layer remains insufficient.

Furthermore, the above method for forming a moisture-proof film not only fails to improve the adhesion between the plastic substrate and the metal layer, but also does not improve the adhesion between the plastic substrate and the metal layer.

Long-term reliability regarding moisture absorption is poor, and it takes time to process elements with complex shapes. There is a problem that the mechanical strength of the membrane is low.

The present invention addresses these problems, firstly by improving the adhesion between the plastic substrate and the metal layer, and secondly by improving the heat resistance and moisture absorption of the element.

(Means for Solving the Problems) The present invention provides a methacrylic acid ester or an acrylic acid ester in which the ester moiety has an alicyclic hydrocarbon group having 5 to 22 carbon atoms [hereinafter referred to as "(meth)acrylic acid alicyclic hydrocarbon group". A resin component containing a polymer obtained by polymerizing 1100 to 5% by weight of the formula ester and 0 to 95% by weight of other copolymerizable unsaturated monomers.

(al General formula (11 [However, in formula 9, #R+' may have hydrogen or a carbon number of 1 to 6 and a further substituent), R" has a carbon number of 1 to 6.
6 alkylene group (which may further have a substituent), R4 is a monovalent to tetravalent aliphatic group having 1 to 30 carbon atoms (which may further have a substituent) , the group may have at least one of at least one of an ether bond and a thioether bond) or an aromatic group, mHR''
The number of repetitions is 0 or 1, and n is an integer of 1 to 4 as the number of substituents.

(bl) Hydroxyphenylbenzotriazole and a substituted compound of hydroxyphenyl benzotriazole and K (C) An optical device having a metal film formed by forming a metal film on a base material blended with at least one compound selected from the group consisting of organic phosphite compounds. Concerning elements.

First, the polymer will be explained.

The polymer is obtained by homopolymerization or copolymerization of alicyclic methacrylic ester and copolymerization of the ester with another copolymerizable unsaturated monomer, Ester is 100-5 based on total monomers
% by weight used.

When the (meth)acrylic acid alicyclic ester is less than 5% by weight, in combination with at least one compound selected from the group consisting of (a), (bl and (C)), the adhesion between the base material and the metal layer is reduced. cannot be improved.

The (meth)acrylic acid alicyclic ester is preferably used in an amount of 100 to 10% by weight based on the total monomers. The polymer not only improves the adhesion with the metal layer, but also itself usually has excellent heat resistance and moisture absorption resistance.

As a (meth)acrylic acid alicyclic ester.

Cyclopentyl methacrylate, cyclohexyl methacrylate, methylcyclohexyl methacrylate.

Trimethylcyclohexyl methacrylate, norbornyl methacrylate, norbornylmethyl methacrylate, inbornyl methacrylate, bornyl methacrylate, menthyl methacrylate, 7-ethyl methacrylate, adamantyl methacrylate, dimethyladamantyl methacrylate,
TricycloC'C5,2,1,0'')dec-8-yl (tricyclodecyl methacrylate), tricyclo[翫41.0''-')dec-4-methyl methacrylate, cyclodecyl methacrylate, etc. There are methacrylic esters and acrylic esters having ester moieties similar to these. Among these, (meth)acrylic acid alicyclic esters having three or more tertiary carbon atoms in the alicyclic hydrocarbon group are preferable from the viewpoint of monothermal property and adhesion with the metal film. .

From the viewpoint of heat resistance, esters of methacrylic acid are preferred. Particularly preferred examples include norbornyl methacrylate, norbornylmethyl methacrylate, tricyclodecyl methacrylate, tricyclo[5,2,
1,0"1 deca-4-methyl, etc.

Examples of unsaturated monomers copolymerizable with (meth)acrylic acid alicyclic esters include methyl acrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate. Acrylic acid alkyl esters, phenyl acrylates, etc.
Acrylic acid aromatic esters such as benzyl acrylate and naphthyl acrylate; substituted aromatic acrylic acids such as fluorophenyl acrylate, chlorophenyl acrylate, bromophenyl acrylate, fluorobenzyl acrylate, chlorobenzyl acrylate, and bromobenzyl acrylate; Acrylic acid halogenated alkyl esters such as esters, fluoromethyl acrylate, fluoroethyl acrylate, chloroethyl acrylate, and bromoethyl acrylate;
Acrylic acid hydroxyalkyl ester, acrylic acid glycidyl acrylate, acrylic acid ethylene glycol ester, acrylic acid polyethylene glycol ester.

