JP3360338B2 - Resin plate with transparent coating and conductive film - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a conductive film having excellent heat resistance, abrasion resistance, transparency, solvent resistance, and excellent durability, gas barrier properties, and low surface resistance of a transparent conductive film. It relates to a resin plate with a film.

[0002]

2. Description of the Related Art In general, plastic materials are light in weight and excellent in impact resistance, workability and mass productivity, and in recent years, demands for materials for optical elements such as optical filters, optical lenses and optical disks have been expanding. As these plastic materials for optical elements, transparent resins such as polymethyl methacrylate, polycarbonate, polyether sulfone, and N-substituted maleimide copolymer are currently known. However, plastic optical elements generally have the disadvantage that their surface hardness is lower than that of inorganic glass, and many attempts to improve this have already been proposed. For example, when the surface of a plastic substrate is SiO
Method of coating an inorganic material such as ₂ by vacuum vapor deposition (JP 58-204031 JP) and polyorganosiloxane-based hard coating film on the surface of the plastic substrate and a method of providing an acrylic hard coat film (USP3,986,99
7, USP 4,211,823, JP-A-57-1689.
No. 22, JP-A-59-38262, JP-A-5-38262
JP-A-9-51908, JP-A-59-51954, JP-A-59-78240, JP-A-59-89
368, JP-A-59-102964, JP-A-59-109528, and JP-A-59-12066.
No. 3, JP-A-59-155437, and JP-A-5-15537.
9-174629, JP-A-59-193969, and JP-A-59-204669).

[0003] A transparent conductive film, an antireflection film,
Studies have been made to improve the function by laminating gas barrier films or the like singly or in combination.

[0004]

The prior art S
Improvement of surface hardness by vacuum deposition of inorganic substances such as iO ₂ has a serious problem that, although it is high in hardness, it deteriorates adhesion to a substrate, heat resistance, light resistance, and the like. In the technology of providing a silane-based and acrylic-based hard coat film disclosed in Japanese Patent No. 38262, JP-A-59-51908, etc., the heat resistance is somewhat improved, but the effect is insufficient. .

In order to enhance the function, when a transparent conductive film, an anti-reflection film, a gas barrier film, etc. are laminated alone or in combination on a plastic material for an optical element having a hard coat film, the transparent conductive film, Since there is a large difference between the linear expansion coefficient and the change in dimensional change in moisture absorption between the prevention film, the gas barrier film, and the resin molded product, there is a problem that these films are easily cracked by heating or the like, resulting in poor durability.

For example, when used for a plastic substrate for liquid crystal, it is necessary to take measures such as reducing the thickness of the transparent conductive film in order to increase the durability of the transparent conductive film. there were.

[0007] The present invention is intended to solve the above-mentioned problems, and comprises providing a transparent film having excellent heat resistance, abrasion resistance and transparency, providing the transparent film of the present invention on a molded body, and further forming a transparent film thereon. When a functional film such as a transparent conductive film, an anti-reflection film, a gas barrier film, etc. is provided on the substrate, the object is to provide a transparent film excellent in durability of the functional film, and a resin plate with a conductive film having a low electric resistance. And

[0008]

The present invention has the following configuration to achieve the above object.

"(1) 20 to 49% by weight of an epoxy resin represented by the following general formula (1) and 51 to 80% by weight of a particulate inorganic oxide, and A resin having a glass transition temperature of 150 ° C. or higher, coated on both sides with a transparent coating made of a cured product having a total weight ratio of the epoxy resin represented by the formula (1) and the particulate inorganic oxide of 70% by weight or more. A liquid crystal display comprising a metal oxide film and / or a metal nitride film on both surfaces or one surface of a molded body, and further having at least one transparent conductive layer thereon.
Resin plate with conductive film for i .

Embedded image (However, R ¹ and R ² are selected from an alkylene group, an alkylidene group, CO, SO ₂ , S and O. R ³ is a hydrocarbon group having 1 to 12 carbon atoms and an ester residue having 1 to 12 carbon atoms. R ^{4 to} R ⁷ are selected from a hydrogen atom, a halogen atom and a hydrocarbon group having 1 to 4 carbon atoms, and a, b, c and d each represent an integer of 1 to 4. x is 0
Represents an integer of 10 to 10, and y and z each represent an integer of 0 or 1. )

First , the epoxy resin represented by the general formula (1) will be described.

R ¹ and R ² are selected from an alkylene group, an alkylidene group, CO, SO ₂ , S and O, but each may be the same or different. Examples of the alkylene group include a methylene group, an ethylene group, and a propylene group, and examples of the alkylidene group include an isopropylidene group and an isopropylidene group. R ³ is selected from a hydrocarbon group having 1 to 12 carbon atoms, an ester residue having 1 to 12 carbon atoms, and a hydrogen atom. Examples of the hydrocarbon group having 1 to 12 carbon atoms include a methyl group, an ethyl group, and a propyl group. And an alkyl group such as a cyclohexyl group and a cyclopentyl group; an aryl group such as a phenyl group and a naphthyl group; and an arylalkyl group such as a benzyl group. As the ester residue having 1 to 12 carbon atoms,
Examples include an alkylcarbonyl group such as a methylcarbonyl group and an ethylcarbonyl group, an arylcarbonyl group such as a benzoyl group, and an aralkylcarbonyl group such as a benzylcarbonyl group. R ^{4 to} R ⁷ are selected from a hydrogen atom, a halogen atom, and a hydrocarbon group having 1 to 4 carbon atoms, and each may be the same or different. As the halogen atom, chlorine and bromine are preferable, and the number of carbon atoms is 1
Examples of the hydrocarbon groups 4 to 4 include a methyl group, an ethyl group, and n-
Examples thereof include a propyl group and an isopropyl group. a,
b, c, and d show the integer of 1-4. X is 0 to 10
And y and z each represent an integer of 0 or 1. Specific examples of the epoxy resin include bisphenol A epoxy resin, tetramethyl bisphenol A epoxy resin, tetrabromobisphenol A epoxy resin, bisphenol F epoxy resin, tetramethyl bisphenol F epoxy resin, bisphenol S epoxy resin,
Tetramethyl bisphenol S type epoxy resin, bisphenol AF type epoxy resin, bisphenol Z type epoxy resin, bisphenol fluorene type epoxy resin,
Biphenol type epoxy resin, tetramethyl biphenol type epoxy resin and the like can be mentioned. These can be used alone or in a mixture of two or more.

Among the above epoxy resins, from the viewpoints of transparency, applicability to a molded article, and durability of functional films such as a transparent conductive film, an antireflection film, and a gas barrier film laminated on a molded article with a transparent film. And bisphenol A type epoxy resin are preferred.

The average epoxy equivalent of the epoxy resin used is preferably 150 to 600 g / equivalent, and more preferably 180 to 400 g / equivalent in consideration of transparency, heat resistance, surface hardness, and applicability to a molded article. . 150
If the amount is less than g / equivalent, the heat resistance and the durability of the functional film will be insufficient, and if it exceeds 600 g / equivalent, the transparency and the applicability to a molded article will be insufficient, or the surface hardness will decrease and the abrasion resistance will decrease. Properties tend to be insufficient. The method for measuring the epoxy equivalent is not particularly limited, and a generally known method such as a dioxane hydrochloride method is used.

