JPH0616732A - Transparent heat-resistant resin - Google Patents

Abstract

PURPOSE:To obtain a resin having excellent heat resistance, transparency, flame retardance and solvent resistance, low water absorption, small change in dimension by water absorption and excellent temporary warpage by copolymerizing a composition comprising a specific maleimide compound and a halogen-containing monomer. CONSTITUTION:A composition comprising >=30wt.% (A) 20-98wt.% monomer of formula I (R<1> and R<2> are H, methyl or ethyl; R<3> is 1-20C alkyl, aryl, aralkyl, etc.) and (B) a halogen atom-containing monomer in amounts to give >=30wt.% total weight ratio of the components A and B is copolymerized to give the objective resin. N-Isopropylmaleimide and N-cyclohexylmaleimide are both used as the component A. A higher fluoroalkyl (meth)acrylate of formula II (b is 5-12) is preferable as the component B. When the copolymerization is carried out by casting polymerization, the composition is preferably heated in a mold at >=170 deg.C for >=10 minutes.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a transparent heat-resistant resin,
It is preferably used for optical filters for display devices, substrates for liquid crystal display devices, optical disc substrates, optical lenses and the like.

[0002]

2. Description of the Related Art In general, plastic materials are lightweight, and have excellent impact resistance, workability, and mass productivity, so that in recent years, they have been used as materials for optical elements such as optical filters for display devices, optical disk substrates, and optical lenses. Demand is growing. Currently, plastic materials for these optical elements include polymethylmethacrylate, polystyrene,
Transparent resins such as polycarbonate, amorphous polyolefin, and polydiethylene glycol bisallyl carbonate are mainly used.

[0003]

However, poly (methyl methacrylate) is inferior in heat resistance represented by heat distortion temperature,
Polystyrene not only has poor heat resistance, but also has the drawback of large birefringence. Further, polycarbonate and amorphous polyolefin also have insufficient heat resistance for use as substrates for liquid crystal display devices, for example.

Further, Japanese Patent Laid-Open No. 56-131654,
Also, Japanese Patent Laid-Open No. 58-126119 discloses an optical disk substrate made of a polymer using a maleimide compound. However, these techniques have a problem that they have poor solvent resistance and chemical resistance. JP-A-64-79208 discloses a thermosetting resin lens using a maleimide compound. However, even in this technique, the heat resistance was insufficient for use in substrates for liquid crystal display devices, for example. Further, these maleimide-based resins have a drawback that they are poor in water absorption dimensional stability due to their large water absorption.

Although thermosetting resins such as polydiethylene glycol bisallyl carbonate are excellent in solvent resistance and chemical resistance, they are still insufficient in heat resistance, so that a transparent heat-resistant resin having sufficient performance can be obtained. I haven't arrived.

The present invention is intended to solve the above problems, and is excellent in heat resistance, transparency, flame retardancy and solvent resistance, and also has low water absorption, a small water absorption dimensional change, and low warpage. It is intended to provide a transparent heat resistant resin.

[0007]

In order to achieve the above object, the present invention has the following constitution.

"If the monomer represented by the general formula (1) is 20 to
A composition containing 98% by weight and a monomer having a halogen atom, and the total weight ratio of the monomer represented by the general formula (1) and the monomer having a halogen atom is 30% by weight or more. A transparent heat-resistant resin characterized by being obtained by copolymerizing.

[0009]

[Chemical 2] (In the formula, R ¹ and R ² represent a substituent selected from hydrogen, a methyl group and an ethyl group. R ³ is selected from an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group and a cycloalkyl group. It represents a substituent.) ”First, the maleimide-based monomer represented by the general formula (1) will be described.

R ¹ and R ² may be the same or different.

Specific examples of R ³ include linear alkyl groups such as methyl group, ethyl group, propyl group, octyl group and octadecyl group, isopropyl group, sec-butyl group and tert-group.
-Branched alkyl groups such as butyl group, isopentyl group,
Examples thereof include cycloalkyl groups such as cyclohexyl group and methylcyclohexyl group, aryl groups such as phenyl group and methylphenyl group, aralkyl groups such as benzyl group and phenethyl group.

Further, R ¹ , R ² and R ³ are various substituents such as halogen groups such as fluorine, chlorine and bromine, cyano group, carboxyl group, sulfonic acid group, nitro group, hydroxy group and alkoxy group. It may be replaced.