Acrylic acid esters such as acrylic acid alkylaminoalkyl ester, acrylic acid cyanoalkyl ester,
Methacrylic acid alkyl esters such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, and 2-ethylhexyl methacrylate; methacrylic acid aromatic esters such as phenyl methacrylate, benzyl methacrylate, and naphthyl methacrylate; fluorophenyl methacrylate;
Substituted aromatic esters of methacrylic acid such as chlorophenyl methacrylate, bromophenyl methacrylate, fluorobenzyl methacrylate, chlorobenzyl methacrylate, bromobenzyl methacrylate, fluoromethyl methacrylate, fluoro-aethyl methacrylate, T methacrylate:
Ir: 1-ethyl, halogenated alkyl methacrylate such as bromoethyl methacrylate, hydroxyalkyl methacrylate, glycidyl methacrylate, ethylene glycol methacrylate, polyethylene glycol methacrylate, alkylaminoalkyl methacrylate, cyanoalkyl methacrylate Methacrylic esters such as esters, α-fluoroacrylic esters, α-chloroacrylic esters,
α-substituted acrylic acid varnish f k fz , such as α-cyanoacrylate ester! There is "l".

Examples of the aromatic vinyl compound include styrene or α-substituted styrenes such as α-methylstyrene, α-ethylstyrene, α-fluorostyrene, and α-chlorostyrene, fluorostyrene, and chlorostyrene.

Nucleically substituted styrenes include bromostyrene, methylstyrene, butylstyrene, and methoxystyrene.

Examples of vinyl cyanide compounds include acrylonitrile and metacyclonitrile.

Unsaturated dibasic acids and their derivatives include N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-methylphenylmaleimide, N-chlorophenyl Maleimide Examples include N-substituted maleimides such as N-methoxyphenylmaleimide and N-carboxyphenylmaleimide, maleic acid, maleic anhydride, and fumaric acid.

Unsaturated fatty acids and their derivatives include acrylamide, methacrylamide, N-dimethylacrylamide, N
- (Meth)acrylamides such as diethylacrylamide, N-dimethylmethacrylamide, N-diethylmethacrylamide, calcium acrylate, calcium methacrylate, barium acrylate, barium methacrylate, lead acrylate, lead methacrylate, tin acrylate , metal salts of acrylic acid or methacrylic acid, such as tin methacrylate, zinc acrylate, and zinc methacrylate.

Examples include acrylic acid and methacrylic acid.

Among these other copolymerizable monomers, it is preferable to use aromatic vinyl compounds in order to reduce the moisture absorption rate.

As a method for producing the polymer of the present invention, known methods such as radical polymerization and ionic polymerization can be applied. For example, it can be produced by methods such as bulk polymerization, solution polymerization, and P+ turbid polymerization in the presence of a polymerization initiator.

Examples of initiators used in the polymerization include benzoyl peroxide, lauroyl peroxide, di-t-butylperoxyhexahydroterephthalate, t-butylperoxy-2-ethylhexanony), and 1,1-di-t- Organic peroxides such as butylperoxy-3,3,5-)limethylcyclohexane, azobisisobutyronitrile, azobis-4
- Azo compounds such as methoxy-2,4-dimethylvaleronitrile, azobiscyclohexanone-1-carbonitrile, azodibenzoyl, water-soluble catalysts such as potassium persulfate, ammonium persulfate, and peroxides or persulfates. Any catalyst that can be used in normal radical polymerization, such as a redox catalyst using reducing agent combination K, can be used. The polymerization catalyst is 0.01~]O based on the total amount of monomers.
It is preferable to use it in a range of t% by weight. Mercaptan compounds, thioglycol, carbon tetrabromide as polymerization regulators.