The transparent film of the present invention has the general formula (1)
The epoxy resin represented by the formula and the particulate inorganic oxide as essential components, the epoxy resin component is 20 to 49% by weight,
And 51 to 80% by weight of a particulate inorganic oxide,
The cured product has a total weight ratio of the epoxy resin represented by the general formula (1) and the particulate inorganic oxide of 70% by weight or more. If the epoxy resin component in the transparent film exceeds 49% by weight or the particulate inorganic oxide is less than 51% by weight, the surface hardness of the transparent film decreases, the scratch resistance becomes insufficient, and molding with a transparent film is performed. The durability of functional films such as a transparent conductive film, an antireflection film, and a gas barrier film laminated on the body becomes insufficient. If the amount of the particulate inorganic oxide exceeds 80% by weight or the amount of the epoxy resin component is less than 20% by weight, the transparency becomes insufficient, poor adhesion to the resin molded body occurs, and the coating film itself may be damaged. Cracks,
The durability of the functional film becomes insufficient. The content of the epoxy resin component is preferably 25 to 49% by weight, and more preferably 30 to 49% by weight. The content of the particulate inorganic oxide is preferably 51 to 75% by weight, and more preferably 51 to 70% by weight. Further, even when the total weight ratio of the epoxy resin represented by the general formula (1) and the particulate inorganic oxide is less than 70% by weight, the transparent conductive film, the antireflection film, The durability of a functional film such as a gas barrier film becomes insufficient. The thickness of the transparent film is preferably from 0.1 to 10 μm. 0.
If it is less than 1 μm, the surface hardness tends to be insufficient, and if it exceeds 10 μm, the transparency tends to be insufficient. More preferably, it is 1 to 5 μm.

In the present invention, a particulate inorganic oxide is used for the purpose of improving the surface hardness, adjusting the refractive index, improving the mechanical strength, improving the thermal characteristics, and improving the conductivity.
The particulate inorganic oxide is not particularly limited as long as it does not impair transparency in a film state. Specific examples include silica, antimony oxide, titania, alumina, zirconia, and tungsten oxide. They are,
One type or a mixture of two or more types may be used. From the viewpoint of improving workability and imparting transparency, it is preferable that these particulate inorganic oxides are uniformly mixed in a coating material as a sol dispersed in a colloidal form. Specific examples of the colloidally dispersed sol include silica sol, titania sol, zirconia sol, ceria sol, antimony oxide sol, magnesium fluoride sol, indium-tin oxide (IT
O, Indium Tin Oxide) sol, tin oxide sol and the like. The average particle diameter of the particulate inorganic oxide is not particularly limited, but is usually 1 to 200 mμ, preferably 10 to 1 μm.
00 mμ, more preferably 30 to 60 mμ is used. When the particles having an average particle diameter of more than 200 μm are used, the resulting coating film tends to be poor in transparency and turbid. If it is less than 10 μm or more than 100 μm, the durability of functional films such as a transparent conductive film, an antireflection film, and a gas barrier film laminated on the molded article with a transparent film tends to be insufficient. Also, even if various fine particle surface treatment is performed to improve the dispersibility of the fine inorganic particles,
Alternatively, there is no problem even if various surfactants or amines are added.

The organic polymer constituting the transparent film of the present invention can be used by mixing a resin other than the epoxy resin represented by the general formula (1) as long as the above properties are not impaired. Specific examples include acrylic resins, silicone resins, polyurethane resins, melamine resins, polyolefin resins, celluloses, polyvinyl alcohol resins, urea resins, nylon resins, polycarbonate resins, and general formula (1). Epoxy resins other than the above-mentioned epoxy resin. These resins can be used alone or in combination of two or more, and three-dimensional crosslinking can be performed using various curing agents, crosslinking agents, and the like. In particular, for applications where surface hardness is important, it is preferable to use a curable resin, such as an acrylic resin, a silicone resin, an epoxy resin other than the epoxy resin represented by the general formula (1), a polyurethane resin, A single system or a composite system such as a melamine resin is preferably used. When various properties such as surface hardness, heat resistance, chemical resistance, and transparency are taken into consideration, copolymerization of a silicone resin as an organic polymer is preferable, and more preferably represented by the following general formula (2). Examples thereof include polymers obtained from an organosilicon compound or a hydrolyzate thereof.

[0017] ^{_{R 8 a R 9 b SiX 4}} -ab (2) ( wherein, R ⁸ is an organic group having 1 to 10 carbon atoms, R ⁹
Is a hydrocarbon group having 1 to 6 carbon atoms or a halogenated hydrocarbon group, X is a hydrolyzable group, and a and b are 0 or 1
It is. Examples of the organosilicon compound represented by the general formula (2) include methyl silicate, ethyl silicate, n
-Propyl silicate, iso-propyl silicate,
Tetraalkoxysilanes such as n-butyl silicate, sec-butyl silicate, and t-butyl silicate, and hydrolysates thereof, further, methyltrimethoxysilane, methyltriethoxysilane, methyltriacetoxysilane, methyltripropoxysilane, Methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ-chloropropyltri Methoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltriacetoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyl Trimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, β-cyanoethyltriethoxy Silane, methyltriphenoxysilane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltrimethoxysilane, α-glycidoxy Ethyltriethoxysilane, β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane,
α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltributoxysilane, γ-glycidoxypropyltriphenoxysilane,
α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-glycidoxybutyltrimethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, δ-glycidoxybutyltrimethoxysilane, δ-
Glycidoxybutyltriethoxysilane, (3,4-epoxycyclohexyl) methyltrimethoxysilane,
(3,4-epoxycyclohexyl) methyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4
-Epoxycyclohexyl) ethyltripropoxysilane, β- (3,4-epoxycyclohexyl) ethyltributoxysilane, β- (3,4-epoxycyclohexyl) ethyltriphenoxysilane, γ- (3,4-epoxycyclohexyl) propyl Trimethoxysilane,
trialkoxysilanes such as γ- (3,4-epoxycyclohexyl) propyltriethoxysilane, δ- (3,4-epoxycyclohexyl) butyltrimethoxysilane, δ- (3,4-epoxycyclohexyl) butyltrimethoxysilane, Triacyloxysilane, or triphenoxysilanes or hydrolysates thereof, and dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldisilane Ethoxysilane, dimethyldiacetoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxy Silane, γ-mercaptopropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, glycidoxymethylmethyldimethoxysilane, glycidoxy Methylmethyldiethoxysilane, α-glycidoxyethylmethyldimethoxysilane, α-glycidoxyethylmethyldiethoxysilane,
β-glycidoxyethylmethyldimethoxysilane, β-
Glycidoxyethylmethyldiethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycidoxypropylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylmethyldiethoxysilane , Γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropyl Methylmethoxyethoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropylmethyldiacetoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane , Dialkoxysilanes such as γ-glycidoxypropylvinyldimethoxysilane, γ-glycidoxypropylvinyldiethoxysilane, γ-glycidoxypropylphenyldimethoxysilane, γ-glycidoxypropylphenyldiethoxysilane, diphenoxy Silane or diacyloxysilanes or their hydrolysates are examples.

These organosilicon compounds may be used alone or in combination.
More than one species can be used. In particular, for the purpose of imparting dyeing properties, the use of an organosilicon compound containing an epoxy group or a glycidoxy group is suitable, and provides high added value.

The organosilicon compound is preferably used after being hydrolyzed in order to lower the curing temperature and accelerate the curing. The hydrolysis is produced by adding pure water or an acidic aqueous solution such as hydrochloric acid, acetic acid or sulfuric acid, followed by stirring. Furthermore, the degree of hydrolysis can be easily controlled by adjusting the amount of pure water or acidic aqueous solution. At the time of hydrolysis, it is preferable to add pure water or an acidic aqueous solution in an amount equal to or more than 3 moles of the hydrolyzable group contained in the compound represented by the general formula (2) from the viewpoint of promoting curing.