Specific examples of the monomer represented by the general formula (1) include N-methylmaleimide, Nn-butylmaleimide, N-phenylmaleimide, N-o-methylphenylmaleimidomaleimide and N-m. -Methylphenylmaleimide, Np-methylphenylmaleimide, N-o-
Hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, N-o-methoxyphenylmaleimide, Nm-
Methoxyphenyl maleimide, Np-methoxyphenyl maleimide, N-o-chlorophenyl maleimide, N
-M-chlorophenyl maleimide, Np-chlorophenyl maleimide, N-o-carboxyphenyl maleimide, Nm-carboxyphenyl maleimide, Np-
Carboxyphenyl maleimide, N-o-nitrophenyl maleimide, Nm-nitrophenyl maleimide, N
Examples include -p-nitrophenyl maleimide, N-ethyl maleimide, N-isopropyl maleimide, N-isobutyl maleimide, N-tert-butyl maleimide, N-cyclohexyl maleimide and the like.

These monomers may be used alone or as a mixture of two or more. Further, among the maleimide monomers, from the viewpoint of colorless transparency, heat yellowing, and weather resistance, alkylmaleimide and cycloalkylmaleimide are particularly preferable, and N-isopropylmaleimide and N- are particularly preferable.
Cyclohexylmaleimide is preferred. Furthermore, from the viewpoint of ease of monomer adjustment during bulk polymerization and the satisfaction of the above characteristics, N-isopropylmaleimide,
Most preferred is the combined use of N-cyclohexylmaleimide,
For applications requiring high heat resistance, for example, substrates for liquid crystal display devices, it is preferable to use N-isopropylmaleimide and N-cyclohexylmaleimide together.

It can be said that N-isopropylmaleimide alone is preferable in terms of easiness of monomer adjustment during bulk polymerization, but the heat resistance becomes insufficient for applications requiring high heat resistance. From the viewpoint of heat resistance, it is preferable that the amount of N-cyclohexylmaleimide is as large as possible.
Since -cyclohexylmaleimide is a solid at room temperature, its solubility is limited, and the content of N-cyclohexylmaleimide is 30% by weight or less based on the total composition in view of balance of ease of monomer adjustment and heat resistance. preferable.
If the amount is larger than this, it tends to be difficult to adjust the monomer during the cast polymerization. The amount is preferably 5 to 25% by weight, more preferably 10 to 20% by weight, in terms of the balance of ease of monomer adjustment and heat resistance.

Further, in order to improve low water absorption, low water absorption dimensional change and flame retardancy, it is necessary to copolymerize a monomer having a halogen atom. Examples of the halogen atom include chlorine, fluorine and bromine. From the viewpoint of color tone, chlorine and fluorine are preferable, and a fluorine atom-containing monomer is preferable from the viewpoint of low water absorption and the like. Further, in order to effectively reduce the water absorption rate and the water absorption dimensional change, it is preferable to contain as many halogen atoms as possible.

Specific examples of the monomer having a halogen atom include p-chlorostyrene, m-chlorostyrene and o-.
Chlorostyrene, p-chloromethylstyrene, p-bromostyrene, p-fluorostyrene, β-fluorostyrene, 2,4-dichlorostyrene, 2,4,6-trichlorostyrene, 2,3,4,6-tetrachloro Styrene, 2,3,4,5,6-pentafluorostyrene,
Aromatic vinyl monomers having halogen atoms such as 2,4-dibromostyrene, p-chloro-α-methylstyrene and 4-chloro-1-vinylnaphthalene, vinyl chloride, vinyl bromide, vinyl fluoride, chlorinated Vinylidene, α-chloroacrolein, chlorotrifluoroethylene, chloroprene, 2-chloro-1-propylene, 3-chloro-1
-Olefin vinyl monomers having halogen atoms such as propylene, tetrafluoroethylene, hexachloro-1,3-butadiene and hexafluoro-1,3-butadiene, and halogen atoms such as α-chloroacrylonitrile and α-bromoacrylonitrile. Vinyl cyanide monomer having, methacrylimide monomer having a halogen atom such as N- (p-chlorophenyl) methacrylimide,
Chloromethyl (meth) acrylate, 2-chloroethyl (meth) acrylate, p-chlorophenyl (meth) acrylate, p-bromophenyl (meth) acrylate, 1,2,2,2-tetrachloroethyl (meth) acrylate Le,
2,4,6-trichlorophenyl (meth) acrylate,
Having a halogen atom such as methyl α-chloro (meth) acrylate, methyl α-bromo (meth) acrylate, methyl α-fluoro (meth) acrylate, and a monomer represented by the following general formula (2) ( Examples thereof include (meth) acrylic acid and ester monomers thereof.