α-methylstyrene dimer or the like may be added as necessary to adjust the molecular weight.

The polymerization temperature is preferably selected appropriately between 0 and 200°C, preferably 1% and 5θ to 120°C.

Solvents for solution polymerization include benzene, toluene,
Xylene, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, dichloroethylene, etc. can be used.

Suspension polymerization is carried out in an aqueous medium, with the addition of suspending agents and, if necessary, suspension aids. Suspending agents include water-soluble polymers such as polyvinyl alcohol, methyl cellulose, and polyacrylamide, and sparingly soluble inorganic substances such as calcium phosphate and magnesium pyrophosphate. 1% by weight and the poorly soluble inorganic substance is 0.05 to 0.5% by weight based on the total amount of monomers.
[Preferably used.

As a suspending agent, there are anionic surfactants such as sodium dodecylbenzenesulfonate, and when a sparingly soluble inorganic substance is used as a suspending agent, it is preferable to use them together.

The suspension aid is O,OO1-0.0 based on the total amount of monomers.
Preferably, 2% by weight is used.

The polymer used in the present invention has a molecular weight of 10.
Those in the range of OOO to 1.000.000 are preferred, and those in this range are particularly preferred when used as a molding material.

Furthermore, from the viewpoint of maintaining particularly excellent low hygroscopicity, the polymer used in the present invention preferably has a carbon atom ratio of 60][71 or more in the molecule as determined by elemental analysis of one polymer.

The above-mentioned polymers in the present invention form the resin component singly or as a blend of two or more thereof, or as a blend of these and other resins or resins.

Here, as a method for producing a blend, the above-mentioned polymers or the above-mentioned polymer and another resin are extruded.

A method of melt-kneading with an injection molding machine, a compression molding machine, a roll, etc., a method of dissolving the above polymer or other resin in a raw material monomer of the above polymer or other resin, and then polymerizing it, a method of polymerizing the above polymers with each other or with the above polymers. There are methods such as dissolving another resin in a solvent and then removing the solvent.

□ Examples of other blended resins include polystyrene,
Polymethyl methacrylate, polycarbonate, styrene-acrylonitrile copolymer, methyl methacrylate-styrene copolymer, vinyl chloride.

Examples include styrene-maleic anhydride copolymer, acrylonitriloptazine-styrene copolymer, acrylic acid ester-acrylonitrile-styrene copolymer, linear polyester, polyphenylene oxide, polyamide, polyacetal, and the like.

The resin component of the present invention contains a (meth)acrylic acid alicyclic ester component in an amount of 100 to 5% by weight based on the weight of the resin component.
It is preferable to contain, particularly preferably 100 to 10% F&%. If this amount is too small, the adhesion between the base material and the metal film will not be sufficiently improved.

Moreover, this resin component also has good heat resistance and moisture absorption resistance. To ensure these benefits, (meta)
It is preferable that the acrylic acid alicyclic ester component is contained in an amount of 10 or more by weight based on the resin component.

In addition, in order to prevent dimensional changes due to moisture absorption of the optical element having the metal film according to the present invention (to ensure dimensional stability), or when creating all 1!4 film layers, it is necessary to In order to prevent the adhesion of the metal film from decreasing due to the dissipation of moisture contained in the resin component, the saturated water absorption rate of the resin component is preferably 1% by weight or less, and preferably 0.6% by weight or less. is more preferable, and most preferably 0.4 weight or less. Further, from the viewpoint of heat resistance, it is preferable that the glass transition point of the resin component is 110° C. or higher.

Next, the compounds (a), (b) and (C) will be explained.

The compound (a) represented by the general formula (■) needs to have a group represented by group 6 (herein, R1 and R2 are the same as above). In this group,
The hydroxyl group is preferably present at the para or ortho position relative to the bond, and when the hydroxyl group is bonded to the para position, it is preferable that the alkyl group is bonded to one or two of the two meta positions. Preferably.

When the hydroxyl group is bonded to the ortho position, it is preferable that the alkyl group is bonded to the para position.