In the hydrolysis, it is possible to carry out the hydrolysis without a solvent because alcohols and the like are generated. However, after the organic silicon compound is mixed with the solvent for the purpose of performing the hydrolysis more uniformly, the hydrolysis is carried out. Decomposition can also be performed. Further, depending on the purpose, it is possible to remove the alcohol or the like after hydrolysis in an appropriate amount by heating and / or under reduced pressure before use, or to add an appropriate solvent thereafter.

The general formula (1) of these organosilicon compounds and the like
The amount of the resin other than the epoxy resin represented by is less than 30% by weight, more preferably 15% by weight or less. 30
If the amount is more than 10% by weight, the transparency and the durability of functional films such as a transparent conductive film, an antireflection film and a gas barrier film laminated on the molded article with a transparent film become insufficient.

The transparent coating of the present invention is usually diluted with a volatile solvent, applied to a molded product as a liquid composition, and cured and molded, for the purpose of improving workability and adjusting the thickness of the coating. No particular limitation is imposed on the solvent used, but it is required that the surface properties of the object to be coated be not impaired, and also consider the stability of the composition, wettability to the substrate, volatility, etc. Should be determined. Further, the solvent may be used as a mixture of not only one kind but also two or more kinds. These solvents include water,
Examples thereof include alcohols, esters, ethers, ketones, halogenated hydrocarbons, aromatic hydrocarbons such as toluene and xylene, and solvents such as aprotic polar solvents.
From the viewpoint of the dispersibility of the particulate inorganic oxide, water, alcohol, dimethylformamide, ethylene glycol, diethylene glycol, triethylene glycol, benzyl alcohol, phenethyl alcohol, phenyl cellosolve, N-methyl-2-pyrrolidone, dimethyl sulfoxide and the like Polar solvents are preferably used.

Various curing agents can be used in combination with the coating composition used for forming the transparent film in the present invention for the purpose of accelerating curing, curing at low temperature, and the like. As the curing agent, various epoxy resin curing agents or various organic silicon resin curing agents are used. Specific examples of these curing agents include various organic acids and their acid anhydrides, nitrogen-containing organic compounds, various metal complex compounds, or metal alkoxides, and also various types of alkali metal organic carboxylate and carbonate. Salt, and even peroxide,
Examples include radical polymerization initiators such as azobisisobutyronitrile. These curing agents can be used as a mixture of two or more kinds. Among these curing agents, the following aluminum chelate compounds are particularly useful for the purpose of the present invention, in view of the stability of the coating composition, the presence or absence of coloring of the coating after coating, and the like.

The aluminum chelate compound mentioned here is, for example, an aluminum chelate compound represented by the general formula: AlX _n Y _3-n . However, X in the formula is OL (L represents a lower alkyl group), Y
Is a ligand derived from a compound represented by the general formula M ¹ COCH ₂ COM ² (M ¹ and M ² are both lower alkyl groups) and the general formula M ³ COCH ₂ COOM ⁴ (where M ³ and M ⁴ are both Is also a lower alkyl group), and n is 0, 1 or 2.

As the aluminum chelate compound represented by the general formula AlX _n Y _3-n , various compounds can be exemplified, and particularly preferred from the viewpoints of solubility in a composition, stability, and effect as a curing catalyst. Are aluminum acetylacetonate, aluminum bisethylacetoacetate monoacetylacetonate, aluminum-di-n-butoxide-monoethylacetoacetate, aluminum-di-iso-propoxide-monomethylacetoacetate and the like. These can be used as a mixture of two or more kinds.

In the transparent coating of the present invention, there are dyes which can be dyed with various dyes, especially disperse dyes. In the case of dyed products, various transition metal compounds or dyes thereof are used for the purpose of improving the light fastness. Preferably, a reaction product has been added. Specific examples of these metal compounds include, for example, acetylacetonate metal salt, bisdithiol-α-diketone metal salt, bisphenylthiol metal salt, bisphenyldithiol metal salt, thiocatechol metal salt, dithiocarbamic acid metal salt, Salicylaldehyde oxime metal salts, thiobisphenolate metal salts, and phosphonous metal salts. Among them, acetylacetonate chelate compounds are preferred because they have good stability in coatings. The amount of these transition metal compounds to be added should be determined experimentally depending on the use of the transparent film, the type of diluent solvent and the type of other components, but the solubility, the whitening of the coating film, etc. 0.001 to
It is preferably used in the range of 10% by weight. If the amount is less than 0.001% by weight, the effect of addition cannot be obtained. Also,
These transition metal compounds have no problem even if the bonding state of the metal changes due to some chemical change during the formation of the transparent film, but it is preferable that the transition metal compound is contained in the film as a chelate compound in order to obtain a greater effect. .

The coating composition used in forming the transparent film of the present invention has various surface active properties for the purpose of improving the flow during application, improving the smoothness of the transparent film and lowering the friction coefficient of the film surface. It is also possible to add an agent, and in particular, a block or graft copolymer of dimethylpolysiloxane and alkylene oxide, and a fluorine-based surfactant are effective. The use amount of these is preferably 0.01 to 5% by weight, and if it exceeds 5% by weight, transparency becomes insufficient, and if it is less than 0.01% by weight, the effect of addition such as uneven coating is not obtained. It tends to be sufficient.

Further, an inorganic oxide other than the finely divided inorganic oxide may be added to the coating composition used in forming the transparent film of the present invention, as long as the film performance and transparency are not significantly reduced. it can. Adhesion with the substrate, chemical resistance, surface hardness,
Various properties such as durability and dyeability can be improved. Examples of the inorganic material that can be added include a metal alkoxide, a chelate compound, and / or a hydrolyzate thereof represented by the following general formula (3).

M (OR) _m (3) (where R is an alkyl group, an acyl group, or an alkoxyalkyl group, and m is the same value as the number of charges of the metal M. M is silicon, titanium, zircon, Antimony, tantalum, germanium, aluminum, etc.) Further, an ultraviolet absorber may be added for the purpose of improving weather resistance, and an antioxidant may be added as a method for improving heat deterioration.

The transparent coating of the present invention is obtained by curing the coating composition, and the curing is performed by a heat treatment. The heating temperature is appropriately selected in consideration of the composition of the coating composition and the heat resistance of the resin molded product, but is preferably 50 to 250 ° C.

As means for applying the coating applied on the resin molded article of the present invention, brush coating, dip coating, roll coating,
Normally applied coating methods such as spray coating, spin coating, and flow coating can be easily used.

In applying the coating composition of the present invention, various pretreatments are also effective means for the purpose of improving cleaning, adhesion, water resistance, and the like. Gas treatment,
Chemical treatment, ultraviolet treatment and the like can be mentioned.

The activation gas treatment is a treatment with ions, electrons or excited gas generated under normal pressure or reduced pressure. Methods for generating these activation gases include, for example, corona discharge, direct current under reduced pressure,
This is due to low-frequency, high-frequency or high-voltage discharge by microwaves. In particular, treatment with low-temperature plasma obtained by high-frequency discharge under reduced pressure is preferably used in terms of reproducibility, productivity, and the like.

The gas used here is not particularly limited, but specific examples include oxygen, nitrogen, hydrogen, carbon dioxide, sulfur dioxide, helium, neon, argon, freon, steam, ammonia, carbon monoxide. , Chlorine, nitric oxide, nitrogen dioxide and the like. These can be used alone or in combination of two or more. Preferred gases among the above include those containing oxygen,
It may exist in the natural world such as air. More preferably, pure oxygen gas is effective for improving the adhesion. Furthermore, for the same purpose, it is possible to raise the temperature of the substrate to be treated during the treatment.

On the other hand, specific examples of chemical treatment include alkali treatment with caustic soda, acid treatment with hydrochloric acid, sulfuric acid, potassium permanganate, potassium dichromate, etc., and organic solvent treatment. It is sufficiently possible to carry out the above pretreatment continuously or stepwise.