Rf (CH ₂ ) _n OCOCR ⁴ ═CH ₂ (2) (Rf is a fluoroalkyl group having 1 or more fluorine atoms, or a perfluoroalkyl group-containing substituent, and n is 1 to 1
An integer of ⁴ , R ⁴ represents hydrogen or a methyl group. ) These monomers having a halogen atom may be used alone or as a mixture of two or more kinds. Among these monomers having a halogen atom, the monomer represented by the general formula (2) is preferable in terms of transparency, heat resistance, low heat coloring, low water absorption, and low water absorption dimensional change. , 1 to 60% by weight is particularly effective. If it is less than 1% by weight, low water absorption and low water absorption dimensional change may occur, and if it exceeds 60% by weight, heat resistance tends to be insufficient.

Specific examples of the monomer represented by the general formula (2) include higher fluoroalkyl (meth) acrylates represented by the following general formulas (3) to (13). .

[0020]

[Chemical 3] (A represents 1 or 2, b represents an integer of 5 to 12, k represents 3)
Represents an integer of 4; m represents an even number of 6 to 14. p is 1
Represents an integer of -10. ^{R 5 ~R 9, R 11,} R 13 ~R 17 represents hydrogen or a methyl group. R ¹⁰ represents an alkyl group having 1 to 4 carbon atoms. R ¹² represents an alkyl group having 1 to 9 carbon atoms. Rf ² represents C ₆ F _{13 to} C ₁₂ F ₂₅ . ) Further, in order to improve heat resistance, transparency, low birefringence, low water absorption, low water absorption dimensional change, and flame retardancy, copolymerization of an aromatic vinyl monomer having a halogen atom is also preferable. . In particular, p
Copolymerization of -chlorostyrene and p-chloro-α-methylstyrene is preferable in terms of heat resistance.

The transparent heat-resistant resin of the present invention may use a polyfunctional monomer for three-dimensional crosslinking. As a result, a product having excellent transparency, heat resistance, chemical resistance, solvent resistance, and mechanical properties can be obtained. As such a polyfunctional monomer,
Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, glycerol (di /
Di-, tri-, tetra- (meth) of polyhydric alcohols such as tri) (meth) acrylate, trimethylolpropane (di / tri) (meth) acrylate and pentaerythritol (di / tri / tetra) (meth) acrylate. Using acrylates, vinyl esters of (meth) acrylic acid, allyl esters of (meth) acrylic acid, diallyl compounds such as diethylene glycol bisallyl carbonate, diallyl phthalate, dienes such as butadiene, hexadiene, pentadiene, and dichlorophosphazene as raw materials A polyfunctional monomer having a phosphazene skeleton having a polymerizable polyfunctional group introduced therein, a polyfunctional monomer having a heteroatom cyclic skeleton such as triallyl diisocyanurate, and a polyfunctional maleimide derivative represented by the general formula (14). Compound, divinylbenze And the like.

[0022]

[Chemical 4] (In the formula, R ¹⁸ and R ¹⁹ each represent a substituent selected from hydrogen, a methyl group and an ethyl group. R ²⁰ represents n having 1 to 4 carbon atoms.
Valent organic groups, the nitrogen and N- of the maleimide, respectively.
It is linked by a C bond. n represents an integer of 2 to 10. ) R ¹⁸ and R ¹⁹ may be the same or different.

R ²⁰ is an n-valent organic group, for example, n 20
Is 2, a divalent organic group, and n is 3, a trivalent organic group. Especially, since it is easy to synthesize,
Those having a valent organic group are most preferable. Specific examples of such a divalent organic group include an alkylene group such as a methylene group, an ethylene group and a propylene group, a cyclohexylene group,
An alicyclic alkylene group such as a methylcyclohexylene group,
Examples thereof include various examples such as a phenylene group and an arylene group such as a methylphenylene group. Further, the organic group may contain atoms such as oxygen, nitrogen, halogen, phosphorus and sulfur. Specific examples other than the above include the following.