Further, in general formula +11, when R4 is a monovalent group.

Alkyl group having 1 to 30 carbon atoms, group -R' -X -R6
.

The group -R7-X-R'-X'-R@ or a phenyl group or an alkyl group, a phenyl group substituted with a halogen or the like is preferable.

Here, the group -R5-X-R6 is as follows. That is, e-R'- is an alkylene group having 1 or more carbon atoms.

R6 is an alkyl group having 1 or more carbon atoms, and X is oxygen or sulfur, and the total number of carbon atoms in R5 and R6 is preferably 2 or more and 30 or less. R5 and R6 may further have a substituent.

Moreover, the group -R'-X-rL''-X'-R'' is as follows. That is, R7 and R1 are each independently an alkylene group having 1 or more carbon atoms, Re is an alkyl group having 1 or more carbon atoms, X and X' are each independently oxygen or sulfur, and #R'#R'' and R9 are The total number of carbon atoms is 3 or more and preferably 30 or less. 1%7. R8 and R9
may further have a substituent.

In addition, when R4 is a divalent group, an alkylene group having 1 to 30 carbon atoms, the above group -R5-X-R@ in which W is trivalent or R6 is divalent, the above group - R7-X-R8
In the -X'-R group, R7 or R1 is preferably trivalent or R group is divalent.

Further, when R4 is trivalent or tetravalent, it is preferably a trivalent or tetravalent aliphatic hydrocarbon group, and when R4 is tetravalent, it may be carbon.

In general formula (1), R1, RF, R3 and R4, and the R5°R6, It, ? , in R' and R9,
Examples of substituents that may be present include halogens such as chlorine atoms and bromine atoms, and phenyl groups.

Examples of compounds represented by the general formula +1) include n-octadecyl 3-(≦5'-di-t-butyl-4'-hydroxyphenyl)-flobionate, n-octadecyl 3-
．． 5-di-t-butyl-4-hydroxyphenylacetate, neo-dodecyl 3-(3,'5'-se-t-butyl-4'-hydroxyphenyl)propionate, dodecyl-β-(3,5-di-t -butyl-4-hydroxyphenyl)globionate, ethyl α-(&5-di-t)
-Butyl-4-hydroxyphenyl)-isobutyrate, octadecyl α-(&5-di-t-butyl-4-hydroxyphenyl-imbutyrate, octadecyl α-
(3,5-di-t-butyl-4-hydroxyphenyl)
- Gropionate, λ4-di-t-butylphenyl-3
:5'-di-t-butyl-4'-hydroxybenzoate, 2-Cn-octylthio)ethyl-3:5'-di-
t-butyl-4'-hydroxybenzony), 2-(n
-octylthio)ethyl-3: s'-t-phthyl-4'-hydroxyphenylacetate, 2-(n-octadecylthio)ethyl A/ r s/-t-butyl-
4'-Hydroxyphenylacetate, 2-(n-octadecylthio)ethyl 5'-t-phthyl 4'-
hydroxybenzony), 2-(2-hydroxyethylthio)ethyl 3:5'-thet-butyl-4'-hydroxybenzoate, 42'-thiodietanol bis<
a s'-sheet t-7'thyl-41-hydroxyphenyl) acetate, diethylene glycol bis(3,5
-di-t-butyl-4-hydroxyphenyl) flobionate, 2-(n-octadecylthio>a-(,3'5
'-')-1-7'thyl-4-hydroxyphenyl)propionate, 2,2'-thiodiethanol-bis-3
-(3,5-di-t-butyl-4-hydroxyphenyl)globionate, 1,2-propylene-glycol bis-[3-(3:5'-di-t-butyl-4'-hydroxyphenyl)propionate , ethylene gelcol bis-(3-(3:s'-di-butyl-4'-hydroxyphenyl) flobionate), neopentyl glycol bis(a-us'-di-t-butyl-4'-hydroxyphenyl) flobionate ), ethylene glycol-bis-(3,5-di-t-butyl-4-hydroquine-7enyl)acetate, glycerin-1-n-octadecylthio)-2,3-bis-kube5'-di- t-Butyl-4'-hydroxyphenyl)acetate, pentaerythritol-tetrakis-2-2-(3:5'-di-t-
butyl-4-hydroxyphenyl)propione), 1
．． 1.1-trimethylol-tris-3-<3:s'-
di-t-butyl-4'hydroxyphenyl)propionate, 1,2,3-butane trio-root tris-[3-
(3:5'-di-t-butyl-4'-hydroxyphenyl)propione-θ, 1.6-n-hexanediol-
Bis[(3:5'-di-t-butyl-4'-hydroxyphenyl)propione.