The transparent coating of the present invention can be applied to all kinds of materials such as resin moldings, metal products, glass, paper products and woodworking products. In particular, the surface protection of the resin moldings and the transparent coating on the resin moldings can be applied. When a functional film such as a conductive film, an antireflection film, or a gas barrier film is used alone or in combination and laminated to impart a function, it is useful as a buffer between the resin molded product and the functional film. For example, heat resistance, transparency, solvent resistance, gas barrier properties, low surface resistance is required, for plastic substrate applications for liquid crystal displays, etc., a transparent heat-resistant cross-linked resin, forming the transparent coating of the present invention, a gas barrier film A transparent conductive film is laminated and used as a resin plate with a conductive film.

The resin molded body used for the above purpose is not particularly limited as long as it is a resin molded body having a glass transition temperature of 130 ° C. or higher, but any resin having a glass transition temperature of 150 ° C. or higher can be used. If it is, the heat resistance is further improved and it is more preferably used. Here, the glass transition temperature refers to a temperature at which a polymer changes from an amorphous glass state to a rubber state.
Various properties such as heat content, refractive index and dielectric constant change. The glass transition temperature can be measured from the change in these characteristics, and specifically, can be evaluated by a known method such as differential scanning calorimetry (DSC) (for example, JIS K712).
1). In the case of measuring the glass transition temperature by differential scanning calorimetry, the glass transition temperature can be obtained by evaluating the resin molded product itself or a product obtained by heat-treating the resin molded product. The glass transition temperature of the article provided with the transparent coating on the body can be regarded as the glass transition temperature of the transparent resin.

The mechanical properties of the resin molded body are preferably 200 kg / mm ² , more preferably 330 kg / cm ² when the flexural modulus at room temperature is used as an index.
/ Mm ² or more. Furthermore, the transparency of the resin molded body is
When the total light transmittance at the time of no coloring is represented as an index, 60
% Or more, more preferably 80% or more.
The resin molded article can be made into a composite system with an inorganic substance or the like as long as the transparency is not impaired, and there is no problem even if an inorganic bond such as a siloxane bond or a phosphazene bond is contained.

Examples of the components of the resin molded product include polyolefin resins represented by polymethacrylic resins such as polymethacrylic acid and polycarboxyphenyl methacrylamide, and polyolefin resins represented by polystyrene resins such as poly (biphenyl) styrene, and poly ( 2,6-dimethyl-1,4-
A polyether resin represented by phenylene oxide), a polycarbonate resin represented by poly (oxycarbonyloxy-1,4-phenyleneisopropylidene-1,4-phenylene), and poly (oxy-2,2,2)
Polyester resins represented by 4,4-tetramethyl-1,3-cyclobutyleneoxyterephthaloyl) and poly (oxy-1,4-phenylenesulfonyl-1,4-)
Phenylene), polysulfone resins represented by poly (oxy-1,4-phenyleneisopropylidene-1,4-phenyleneoxy-1,4-phenylenesulfonyl-1,4-phenylene), and poly (iminoisophthaloyl) Polyamide resin represented by imino-4,4'-biphenylene), polysulfide resin represented by poly (thio-1,4-phenylenesulfonyl-1,4-phenylene), unsaturated polyester resin, epoxy resin Resins, melamine-based resins, phenol-based resins, diallyl phthalate-based resins, polyimide-based resins, polyphosphazene-based resins, and the like, and resins exhibiting the above-mentioned thermal characteristics by introducing a crosslinked structure in these polymer groups. It is possible to obtain a shaped body. In particular, a glass transition temperature of 150
Maleimide-based resins are preferred from the viewpoint of heat resistance of not less than ℃, transparency and moldability, and maleimide-based copolymers obtained by polymerizing a composition containing a polyfunctional monomer having two or more unsaturated groups Is more preferably used.

As the above copolymer, the following general formula (4)
20 to 98% by weight of the monomer represented by the formula, and 2 to 80% by weight of the polyfunctional monomer having two or more unsaturated groups, and a monomer represented by the general formula (4). Weight ratio of the monomer and the polyfunctional monomer having two or more unsaturated groups,
A copolymer obtained by polymerizing a composition having a content of 30% by weight or more is preferably used.

[0041]

Embedded image (In the formula, R ¹⁰ represents a substituent selected from hydrogen and a hydrocarbon group having 1 to 20 carbon atoms. R ¹¹ and R ¹² each represent a substituent selected from hydrogen, a methyl group and an ethyl group.) R contained in the maleimide derivative compound represented by (4)
¹¹ and R ¹² may be the same or different.

When R ¹⁰ is a hydrocarbon group, specific examples include a methyl group, an ethyl group, a propyl group, an octyl group,
Linear alkyl group such as octadecyl group, branched alkyl group such as isopropyl group, sec-butyl group, tert-butyl group and isopentyl group; alicyclic hydrocarbon group such as cyclohexyl group and methylcyclohexyl group; phenyl group And aryl groups such as methylphenyl group, and aralkyl groups such as benzyl group and phenethyl group.

Further, R ¹¹ , R ¹² and R ¹⁰ are substituted with various substituents such as a halogeno group such as fluorine, chlorine and bromine, a cyano group, a carboxyl group, a sulfonic acid group, a nitro group, a hydroxy group and an alkoxy group. May be done.

Specific examples of the compound represented by the general formula (4) include N-methylmaleimide, N-butylmaleimide, N-phenylmaleimide, No-methylphenylmaleimide, Nm-methylphenylmaleimide, −
p-methylphenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, N-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, Np-methoxyphenyl Maleimide, N
-O-chlorophenylmaleimide, Nm-chlorophenylmaleimide, Np-chlorophenylmaleimide,
No-carboxyphenylmaleimide, Np-carboxyphenylmaleimide, Np-nitrophenylmaleimide, N-ethylmaleimide, N-cyclohexylmaleimide, N-isopropylmaleimide and the like.

These monomers may be used alone or in combination with two or more.
It may be used as a mixture of more than one species. Among these maleimide compounds, from the viewpoint of yellowing after the heat resistance test and weather resistance, N-alkylmaleimides and N-alicyclic alkylmaleimides are particularly preferred, and N-iso-propylmaleimide and N-cyclohexylmaleimide are particularly preferred. Is preferred. Further, from the viewpoint of ease of preparation of a monomer solution at the time of cast polymerization and satisfying the above characteristics, N-alkylmaleimides such as N-iso-propylmaleimide and N-cyclohexylmaleimide and N-alicyclic alkyl Most preferred is the use of a maleimide. The ratio of N-alkylmaleimide to N-alicyclic alkylmaleimide when used in combination should be appropriately determined experimentally depending on the type and amount of the polyfunctional monomer having two or more unsaturated groups. However, usually, in order to exhibit the effect of the combined use, N-alkyl maleimide 100 parts by weight of N
-It is preferable to use the alicyclic maleimide in the range of 10 parts by weight to 500 parts by weight. Next, a polyfunctional monomer having two or more unsaturated groups will be described. That is,
The polyfunctional monomer having two or more unsaturated groups is a monomer having two or more unsaturated functional groups copolymerizable with the maleimide, and the copolymerizable functional group includes a vinyl group,
Examples include a methylvinyl group, an acryl group, and a methacryl group. Further, a monomer containing two or more different copolymerizable functional groups in one molecule is also included in the polyfunctional monomer in the present invention.