[0024]

[Chemical 5] These polyfunctional monomers may be one kind or a mixture of two or more kinds.

Among these polyfunctional monomers, transparency,
From the viewpoint of heat resistance and moldability, divinylbenzene is the most preferable.

Divinylbenzene may be mixed with various isomers, but from the viewpoint of heat resistance of the transparent heat-resistant resin, the proportion of para-form in divinylbenzene is 30% by weight.
The above is preferable. If it is less than this, sufficient heat resistance tends not to be obtained. The heat resistance is preferably 60% by weight or more, more preferably 90% by weight or more. Also,
Industrially available divinylbenzene impurities such as ethylvinylbenzene and diethylbenzene are preferably as small as possible. Ethyl vinyl benzene and diethyl benzene tend to reduce the heat resistance and cause surface defects when cast polymerization is performed. The purity of divinylbenzene is preferably 50% by weight or more, more preferably 80% by weight or more.

Further, the transparent heat-resistant resin used in the present invention has improved mechanical strength, low birefringence, high refractive index, low water absorption, improved dyeability, improved heat resistance, and improved impact resistance. For example, various polymerizable monomers can be used for the purpose.

Examples of usable monomers include aromatic vinyl monomers, olefin vinyl monomers, cycloalkene monomers, methacrylic acid (meth) acrylic acid and its ester monomers, Examples thereof include polycarboxylic acid anhydrides. Specific examples of preferably used monomers include methyl methacrylate, cyclohexyl methacrylate, normalbornyl (meth) acrylate, isobornyl (meth) acrylate, norbornyl (meth) acrylate, adamantyl (meth) acrylate, phenyl (meth) acrylate. Acrylic monomers that give high glass transition temperatures to homopolymers such as Further, styrene-based monomers such as styrene and α-methylstyrene, maleic anhydride and the like can be mentioned.

In the present invention, among the monomer represented by the general formula (1) and the monomer copolymerizable with the monomer having a halogen atom, the balance of optical properties, heat resistance and mechanical strength is obtained. The most preferable monomer used is styrene and α-methylstyrene. These may be used alone or in combination.

Styrene is preferably copolymerized in an amount of 10% by weight or more from the viewpoint of optical characteristics and mechanical strength, and more preferably 15 to 60% by weight, and if it exceeds 60% by weight, heat resistance becomes insufficient. Tends to be sufficient. It is preferable that α-methylstyrene is copolymerized in an amount of 3 to 20% by weight, and if it is less than 3% by weight, heat resistance becomes insufficient, and
When the content exceeds the weight%, the coloring by heating becomes large and the optical properties tend to be problematic. Furthermore, weather resistance, oxidation deterioration resistance,
It is also useful to add various ultraviolet absorbers, antioxidants, and antistatic agents for the purpose of improving antistatic properties and the like. In particular, since it is possible to improve these properties without lowering chemical resistance and heat resistance, it is preferable to copolymerize a monomer having an ultraviolet absorbing property or an antioxidant property. Preferred examples of such a monomer include a benzophenone-based UV absorber having an unsaturated double bond,
Examples thereof include a phenylbenzoate-based ultraviolet absorber having an unsaturated double bond and a (meth) acrylic monomer having a hindered amino group as a substituent.

Examples of the benzophenone-based ultraviolet absorber having an unsaturated double bond include those having a structure represented by the following general formula (15).

[0032]

[Chemical 6] At least one of R ²¹ , R ²² , R ²³ , and R ²⁴ is an organic group having an unsaturated double bond, and the other functional groups are
Hydrogen, or alkyl group, alkenyl group, aralkyl group, aryl group, alkoxy group, aralkoxy group, aryloxy group, hydroxy group, halogen group, sulfonic acid group, sulfonic acid ester group, carboxylic acid group, carboxylic acid ester group, phosphoric acid The group and the phosphoric acid ester group are not particularly limited, and further, they may be the same or different.

Examples of the phenylbenzoate-based UV absorber having an unsaturated double bond include those having a structure represented by the following general formula (16).

[0034]

[Chemical 7] Here, at least one of R ^{25 to} R ³⁰ is an organic group having an unsaturated double bond, and the other functional group is hydrogen, or an alkyl group, an alkenyl group, an aralkyl group,
Aryl group, alkoxy group, aralkoxy group, aryloxy group, hydroxy group, halogen group, sulfonic acid group, sulfonic acid ester group, carboxylic acid group, carboxylic acid ester group, phosphoric acid group, phosphoric acid ester group, etc. Moreover, each may be the same or different.