Hydroxyphenylbenzotriazole and its substituted product (b) are represented by the general formula tll) [however, in formula 9, #R
IO and R'' are each independently hydrogen or carbon number 1-3
0 aliphatic hydrocarbon (which may be substituted), and R" is hydrogen, halogen such as chlorine, or a carbon atom having 1 to 1 carbon atoms.
A compound represented by the following is preferred.

In the general formula fIIl, it is most preferable that the submerged hydroxyl group is bonded to the ortho position to the zotriazole group.

Examples of hydroxyphenylbenzotriazole and its substituents include 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'-di-t-butylphenyl)benzotriazole, 2- (2'-hydroxy-3'-t-butyl 5'
-methylphenyl)benzotriazole, 2-(,5s
'-di-t-amyl-2'-hydroquinphenyl)benzotriazole, 2-(2'-1= )" Roxy 51
++ t-butylphenyl)benzotriazole, 2
-(2'-hydroxy-4'-octoxyphenyl)benzotriazole, 2-[2'-hydroxy-3:5'
-bis(α,α-dimethylbenzyl)phenyl]-2H
-penztriazole, 2-(2'-hydroxy-5'
-methoxyphenyl)benzotriazole, 2-(3
'-t-butyl-5'-/thi-27-hydrofoxyphenyl)-5-chlorobenzotriazole, 2-(3:
5'-di-t-)f-ru-2'-hydroxyphenyl)
-5-10 Lopenzotriazole and the like.

The organic phosphite compound (C) is a monophosphite,
Including diphosphite and triphosphite.

These thiophosphites are also included. Examples of the organic phosphite include tris(2-hydroxyethyl)
Phosphite, hydroxyalkyl phosphite such as tris(dipropylene glycol) phosphite, bis(dipropylene glycol) phosphite, tris(polytetramethylene glycol) phosphite, tributyl phosphite, trihexyl phosphite, trioctyl phosphite alkyl phosphites such as tridecyl phosphite, trilauryl phosphite, trimyristyl phosphite, triotadecyl phosphite, dilauryl phosphite, dihexadecyl phosphite, dioctadecyl phosphite; phyto, tri(octylphenyl) phosphite, dioctylphenyl phosphite, tri(vinylphenyl) phosphite, di(vinylphenyl) phosphite, )'J(y sylphenyl) phosphite, tri(octadecylphenyl) phosphite, Tris Aryl phosphites such as (nonylphenyl) phosphites, decyl diphenyl phosphites, and didecyl phenyl phosphites.

Dodecyl phenyl phosphite, didodecyl 7-enyl phosphite, octadecyl diphenyl phosphite, dioctadecyl phenyl phosphite.

Alkylaryl phosphites such as bis(nonylphenyl)decyl phosphite, didecyl(nonylphenyl) phosphite, bis(octylphenyl)octadecyl phosphite, alkylthiophosphites such as trilauryl trithiophosphite, triotadecyl trithiophosphite, tris (lauryl-2-thioethyl)
Monophosphites such as phosphites; tetrakis ()
(nylphenyl) polypropylene gelyl diphosphite, tetrakis octadecyl polyethylene/IJ cold diphosphite, tetrakis decyl hexamethylene-
1,6-thiol diphosphite.