Preferred specific examples of the polyfunctional monomer having two or more unsaturated groups include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and triethylene glycol di (meth) acrylate. , Glycerol (di / tri) (meta)
Acrylate, trimethylolpropane (di / tri)
Di-, tri-, tetra- (meth) acrylates of polyhydric alcohols such as (meth) acrylate and pentaerythritol (di / tri / tetra) (meth) acrylate;
Aromatic polyfunctional monomers such as p-divinylbenzene and o-divinylbenzene, esters such as vinyl (meth) acrylate and allyl (meth) acrylate, dienes such as butadiene, hexadiene and pentadiene, and dichlorophosphazene Examples of the raw material include a monomer having a phosphazene skeleton into which a polymerized polyfunctional group is introduced, and a polyfunctional monomer having a heterocyclic ring skeleton such as triallyl isocyanurate. It is preferable that the maleimide-based copolymer composition contains 20 to 98% by weight of the monomer represented by the general formula (3),
If less than 20% by weight, sufficient heat resistance, mechanical strength,
In some cases, characteristics such as optical isotropy cannot be satisfied. On the other hand, if it exceeds 98% by weight, the degree of cross-linking is reduced, and the solvent resistance, low water absorption and the like may be insufficient. Further, it is preferably 30 to 80% by weight, more preferably 40 to 60% by weight.

On the other hand, the polyfunctional monomer having two or more unsaturated groups is preferably contained in the crosslinked polymer composition at a ratio of 2 to 80% by weight, and when less than 2% by weight. , The crosslinking does not proceed sufficiently, and a decrease in heat resistance, solvent resistance and the like tends to be observed. On the other hand, if the content exceeds 80% by weight, there may be a problem that the impact resistance and the like are reduced, and the characteristics of the plastic are significantly reduced.

Further, in the maleimide copolymer composition, mechanical strength, optical isotropy, high refractive index, low water absorption, dyeability, heat resistance, impact resistance are improved. For the purpose of improvement and the like, various copolymerizable monomers are preferably used in combination. Examples of such a monomer that can be used in combination include an aromatic vinyl monomer, an olefin vinyl monomer, (meth) acrylic acid and its ester monomer, and a polycarboxylic anhydride. Specific examples of such aromatic vinyl monomers include styrene, α-methylstyrene, p-methylstyrene, p-tert-butylstyrene, chlorostyrene, bromostyrene, and the like. Usually, styrene, α-methylstyrene, p-methylstyrene and the like are used from the viewpoints of performance and industrial availability. As other vinyl monomers, acrylonitrile, vinyl cyanide monomers such as methacrylonitrile, methyl methacrylate, methyl acrylate, cyclohexyl methacrylate, t-butyl methacrylate, benzyl methacrylate, acrylic Preferred specific examples include (meth) acrylic acid (ester) monomers such as acid and methacrylic acid, and maleic anhydride. For applications requiring low water absorption, copolymerization of vinylcycloalkane such as vinylcyclohexane is effective.

The total content of the monomer represented by the general formula (4) and the polyfunctional monomer having two or more unsaturated groups in the maleimide-based copolymer composition is as follows: It is preferably at least 30% by weight, more preferably at least 40% by weight. That is, if it is less than 30% by weight, a polymer having insufficient transparency, heat resistance, chemical resistance, impact resistance, and the like may be obtained.

It is also useful to add various ultraviolet absorbers, antioxidants and antistatic agents to the resin molded article for the purpose of improving light resistance, oxidation deterioration resistance and antistatic properties. It is possible to improve these properties without lowering chemical resistance and heat resistance, so UV absorption,
Alternatively, it is preferable to copolymerize a monomer having antioxidant properties. Preferred examples of such a monomer include a benzophenone-based ultraviolet absorber having an unsaturated double bond, a phenylbenzoate-based ultraviolet absorber having an unsaturated double bond, and a (meth) acryl monomer having a hindered amino group as a substituent. Is mentioned. These copolymerized monomers are preferably used in the range of 0.5 to 20% by weight. When the amount is less than 0.5% by weight, the effect of addition is not recognized, and when the amount exceeds 20% by weight, heat resistance,
Mechanical strength and the like tend to decrease.

The method for polymerizing the resin molded article is not particularly limited, and the resin can be polymerized by a generally known method. When the resin molded product is a vinyl copolymer, polymerization can be carried out by maintaining the above monomer mixture under a predetermined temperature condition in the presence or absence of a radical initiator. Various methods such as bulk polymerization, solution polymerization, suspension polymerization, and cast polymerization can be used. The degree of polymerization of the resin molded product of the present invention is not particularly limited, but the higher the degree of polymerization, the more preferable it is, and preferably 90% or more in consideration of post-processing such as solution coating such as a transparent film and vacuum deposition. The polymerization of the transparent resin of the present invention can be carried out in a temperature range of 30 to 250 ° C., but the polymerization rate can be increased by setting the polymerization temperature to 130 ° C. or higher, more preferably 150 ° C. or higher.

There is no particular limitation on the molding method of the resin molded body, but an effective molding method includes a casting polymerization method.

The mechanical properties of the resin molded article according to the present invention are as follows when the flexural modulus at 170 ° C. is represented as an index.
For applications where heat resistance is important, 20 kg / mm ^{2 to} 300 kg / mm
It is preferably ² . If it is less than 20 kg / mm ² ,
Insufficient rigidity causes problems in mechanical properties.
If it exceeds kg / mm ² , cracks may occur in the crosslinked resin during handling, and problems such as poor yield may occur. In order to achieve the above-mentioned flexural modulus, in the present invention, it is preferable to heat-treat the crosslinked resin and the transparent coating obtained above. As the heat treatment method, a known method such as a method using a heater or the like and a method using light irradiation such as infrared rays can be used.

The heat treatment atmosphere may be a gas, a solution, or under reduced pressure. Preferably, yellowing due to oxidation of the object to be treated, from the viewpoint of ease of operation, particularly under reduced pressure or nitrogen, carbon dioxide, helium, neon,
A gas atmosphere such as argon is applied. They are,
Not only one kind but also a mixture of two or more kinds can be used.
The heat treatment temperature should be determined by the applied substrate and the transparent coating, but is usually 100 to 300.
C, more preferably 120-250C. If the temperature is lower than this, no obvious effect is recognized, and if the temperature is higher than this, thermal decomposition, crack generation, etc. occur, and furthermore, problems such as yellowing are likely to occur. Further, the heat treatment time is appropriately selected in consideration of the shape of the applied crosslinked resin, the transparent film and the heat treatment temperature, but is preferably 1 second to 24 hours, more preferably 1 minute to 12 hours. If it is shorter than this, no clear effect is recognized, and if it is longer than this, problems tend to occur in terms of yellowing and workability. Further, as a method of fixing the object to be processed at the time of heat treatment, a known method can be used, but the shape, thickness and heat treatment temperature of the object to be processed, the heat treatment time, should be experimentally determined, for example, When the object to be processed is a sheet, heat treatment on a plate-shaped support is preferable, and particularly when the surface smoothness of the object is required, the surface smoothness of the plate-shaped support becomes important, As the support, glass materials such as polished glass and ground glass, metal materials such as aluminum and stainless steel, and polymer materials such as Teflon and polyimide are preferably used.

A transparent conductive film such as ITO can be formed on the resin molded product with a transparent film obtained as described above, and can be used as a transparent conductive film material. Transparent conductive film materials include electrical component circuit materials such as capacitors and resistors, copy materials such as electrophotography and electrostatic recording, liquid crystal displays, electrochromic displays, electroluminescent displays, and signal input transparent materials for touch panels. In addition to photoelectric conversion elements such as electrodes, solar cells, and optical amplifiers, they can be used for various applications such as antistatic, electromagnetic wave shielding, surface heating elements, and sensors. When a resin molded body on which a transparent conductive film such as ITO is formed is used, its conductivity is maintained even at high temperatures, so that it can be used as a heat-resistant transparent conductive film material.