In the acrylic and methacrylic monomers having a hindered amino group as a substituent, examples of the hindered amino group include a substituent represented by the following structural formula (17).

[0036]

[Chemical 8] (In the formula, R ³¹ , R ³² , R ³⁴ and R ³⁵ have 1 to 5 carbon atoms.
R ³³ is selected from an alkyl group having 1 to 5 carbon atoms and hydrogen. ) Such an acrylic monomer having a hindered amino group as a substituent and a methacrylic monomer are esterified with hydroxyhindered amine and various (meth) acrylic acid, or (meth) acrylic acid chloride, etc. Adjusted by reaction.

Specific examples of the acrylic monomer and the methacrylic monomer having the hindered amino group as a substituent include 2,2,6,6-tetramethyl-4.
-Piperidinyl acrylate, 2,2,6,6-tetramethyl-4-piperidinyl methacrylate, 1,2,
2,6,6-pentamethyl-4-piperidinyl acrylate, 1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate and the like can be mentioned.

The method for polymerizing the transparent heat-resistant resin of the present invention is not particularly limited, and it can be polymerized by a generally known method.

For example, when an epoxy resin is used, it is possible to use an amine-based, acid anhydride-based, imidazole-based, various metal compound-based curing agent or curing accelerator. Further, a polymer having active hydrogen such as a hydroxyl group,
It is also possible to polymerize an oligomer and further a monomer with an isocyanate compound. Furthermore, when polymerizing a maleimide-based monomer, a vinyl-based monomer such as an acrylic monomer or styrene, in the presence or absence of a radical-generating initiator, the above-mentioned monomer mixture is used. It can be polymerized by keeping it under a predetermined temperature condition. Examples of the polymerization method include bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, and cast polymerization.

Examples of the radical-generating initiator include various peroxide compounds and azo compounds. In particular,
An azo compound is preferably used from the viewpoint of preventing yellowing after heating. Specific examples include 2,2'-azobisisobutyronitrile and 1,1'-azobis (cyclohexane-
1-carbonitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-
Azobis (2-cyclopropylpropionitrile),
2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-methylbutyronitrile), 1-[(1-cyano-1-methylethyl) azo]
Formamide, 2-phenylazo-4-methoxy-
Azonitrile compounds such as 2,4-dimethylvaleronitrile, azoamidine compounds such as 2,2′-azobis (2-methyl-N-phenylpropionamidine) dibasic acid salt, 2,2′-azobis [2- (5- Methyl-2-imidazolin-2-yl) propane] dibasic acid salt and other cyclic azoamidine compounds, 2,2′-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] ] Propionamide} and other azoamide compounds, and 2,2′-azobis (2,4,4-trimethylpentane) and other alkylazo compounds. Further, the polymerization conditions should be appropriately determined experimentally depending on the monomer used and the initiator, but from the viewpoint of increasing the polymerization rate and reducing unreacted monomers as much as possible, In the mold polymerization, it is preferable that the mold is heated to 100 ° C. or higher, more preferably 170 ° C. or higher for at least 10 minutes or longer. Further, raising the polymerization temperature continuously or semi-continuously is also a preferable method for obtaining an optically uniform resin.

The degree of polymerization of the resin of the present invention is not particularly limited, but higher is preferable, and when a hard coat, an antireflection film, a gas barrier film, a conductive film or the like is applied as a post-treatment, solution coating or vacuum is applied. Considering vapor deposition and the like, 90% or more is preferable.

The method for molding the resin of the present invention is not particularly limited, and examples thereof include injection molding, extrusion molding, compression molding, belt press molding and cast molding. An effective molding method is a cast polymerization method.

As the mold used in the cast polymerization method, glass, especially glass plate by float method or surface-polished glass plate, is suitable for obtaining a transparent heat-resistant resin having excellent surface accuracy. On the other hand, a method of using a metal belt, which is a belt press molding, as the continuous casting polymerization is also preferable from the viewpoints of productivity and good thickness accuracy in a thin plate.