Tetrakis dodecyl ethylene glycol diphosphite, tetrakis dodecyl tripropylene glycol tetrathiodiphosphite, bisneopentyl glycol triethylene glycol diphosphite, diisododecyl pentaerythritol diphosphite, di-tetradecyl pentaerythritol diphosphite , bis(neopentyl glycol)-1,4-cyclohexadimethylene phosphite, distearylpentaerythritor diphosphite, diinodecylpentaerythritor diphosphite, tetra(012-C1s mixed alkyl)-4, 4′
Diphosphites such as -isopropylidene diphenyl diphosphite, tetra(tridecyl) -4,4'-butylidenebis(3-methyl-6-t-butylphenyl) diphosphite, polydiphosphite: heptakis alkylene glycol triphosphite, heptakis propylene Glycol triphosphite, heptakis ethylene glycol triphosphite, heptakis ethylene glycol triphosphite, heptakis dipropylene glycol triphosphite, heptakis cyclohexane dimetatool triphosphite, heptakis polypropylene glycol triphosphite, heptakis hexamethylene-1,6- Thioltriphosphite, heptakis 1
．． 9-7 Nanediol Triphosphite, Heptakis 1
．． There are triphosphites such as 2-octadecanethiotriphosphite.

In the present invention, one of the compounds (al, (bl) and (C) above is particularly preferred from the standpoint of promoting improvement in the adhesion of the light reflective layer.

For example, in compound (a), n-octadecyl-3
-(4'-hydroxy-3:5'-di-t-butylphenyl)propionate, 1,6-hexanethiol bis[3-(3:5'-di-t-butyl-4'-hydroxyphenyl) ) propionate] and tetrakis[methylene-3(3:5'-di-t-butyl-4'-hydroxyphenyl)propionate comethane, among the compounds of (b), 2(2'-hydroxy-3, '5'-sheet t
-butylphenyl)penztriazole and among the compounds of (C), tetra(tridecyl) -4,4'-
Mention may be made of butylidene bis(3-methyl-6-t-butylphenyl) diphosphite and tetra(C1~CIS mixed alkyl)-4,4'-isopropylidene diphenyl diphosphite.

At least one compound selected from the group consisting of compounds (a), Tb) and (C) is preferably blended in an amount of 0.01 to 5% by weight, and preferably 0.1 to 5% by weight based on the resin component.
Double f! It is preferable to mix % in . If this amount is too small, the adhesion between the base material and the metal film will be insufficiently improved, and if it is too large, the mechanical properties of the base material will tend to deteriorate.

A method for blending at least one compound selected from the group consisting of the compounds (a), (b) and (C) into a resin component includes mixing the resin component and the compound in an extruder, an injection molding machine, a compression molding machine, A method in which the resin component and the compound are dissolved or dispersed in a solvent, and then kneaded as necessary and the solvent is removed.

There are methods of synthesizing the resin component by dissolving or dispersing the compound in the raw material of the resin component and then polymerizing it.The last method described has a relatively small range of variation in properties.

Workability is also good.

Further, other additives such as a solvent and a plasticizer may be added to the resin component. The blending method is the same as above, and the blending amount of each additive is preferably 3% by weight or less based on the resin component.

As lubricants, butyl stearate, stearyl alcohol, monoglycerol wintertearic acid ester, sorbitan monopalmitate, mannitol, stearic acid, hydrogenated castor oil stearamide, oleic acid amide, ethylene bisstearyl, octyl alcohol, decyl alcohol.

Examples include lauryl alcohol, myristyl alcohol, and cetyl alcohol, and examples of plasticizers include di-2-ethylhexyl phthalate, di-normal octyl phthalate, and di-normal dodecyl phthalate.

Ditridecyl phthalate, butyl oleate, diyne butyl adipate, diisodecyl adipate.

Tri-2-ethylexyl trimellitate and the like.

Other additives include the above fat, (b) and fc)
In addition to these compounds, there are other compounds that are classified as antioxidants, ultraviolet absorbers, mold release agents, antistatic agents, flame retardants, heavy metal deactivators, etc.

The base material in the present invention can be obtained by molding into a suitable shape by injection molding, press molding, extrusion molding, etc. after or while blending the above compound with a resin component.