For use in a substrate for a liquid crystal display, for example, one or both surfaces of the transparent film of the present invention formed on a resin molded article may be used to improve gas barrier properties and durability of the transparent conductive film. Preferably, a metal oxide film and / or a metal nitride film is formed, and a transparent conductive film is formed thereon. The method for forming the metal oxide film and / or the metal nitride film is not particularly limited, and a generally known film forming method such as a high-frequency discharge sputtering method or a DC discharge sputter link method can be used. For example, a metal oxide film and / or a metal nitride film formed by a high-frequency discharge sputtering method uses a metal oxide or a metal nitride which is a dielectric or an insulator as a sputtering gate under an inert gas atmosphere and / or The film is formed under an active gas atmosphere. Examples of the metal oxide film and / or metal nitride film include Al, Si, Zr, and T.
Metal oxides and / or nitrides of one kind or a mixture of two or more kinds selected from i, Y, Yb, Mg, Ta, Ce, Hf, etc., are mentioned, but cost, transparency, gas barrier properties, From the viewpoint of the durability of the transparent conductive film provided on the metal oxide film and / or the metal nitride film, Al, S
Metal oxides and / or nitrides of one or a mixture of two or more selected from i and Ti are preferred. He, Ne, A
Although an inert gas such as r, Kr, Xe, or Rn is preferably used, Ar is particularly preferably used in terms of cost, availability, and sputtering rate. As the active gas, O ₂ , N ₂ , CO, CO ₂ or the like is used. In forming a metal oxide film, O ₂ is preferably used to compensate for O ₂ deficiency during sputtering. O
_{2 The} concentration (partial pressure with respect to the inert gas) is appropriately selected depending on the type of the transparent coating, the substrate temperature, the target material, the sputtering rate, and the input power.
0% is common. In the present invention, 5% or less is preferable from the viewpoint of reducing plasma damage of the transparent film,
More preferably, it is 1% or less. Metal oxide film and / or
Alternatively, the thickness of the metal nitride film is not particularly limited, but is preferably 50 to 2000 Å, more preferably 100 to 1200 Å, from the viewpoints of the film formation time, the gas barrier properties, and the durability of the transparent conductive film.

The transparent conductive film provided on the resin molded product with a transparent film of the present invention includes metal oxides such as ITO, tin oxide and cadmium oxide, gold, silver, copper, palladium, nickel, aluminum and chromium. A conductive thin film such as a metal or a conductive polymer is used. Above all, ITO is preferably used in consideration of various properties such as transparency and low resistance. As a method for forming a metal oxide thin film such as an ITO film or a metal thin film, a known method such as a vacuum evaporation method, an ion plating method, a sputtering method, a coating method, and a spray method can be used. For example, as the sputtering method, a known method such as a direct current method, a high frequency method, and a magnetron method is used [see the sputtering phenomenon (Kanbara Kan, published by The University of Tokyo Press, 1984)]. The substrate temperature at the time of film formation is appropriately selected depending on the type of the resin molded body, the transparent film, and the like in consideration of transparency, low resistance, adhesion, heat resistance, and chemical resistance. Further, the composition ratio of ITO is preferably determined by the surface resistance, specific resistance, transparency, etc. required for the transparent conductive film. From the viewpoint of low resistance and transparency, the content of SnO ₂ is reduced. It is preferable that the content be 25% by weight or less, and in order to further reduce the resistance value, it is preferable to use a high-density ITO target in which the ITO target is close to the true density of ITO. The thickness of the transparent conductive film is not particularly limited, but is preferably selected appropriately from the range of 150 to 5000 Å from the viewpoints of conductivity and film formation time.

The thickness of the resin plate with a transparent conductive film of the present invention is preferably 0.1 to 10 mm in consideration of mechanical properties, and 0.2 to 10 mm when used for a liquid crystal display substrate. 1.0 mm is preferred. If it is less than 0.2 mm, the shape retention is insufficient, and if it exceeds 1.0 mm, it is thin,
Light weight effect is reduced.

Further, by using the resin plate coated with the transparent film of the present invention, a resin plate with a conductive film having a small surface resistance and excellent durability of the transparent conductive film can be obtained. As a surface resistance value, for example, when used for a liquid crystal display substrate, a resistance value of 60 Ω / cm ² or less is preferable, but in order to produce a larger liquid crystal display, a resistance value of 40 Ω / cm ² or less. Is preferred,
Above this, the display quality tends to be insufficient.

The resin plate with a conductive film of the present invention is formed of TN (Twi)
STed Nematic) type, STN (Super)
Twisted Nematic type, ferroelectric liquid crystal (F
LC: Ferroelectric Liquid C
Ristal) type and other simple matrix types, MIM
(Metal-Insulator-Metal) type,
TFT (Thin-Film Transistor)
The present invention can be applied to a liquid crystal display such as an active matrix type such as a liquid crystal display.

When the resin plate with a conductive film of the present invention is used as a substrate for a liquid crystal display, a configuration is adopted in which liquid crystal is sandwiched between the resin plates with a conductive film. That is, in a liquid crystal display using a conventional glass substrate, the glass substrate is replaced by the resin plate with a conductive film of the present invention. Specifically, a structure in which a transparent film, a gas barrier film, and a transparent conductive layer are provided on a resin molded body, and a liquid crystal layer is sandwiched between substrates provided with a passivation film and an alignment film thereon if necessary. A deflection plate is provided outside the substrate holding the liquid crystal layer. A retardation plate, a light reflection plate, and the like are further used as necessary for the liquid crystal display.

As a method for manufacturing a liquid crystal display using the resin plate with a conductive film of the present invention, a known method can be applied. For example, in the case of a simple matrix type liquid crystal display [Liquid Crystal Device Handbook (edited by the 142nd Committee of the Japan Society for the Promotion of Science, published by Nikkan Kogyo Shimbun, 198)
9) p. 531], after cleaning the substrate, forming a transparent conductive film, fine processing of the transparent conductive film (resist coating, development, etching, resist cleaning and removal), alignment film formation, rubbing treatment, cleaning, sealing agent printing, substrate bonding, A liquid crystal display element can be obtained by sequentially performing steps such as heating and pressurization, vacuum degassing, liquid crystal injection, sealing of an injection port, separation of a liquid crystal cell, and attachment of a polarizing plate and a light reflecting plate. In these liquid crystal display manufacturing steps, manufacturing conditions should be set in consideration of various properties such as heat resistance, mechanical properties, and mechanical properties of a liquid crystal display substrate using a resin plate with a conductive film.

The transparency of the resin molded article with a transparent coating of the present invention is expressed by the total light transmittance at the time of no coloring as an index.
It is preferably 60% or more, more preferably 80%.
Further, when applied to applications requiring optical isotropy, such as substrates for liquid crystal displays and optical disc substrates, the birefringence of the resin molded product is preferably 30 nm or less, more preferably 15 nm or less.

The transparent film obtained according to the present invention is excellent in transparency, heat resistance, scratch resistance, impact resistance, chemical resistance, etc., and is therefore suitable for eyeglass lenses, sunglass lenses, camera lenses, video camera lenses, For optical lenses such as lenses for goggles and contact lenses, as well as substrate materials for various displays such as optical disc substrates, liquid crystal display substrates, liquid crystal display light guide plates, electrochromic display substrates, and electroluminescent display substrates. It is suitable for coating windows and the like of fronts, rears, roofs and the like of automobiles, aircrafts, and the like. Further, the resin plate with a transparent conductive film of the present invention has a low resistance value, and can be used for chemicals, heating, and wet heat of the transparent conductive film. It has good durability against various types of display such as liquid crystal display substrates. It is suitable for a substrate material of the ray.

[0065]

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples.