The transparent heat-resistant resin obtained by the present invention is
Transparency, heat resistance, weather resistance, impact resistance, glazing,
Since it is excellent in solvent resistance, chemical resistance, low water absorption, low water absorption dimensional stability, flame retardancy, low birefringence, heat coloring property, etc.,
Optical lenses such as eyeglass lenses, sunglasses lenses, camera lenses, video camera lenses, and contact lenses, as well as optical filters for display devices and substrates for liquid crystal displays, light diffusion plates for liquid crystal displays, substrates for electroluminescence, and liquid crystals. It is preferably applied to a light valve substrate, an optical disc substrate, and a window for automobiles, aircrafts, houses, household electric appliances, and the like. For liquid crystal display substrates, TN type, STN type, TFT type, ferroelectric liquid crystal, etc.
Although applicable to any of them, it is particularly preferably used for reducing the thickness and weight of a liquid crystal display using an STN type or a ferroelectric liquid crystal.

[0045]

EXAMPLES The present invention will be described more specifically below based on examples.

The glass transition temperature used in the examples is according to JIS K-7121, Mettler.
It was measured by DSC 30 manufactured by the company. Values represent Tmg.

The YI value was measured using an SM color computer manufactured by Suga Test Instruments Co., Ltd. 1 in air atmosphere
Heat treatment was carried out at 70 ° C. for 2 hours, and the difference between the YI value and the YI value before the heat treatment was defined as ΔYI.

The saturated water absorption was shown by the rate of change in weight before and after immersing the sample piece absolutely dried by vacuum drying in pure water kept at 23 ° C. for 7 days.

The dimensional change in water absorption was shown by the dimensional change rate before and after the same treatment as the saturated water absorption rate. The dimensions were measured using a digital precision length measuring machine DR-800-B manufactured by Dainippon Screen Mfg. Co., Ltd.

Example 1 32 g of N-isopropylmaleimide, 15 g of N-cyclohexylmaleimide, 18 g of styrene, 7 g of α-methylstyrene, "Viscoat 17" manufactured by Osaka Organic Chemical Industry Co., Ltd.
FM "20g, Nippon Steel Chemical Co., Ltd." DVB-810 "
8 g and 0.5 g of azobisisobutyronitrile were mixed and dissolved, and the compounded monomer was molded by cast polymerization. Cast polymerization was performed as follows.

Size 150 mm × 150 mm, thickness 5 m
The outer peripheral irregularities of the two glass plates of m were adhered with a gasket made of soft vinyl chloride, and assembled so that the distance between the two glass plates was 2 mm. The above-mentioned monomer mixture was poured into the assembled glass plate until the inside of the gasket was completely filled, and the mixture was polymerized at 70 ° C for 8 hours and 180 ° C for 1 hour to obtain a transparent plate-like polymer. Obtained. The characteristic values of this plate polymer are shown in Table 1.

The obtained plate-like polymer was used as a substrate, and γ-glycidoxypropyltrimethoxysilane hydrolyzate, bisphenol A type epoxy resin (solid content weight ratio 50:50) and aluminum were placed on the substrate. Providing an organopolysiloxane hard coat consisting of a system curing catalyst,
Further, zirconium oxide, tantalum oxide, and silicon dioxide were used in this order to obtain optical film thicknesses of 1 / 4λ (λ = 5).
20 nm) and a multilayer antireflection film made of an inorganic oxide was coated by a vacuum deposition method. The transparent heat-resistant resin having this anti-reflection film has excellent heat resistance as an optical filter for a display device, even in a heat resistance test at 100 ° C. for 2 hours, no cracks or changes in anti-reflection effect were observed. Was there.

Example 2 36 g of N-isopropylmaleimide, 17 g of N-cyclohexylmaleimide, 20 g of styrene, 9 g of α-methylstyrene, "Viscoat 17" manufactured by Osaka Organic Chemical Industry Co., Ltd.
FM "10g," DVB-810 "manufactured by Nippon Steel Chemical Co., Ltd.
9 g and azobisisobutyronitrile 0.5 g were mixed and dissolved, and the compounded monomer was molded by cast polymerization. Cast polymerization was carried out in the same manner as in Example 1 except that the distance between the two glass plates was changed to 0.6 mm and polymerization was performed at 70 ° C. for 8 hours and 190 ° C. for 1 hour. A transparent plate polymer was obtained. The characteristic values of this plate polymer are shown in Table 1.