Further, the base material can be obtained by molding by cast molding. In cast molding, the above-mentioned (a), (
After dissolving at least one compound selected from the group consisting of compounds of BL and (C1), a polymerization initiator, and other additives as necessary, prepolymerization is performed as necessary, and the mixture is poured into a mold and subjected to double polymerization. It is done.

The method for forming a metal film on the base material includes aluminum, zinc, 5R, nickel, chromium, and tin.

Silver, gold + platinum, manganese, titanium, germanium.

Vacuum evaporation method using metals such as tungsten, lead, cadmium, etc. singly or in mixtures or alloys.

It is formed using a sputtering method, an ion blating method, or the like.

Optical elements according to the present invention manufactured in this manner include fender mirrors and rearview mirrors.

Automotive parts such as under mirrors, compact mirrors,
Total reflection mirrors for copying machines, roof mirrors, etc.

Total reflection mirrors for facsimiles, condensing mirrors for laser beam printers, reflective mirrors, half mirrors, rotating polygon mirrors that deflect laser beams, etc.

Total reflection mirror for cameras, optical path splitting prism (for total reflection,
For half mirrors, etc.), curved mirrors for roads.

Examples include guichroic mirrors, cold mirrors, mirrors for lasers, disks for information recording media, optical filters, and concave mirrors.

An optical element having a metal film according to the present invention includes:

On the metal film, Altos, CrzOs, Si
n, 5iOz, TiO.

The protective film may be formed using TiCh or the like. The protective film can be formed using a vacuum evaporation method, a sputtering method, an ion blasting method, or the like.

(Example) Next, examples of the present invention will be shown.

Example 1 500m1 equipped with a gas jet pipe with a 0-pass plate! 200 g of tricyclodecyl methacrylate (monomer) in a round bottom flask.
Tert-butyl peroxy-2-ethylhexanoate (polymerization initiator) 0.89,1° 1-bis(tert-butylperoxy) 3,3° 5-trimethylcyclohexane (polymerization initiator) 02 g, n -Octadecyl-3-(4'-hydroxy-3,'5'-di-tert-butylphenyl)propionate (additive)
0.29, mix and dissolve, and bring the inside of the flask to 1o.
After replacing the solution with nitrogen gas at a flow rate of 1/2 oz/min for 30 minutes and confirming that the amount of dissolved oxygen is 2 mg/l or less, inject this solution into the glass cell and place it in an ultrasonic cleaner. The glass cell was left for 20 minutes to degas. Next, this glass cell was transferred to a constant temperature bath and incubated at 60°C for 6 hours.
Polymerize at 0°C for 2 hours, at 130°C for 8 hours, and at 150°C for 2 hours t 100anuX 100n+tuX 10
A polymeric board of m was obtained.

Next, the saturated water absorption rate and glass transition point were measured using the obtained polymeric board. Each value is 0.2%.

The temperature was 173°C. First of all, the saturated water absorption rate.

After drying the polymer board and measuring its dry weight, the polymer board was then immersed in warm water at 70°C for 72 hours.

The weight (water absorption weight) was determined using the following equation.

Furthermore, the glass transition point was defined as the temperature at the endothermic peak in a differential scanning calorimeter (DSC).

Next, dimensional changes in the thickness direction of the polymeric board during drying and saturated water absorption were measured using a micrometer, but no changes could be detected.

Next, the small vacuum evaporation device VPC-26 manufactured by X Kuukiko
A mirror was fabricated by depositing aluminum on a polymeric plate under a reduced pressure of 10-' Torr using a vacuum cleaner. The vapor-deposited polymer board was left together with 810 mending tape manufactured by Sumitomo 3M Co., Ltd. in an atmosphere of 23°C ± 2°C and relative humidity of 65 ± 5°C for 2 hours.

The mending tape was pressed onto the vapor deposition surface using a roller covered with a rubber layer, and after 40 minutes had passed, the mending tape was peeled off. The adhesion rate at this time was determined using the following formula. The adhesion rate was 98 inches.

Ram adhesion area (18 au x 20 m) Examples 2 to 10 and Comparative Example 1 Synthesis and evaluation were performed using the same method and composition as in Example 1, except that the amount and type of additive were changed.