The total light transmittance and yellowness were measured by Suga Test Machine Co., Ltd.
Was measured using an SM computer. Haze is
The measurement was performed using a fully automatic direct reading haze computer meter HGM-2DP type manufactured by Suga Test Instruments Co., Ltd. For solvent resistance, rub the surface with gauze impregnated with acetone,
The gloss change at that time was visually evaluated. The glass transition temperature was measured using a Mettler DSC30. The value is 2nd according to JIS K-7121.
The run Tmg was read.

The abrasion resistance of the transparent film was determined by rubbing the surface with # 0000 steel wool and judging from the degree of scratching. 100 pieces were inserted with a steel knife, and a cellophane adhesive tape (trade name: "Cellotape", manufactured by Nichiban Co., Ltd.) was strongly adhered, and quickly peeled in a 90-degree direction, and the presence or absence of peeling of the coating film was examined. The film thickness of the transparent film was measured with a surface roughness measuring instrument SE-3300 manufactured by Kosaka Laboratory Co., Ltd.

The surface resistance of the resin plate with a conductive film was measured by Loresta MCP-TESTER manufactured by Mitsubishi Yuka Co., Ltd.
Measured at room temperature using -FP. The gas barrier property was evaluated by measuring the oxygen permeability by a differential pressure steady-state method using a differential pressure gas permeability measurement system GTR-30XD manufactured by Yanagimoto Seisakusho. Furthermore, as the durability evaluation of the conductive film,
The heat resistance was measured by heating in an oven set at 180 ° C. for 2 hours, cooling to room temperature, and visually observing the appearance of the resin plate with a conductive film. Chemical resistance, 3% sodium hydroxide aqueous solution heated to 40 ℃, immersed resin plate with conductive film for 5 minutes,
After washing with running water for 5 minutes and replacing with purified water,
Draining was performed with gauze, and the appearance was visually observed.

Example 1 (1) Method for Producing a Resin Molded Article An example of a method for producing a resin molded article is described below.

N-isopropylmaleimide 20.5 g N-cyclohexylmaleimide 6.0 g Styrene 18.5 g Divinylbenzene 5.0 g Azobisisobutyronitrile 0.05 g was mixed and dissolved, and cast and molded by cast polymerization.
Cast polymerization was performed as follows.

2 of 150 mm × 150 mm size and 5 mm thickness
The outer peripheral portions of the two glass plates were attached with a soft vinyl chloride gasket and assembled so that the distance between the two glass plates was 0.5 mm. The monomer mixture was poured into the assembled glass plate, and polymerized at 70 ° C. for 8 hours, at 100 ° C. for 1 hour, and further at 150 ° C. for 1 hour to obtain a transparent resin molded product.

The glass transition temperature of this resin molded product was 185.
° C, and the total light transmittance was 90%. The solvent resistance was also good.

(2) Formation of Transparent Coating In a reactor equipped with a rotor, 10 g of phenyltrimethoxysilane was charged, and the solution temperature was maintained at 20 ° C., while stirring with a magnetic stirrer, a 0.01 N hydrochloric acid aqueous solution 2 was added. 0.7 g was gradually added dropwise. Stop cooling after dropping,
A hydrolyzate of phenyltrimethoxysilane was obtained.

To the hydrolyzate of phenyltrimethoxysilane, 43 g of diacetone alcohol, 30 g of dimethylformamide, 73 g of benzyl alcohol, 0.7 g of a silicone-based surfactant, and a bisphenol A type epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd.) Name epicoat 827)
After adding and mixing 43 g, 337 g of colloidal silica sol (trade name: OSCAL-1235, average particle size: 45 mμ, manufactured by Catalyst Chemical Industry Co., Ltd.) and 2.8 g of aluminum acetylacetonate were added, and the mixture was sufficiently stirred. Things.

The resin composition obtained by the above (1) was dip-coated with the coating composition at a pulling rate of 20 cm / min, followed by pre-curing at 90 ° C./10 min.
Further heating was performed at 150 ° C. for 1 hour to form a transparent coating on the resin molded body. Table 1 shows properties of the obtained resin molded body with a transparent coating.

[0076] (3) the electrically conductive film-attached resin sheet manufacturing method (2) above by the resulting transparent film with resin molding on the SiO ₂ by RF magnetron sputtering method, data - using the SiO ₂ to get material , The ultimate vacuum was set to 5 × 10 ^-5 Tool, and A
r, sputter deposition vacuum degree 2 × 10 ⁻³ Toor, input power 1.5 kw, substrate temperature 120 ° C., sputtering rate 50 Å / min. sputtering conditions, 600 Å film formation, and further, A transparent conductive thin film containing indium-tin mixed oxide (ITO) as a main component was subjected to direct current magnetron sputtering to form ITO (SnO ₂ 10 wt.
%), The ultimate degree of vacuum is set to 5 × 10 ⁻⁵ Toor, and Ar and O ₂ are used as sputter introduction gases, the sputter deposition vacuum degree is 2 × 10 ⁻³ Toor, and the input power is 1.5 k.
w, substrate temperature 120 ° C, sputtering rate 100
Under sputtering conditions of Angstrom / min, 200
A 0 angstrom film was formed. The surface resistance of the surface on which the ITO film was formed at room temperature was ²⁰ Ω / cm ² . The resin plate with the conductive film was evaluated for heat resistance and chemical resistance. As a result, there was no change in the appearance, and the surface resistance was measured to be 20 Ω / cm ² , the same as the initial value. And chemical resistance. Further, the oxygen transmission rate was 0.4 cc / m ² · day · atm, and the gas barrier property was good.

Example 2 In Example 1, the bisphenol A type epoxy resin “Epicoat 827” manufactured by Yuka Shell Epoxy Co., Ltd. was replaced with the bisphenol A type epoxy resin “Epicoat 83” manufactured by Yuka Shell Epoxy Co., Ltd.
4 "50 g, 15 g of diacetone alcohol and 40 g of dimethylformamide in the coating composition.
g, 116 g of benzyl alcohol, colloidal silica sol (trade name: OSCAL-12, manufactured by Catalyst Chemical Industry Co., Ltd.)
35, an average particle diameter of 45 mμ) was changed to 312 g to form a transparent coating in the same manner as in Example 1. Table 1 shows properties of the obtained resin molded body with a transparent coating. Further, as in the case of Example 1, SiO _{2 was}
When a film and an ITO film were formed, the surface resistance at room temperature of the surface on which the ITO film was formed was 23 Ω / cm ² .
The resin plate with the conductive film was evaluated for heat resistance and chemical resistance. As a result, there was no change in the appearance, and the surface resistance was measured to be 23 Ω / cm ² , the same as the initial value. And chemical resistance. Also,
The oxygen transmission rate was 0.4 cc / m ² · day · atm, indicating that it had good gas barrier properties. Example 3 In Example 2, the epoxy resin was replaced with “Epicoat 83”.
A transparent film was formed in the same manner except that a mixture of 4 ″ 35 g and “Epicoat 827” 15 g was used.The properties of the obtained resin molded product with a transparent film are shown in Table 1. Further, the resin molding with the transparent film was formed. An SiO ₂ film as in Example 1
When the ITO film was formed, the surface resistance of the surface on which the ITO film was formed at room temperature was 22 Ω / cm ² . When the heat resistance and the chemical resistance were evaluated using this resin plate with a conductive film, there was no change in the appearance, and the surface resistance was measured to be 22 Ω / cm ² , the same as the initial value. And chemical resistance. Further, the oxygen transmission rate indicates 0.4 cc / m ² · day · atm,
It had good gas barrier properties.