On the plate-like polymer, a hard coat comprising the organopolysiloxane type hard coat composition used in Example 1 and 50 parts by weight of silica sol having an average particle size of 50 mμ was further added. Further, a transparent conductive film made of indium tin oxide was coated on the hard coat film by a sputtering method to a thickness of about 1000 angstrom. With the transparent heat-resistant resin having this transparent conductive film, no problems such as crack generation or film peeling were observed even in a heat resistance test at 150 ° C. for 2 hours,
It had excellent heat resistance as a liquid crystal display substrate.

Example 3 36 g of N-isopropylmaleimide, 17 g of N-cyclohexylmaleimide, 27 g of p-chlorostyrene, p-
Chloro-α-methylstyrene 10g, Nippon Steel Chemical Co., Ltd.
"DVB-810" (9 g) and azobisisobutyronitrile (0.2 g) were mixed and dissolved, and cast polymerization was performed under the same conditions as in Example 2 to obtain a transparent plate-shaped polymer. The characteristic values of this plate polymer are shown in Table 1.

Comparative Example 1 47 g of N-isopropylmaleimide, 10 g of N-cyclohexylmaleimide, 31 g of styrene, 12 g of "DVB-570" manufactured by Nippon Steel Chemical Co., Ltd., and 0.2 g of azobisisobutyronitrile were mixed and dissolved. Cast polymerization was carried out under the same conditions as in Example 1 to obtain a transparent plate-shaped polymer. The characteristic values of this plate polymer are shown in Table 1.

Comparative Example 2 40 g of N-isopropylmaleimide, 19 g of N-cyclohexylmaleimide, 22 g of styrene, 9 g of α-methylstyrene, "DVB-810" 10 manufactured by Nippon Steel Chemical Co., Ltd.
g and 0.2 g of azobisisobutyronitrile were mixed and dissolved, and cast polymerization was performed under the same conditions as in Example 2 to obtain a transparent plate-shaped polymer. The characteristic values of this plate polymer are shown in Table 1.
Shown in.

Comparative Example 3 35 g of N-isopropylmaleimide, 60 g of methyl methacrylate, 5 g of trimethylolpropane trimethacrylate and 0.5 g of azobisisobutyronitrile were mixed and dissolved, and cast polymerization was carried out under the same conditions as in Example 1,
A transparent plate polymer was obtained. The characteristic values of this plate polymer are shown in Table 1.

Comparative Example 4 "Viscoat 17FM" 30 manufactured by Osaka Organic Chemical Industry Co., Ltd.
g, methyl methacrylate 60 g, and trimethylolpropane trimethacrylate 10 g were mixed and dissolved, and cast polymerization was performed under the same conditions as in Example 1 to obtain a transparent plate-shaped polymer. The characteristic values of this plate polymer are shown in Table 1.

[0060]

[Table 1]

[0061]

The transparent heat-resistant resin obtained by the present invention is
Since it is excellent in heat resistance, optical characteristics, low water absorption, and water absorption dimensional stability, it is possible to provide a material suitable for an optical filter for a display device, a liquid crystal display substrate, an optical disc substrate, and the like.

Claims (5)

[Claims] 1. A monomer represented by the general formula (1) is added in an amount of 20 to 9
A composition containing 8% by weight and a monomer having a halogen atom, and the total weight ratio of the monomer represented by the general formula (1) and the monomer having a halogen atom is 30% by weight or more. A transparent heat-resistant resin characterized by being obtained by copolymerizing. [Chemical 1] (In the formula, R ¹ and R ² represent a substituent selected from hydrogen, a methyl group and an ethyl group. R ³ represents a substituent selected from an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group and a cycloalkyl group. Represents a group.) 2. A transparent heat resistant resin according to claim 1, wherein the monomer represented by the general formula (1) is N-isopropylmaleimide and / or N-cyclohexylmaleimide. 3. The transparent heat-resistant resin as claimed in claim 1, wherein the composition contains 1% by weight or more of a polyfunctional monomer. 4. The transparent heat resistant resin according to claim 3, wherein the polyfunctional monomer is divinylbenzene. 5. The transparent heat resistant resin according to claim 1, wherein the monomer having a halogen atom is a (meth) acrylic acid ester monomer represented by the general formula (2). ^{_{Rf (CH 2) n OCOCR 4}} = CH 2 (2) (Rf is a fluorine atom of 1 or more fluoroalkyl group or a perfluoroalkyl group-containing substituents,, n is 1 to
An integer of ⁴ , R ⁴ represents hydrogen or a methyl group. )