The amount of one type of additive and the adhesion rate are shown in Table 1 together with those of Example 1.

As is clear from Table 1, when additives are used (Examples 1 to 10), the aluminum adhesion rate is excellent, but when no additives are used (Comparative Example 1), the aluminum adhesion rate is poor. It was low.

Examples 11 to 17 and Comparative Examples 2 to 3 Below, based on the apparatus and method used in Example 1, n-octadecyl-3-(4'-hydroxy'/-,
Using 012 g of 55'-di-tert-butylphenyl) propionate and 0.29 g of 2(2'-hydroxy-5'-methylphenyl) benzotriazole, a monomer having the monomer composition shown in Table 2 was used as the monomer. Example 1 was carried out in the same manner as in Example 1 except that a mixture was used. Table 2 shows the results.
Shown below.

Example 18 51 equipped with a stirrer! Basic calcium phosphate 10% by weight water suspension gsag as a dispersant in an autoclave,
Dodecylbenzenesulfonic acid) IJum 0.0
049 and 1 g of sodium sulfate were added together with pure water 24009 and stirred and mixed to obtain a suspension medium. A composition having the following composition was added thereto, the stirring rotation speed was set to 20 Orpm, and the mixture was stirred at 70°C for 5 hours and at 90°C for 2 hours under a nitrogen atmosphere at 120°C.
Polymerization was carried out at ℃ for 3 hours.

Composition Tricyclodecane methacrylate 560g Methyl methacrylate 400g Steel 10409 Stearyl alcohol 2g The resulting polymer particles were pickled, washed with water, dehydrated, and then vacuum dried to obtain a particulate polymer. Mold temperature 230℃.

Press molded at a pressure of 200 kg/c-, 100wX1
I got a board of 00-×10 cabinets. The results are shown in Table 2.

Example 20 Suspension polymerization was carried out in the same manner as in Example 19, except that the monomer composition was changed to the following.

The obtained polymer particles 2 were mixed with 1.45 kg of 9 and 7 acrylonitrile-styrene copolymer (a copolymer of 24% by weight of acrylonitrile and 76% by weight of styrene) in a plastic bag, and the temperature was set at 250°C. Melted by an extruder
Knead to obtain pellets.

The pellets were placed in a mold at a temperature of 250°C and a pressure of 200 kg/cm.
"Press molded with 100wX 100annX
A 10 mm plate was obtained. The results are shown in Table 2.

As is clear from Table 2, when additives were added to the resin component of the present invention (Examples 12 to 21).

Although the adhesion rate of aluminum is excellent, when an additive is added to the resin component other than the one according to the present invention (Comparative Examples 2 to 3), the adhesion rate of aluminum is significantly inferior.

(Effects of the Invention) The optical element according to the present invention is crushed by the adhesion between the base material and the metal and has good heat resistance. Furthermore, hygroscopicity can be improved compared to conventional materials.

Claims (1)

[Claims] 1. 100 to 5% by weight of methacrylic ester or acrylic ester in which the ester moiety has an alicyclic hydrocarbon group having 5 to 22 carbon atoms and other copolymerizable unsaturated monomers Resin components containing polymers obtained by polymerizing 0 to 95% by weight include (a) General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (I) [However, in the formula, R^1 is Hydrogen or an alkyl group having 1 to 6 carbon atoms (which may further have a substituent). R^2 is hydrogen or an alkyl group having 1 to 6 carbon atoms (this is
may further have a substituent), R^3 has 1 carbon number
~6 alkylene group (which may further have a substituent), R^4 is a monovalent to tetravalent aliphatic group having 1 to 30 carbon atoms (which may further have a substituent) or an aromatic group, m is the repeating number of R^3 and n is 0 or 1, and n is the number of substituents. 1
An integer of ~4], (b) hydroxyphenylbensotriazole and its substituted products, and (c) an organic phosphite compound. An optical element having a metal film formed by forming a metal film. 2. An optical element having a metal film according to claim 1, wherein the resin component containing the polymer has a saturated water absorption rate of 1% by weight or less.