Example 4 In Example 1, the epoxy resin was replaced with “Epicoat 82”.
7 "48 g, a mixture of 12 g of Bisphenol A type epoxy resin" Epicoat 1001 "manufactured by Yuka Shell Epoxy Co., Ltd. 73 g of diacetone alcohol, 42 g of dimethylformamide, 106 g of benzyl alcohol, colloidal silica sol in the coating composition Example 1 (Catalyst Kasei Kogyo Co., Ltd., trade name OSCAL-1235, average particle diameter 45 mμ) was changed to 280 g.
A transparent film was formed in the same manner as described above. Table 1 shows properties of the obtained resin molded body with a transparent coating. Further, when a SiO ₂ film and an ITO film were formed on the resin molded body with the transparent film in the same manner as in Example 1, the surface resistance at room temperature of the surface on which the ITO film was formed was 21 Ω / cm ² . When the heat resistance and the chemical resistance were evaluated using this resin plate with a conductive film, there was no change in the appearance, and the surface resistance was measured to be 21 Ω / cm ² , the same as the initial value. ,
It was confirmed that it had chemical resistance. Further, the oxygen transmission rate was 0.4 cc / m ² · day · atm, and the gas barrier property was good.

Comparative Example 1 In Example 1, no colloidal silica sol was used.
Changed to Bisphenol A type epoxy resin manufactured by Yuka Shell Epoxy Co., Ltd., 130 g of diacetone alcohol and 74 g of dimethylformamide in the coating composition,
Example 1 except that 181 g of benzyl alcohol was used.
A transparent film was formed in the same manner as described above. Table 1 shows properties of the obtained resin molded body with a transparent coating. When a SiO ₂ film and an ITO film were formed on the resin molded body with the transparent film in the same manner as in Example 1, the surface resistance of the surface on which the ITO film was formed at room temperature was 21 Ω / cm ² . When the heat resistance and the chemical resistance were evaluated using the resin plate with the conductive film,
Many cracks were observed on the surface of the ITO film, and heat resistance and chemical resistance were insufficient.

Comparative Example 2 In Example 1, 14 g of bisphenol A type epoxy resin “Epicoat 827” was added to a colloidal silica sol (trade name: OSCAL-123, manufactured by Catalyst Chemical Industry Co., Ltd.).
5, average particle diameter 45 mμ) was changed to 450 g, 31 g of diacetone alcohol, 16 g of dimethylformamide and 41 g of benzyl alcohol in the coating composition.
A transparent coating was formed in the same manner as in Example 1 except that the amount was changed to g. Table 1 shows properties of the obtained resin molded body with a transparent coating. When a SiO ₂ film and an ITO film were formed on the resin molded body with the transparent coating in the same manner as in Example 1, the ITO
The surface resistance of the surface on which the film was formed at room temperature was 24 Ω / c.
m ² , but using this resin plate with a conductive film,
When the chemical resistance was evaluated, many cracks were observed on the surface of the ITO film, and the heat resistance and the chemical resistance were insufficient.

Comparative Example 3 105.4 g of γ-glycidoxypropyltrimethoxysilane was charged into a reactor equipped with a rotor, and the liquid temperature was set at 10 ° C.
While stirring with a magnetic stirrer.
24.1 g of a 01N aqueous hydrochloric acid solution was gradually added dropwise. After completion of the dropwise addition, cooling was stopped to obtain a hydrolyzate of γ-glycidoxypropyltrimethoxysilane.

To the hydrolyzate of γ-glycidoxypropyltrimethoxysilane, 31.3 g of ethanol, 31.3 g of n-propyl alcohol, and 0.75 of a silicon surfactant were added.
g, and 248.8 g of colloidal silica sol (trade name: OSCAL-1132, manufactured by Catalysts & Chemicals, Inc., average particle size: 13 mμ), and 7.5 g of aluminum acetylacetonate were added. Things.

Using the above coating composition, a transparent film was provided in the same manner as in Example 1. Table 1 shows properties of the obtained resin molded body with a transparent coating. When a SiO ₂ film and an ITO film were formed on the resin molded body with the transparent film in the same manner as in Example 1, the surface resistance of the surface on which the ITO film was formed at room temperature was 50 Ω / cm ^2. Heat resistance and chemical resistance were evaluated using a resin plate with a film.
Many cracks were observed on the surface of the O film, and heat resistance and chemical resistance were insufficient.

Comparative Example 4 In Example 1, the resin molded body was 0.5 mm thick, the glass transition temperature was 70 ° C., the total light transmittance was 92%, the flexural modulus at room temperature was 230 kg / mm ² , and the flexural strength was 7 kg / mm.
^2, diethylene glycol bis allyl carbonate thermosetting resin plate obtained from (Mitsui Petrochemical Co., Ltd., trade name RAV7 sheet) was changed to provided the same transparent film as in Example 1, SiO ₂ film, Forming an ITO film,
A resin plate with a conductive film was prepared. However, many cracks were observed on the surface of the ITO film, and it was difficult to use it as a resin plate with a conductive film.

[0085]

[Table 1]

[0086]

By providing the transparent film of the present invention on a molded article, heat resistance, scratch resistance, and transparency are excellent, and further, a functional film such as a transparent conductive film, an antireflection film, and a gas barrier film is further provided thereon. Is provided, the functional film has excellent durability, and a resin plate with a conductive film having low electric resistance can be obtained.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-62-89902 (JP, A) JP-A-61-169240 (JP, A) JP-A 1-232034 (JP, A) JP-A-2-2 5308 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) G02F 1/13-1/141 B32B 27/00-27/42 C08J 7/04 C09D 1/00-201/10

Claims (4)

(57) [Claims] 1. An epoxy resin represented by the following general formula (1): 20 to 49% by weight;
Both sides are coated with a transparent coating composed of a cured product containing 1 to 80% by weight and having a total weight ratio of the epoxy resin represented by the general formula (1) and the particulate inorganic oxide of 70% by weight or more. The resin molded body having a glass transition temperature of 150 ° C. or higher has a metal oxide film and / or a metal nitride film on both surfaces or one surface thereof, and further has at least one transparent conductive layer thereon. Resin plate with conductive film for liquid crystal display . Embedded image (However, R ¹ and R ² are selected from an alkylene group, an alkylidene group, CO, SO ₂ , S and O. R ³ is a hydrocarbon group having 1 to 12 carbon atoms and an ester residue having 1 to 12 carbon atoms. R ^{4 to} R ⁷ are selected from a hydrogen atom, a halogen atom and a hydrocarbon group having 1 to 4 carbon atoms, and a, b, c and d each represent an integer of 1 to 4. x is 0
Represents an integer of 10 to 10, and y and z each represent an integer of 0 or 1. ) 2. The method according to claim 1, wherein the finely divided inorganic oxide is one kind or a mixture of two or more kinds selected from silica, antimony oxide, titania, alumina, zirconia and tungsten oxide having an average particle diameter of 10 to 100 μm. A resin plate with a conductive film for a liquid crystal display , characterized by that: 3. The epoxy resin according to claim 1, wherein the epoxy resin represented by the general formula (1) has an average epoxy equivalent of 150 to 600 g /
A resin plate with a conductive film for a liquid crystal display, which is an equivalent amount of a bisphenol A type epoxy resin. 4. The cured product is a copolymer containing 1 to 30% by weight of a compound selected from an organosilicon compound represented by the following general formula (2) and / or a hydrolyzate thereof. 4. A liquid crystal according to claim 1,
Resin plate with conductive film for display . _{^{R 8 a R 9 b SiX 4}} -ab (2) ( wherein, R ⁸ is an organic group having 1 to 10 carbon atoms, R ⁹
Represents a hydrocarbon group having 1 to 6 carbon atoms or a halogenated hydrocarbon
The group, X is a hydrolyzing group, and a and b are 0 or 1
is there. )