JPH0611704A - Plastic optical product - Google Patents

Abstract

PURPOSE:To obtain a plastic optical product having excellent conductivity, transparency, heat resistance, chemical resistance and durability. CONSTITUTION:This plastic optical product consists of the following members A, B, C, D deposited in this order. A: transparent resin, B: hardened film containing inorg. fine particles, C: metal oxide film formed by high frequency discharge sputtering method, and D: transparent conductive film essentially comprising mixture oxide of indium and tin. The obtd. plastic optical product has excellent conductivity, transparency, heat resistance, chemical resistance and durability and is preferably used for electrode substrates of various display devices.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plastic optical article having excellent conductivity, transparency, heat resistance, chemical resistance and durability.

[0002]

2. Description of the Related Art In general, plastic materials are lightweight, and are excellent in impact resistance, workability and mass productivity, so that demand for optical elements such as optical filters, optical lenses and optical disks has been expanding in recent years. At present, transparent resins such as methyl methacrylate, polystyrene and polycarbonate are mainly used as plastic materials for these optical elements.

It has been studied to impart conductivity to these plastic moldings to enhance their function. As a method for forming a coating having conductivity on the moldings, a mixed oxide of indium and tin (hereinafter referred to as a mixed oxide) is used. , ITO), SnO ₂
A physical method in which a metal oxide such as or a metal such as Au or Ag is provided by a vacuum deposition method or a sputtering method is general. However, there is a problem that the transparent conductive film obtained from the above-mentioned metal oxide has a large difference in linear expansion coefficient from the plastic molded body and cracks easily occur due to heating or the like. As a concrete proposal for improving the above-mentioned problems, Japanese Patent Laid-Open No. 2-5308 can be cited. Japanese Patent Application Laid-Open No. 2-5308 discloses a technique in which a hard coat film is provided on both surfaces of a plastic molded body, a conductive film is provided on one surface, and a metal oxide film is provided on the opposite surface of the substrate. ing.

[0004]

The technique disclosed in Japanese Unexamined Patent Publication (Kokai) No. 2-5308 certainly does not cause bending due to thermal expansion and contraction, but has poor heat resistance and tends to cause cracks in the conductive film. There was a point.

The present invention is intended to solve the above problems, and an object of the present invention is to provide a plastic optical article having conductivity, transparency, and excellent heat resistance and durability.

[0006]

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

"A plastic optical article in which the following A, B, C and D are laminated in this order.

A: Transparent resin B: Hardened film containing inorganic fine particles C: Metal oxide film formed by high frequency discharge sputtering method D: Transparent conductive film containing indium and tin mixed oxides as main components The transparent resin is not particularly limited, but a transparent resin having a glass transition temperature of 160 ° C. or higher is preferably used because it has good heat resistance. Here, the glass transition temperature is a temperature at which a polymer changes from an amorphous glass state to a rubber state. Since various properties such as elastic modulus, expansion coefficient, heat capacity, refractive index, and dielectric constant change with this transition temperature as a boundary, it is possible to measure the glass transition temperature from changes in these properties. It can be evaluated by a known method such as scanning calorimetry (DSC) (for example, JIS K7121). When measuring the glass transition temperature by differential scanning calorimetry, the glass transition temperature can be determined by evaluating the transparent resin itself or heat-treated transparent resin, but if the cured film is sufficiently thin, the transparent resin It is also possible to regard the glass transition temperature of the cured coating provided as the glass transition temperature of the transparent resin.

The mechanical properties of the transparent resin are preferably 200 k when the flexural modulus at room temperature is used as an index.
g / mm ² or more, more preferably 330 kg / m
m ² or more. Furthermore, the transparency of the transparent resin is preferably 60% or more, and more preferably 80% or more, when the total light transmittance in the uncolored state is used as an index.
The transparent resin can be made into a composite system with an inorganic substance or the like as long as the transparency is not impaired, and may include an inorganic bond such as a siloxane bond or a phosphazene bond.

Examples of the transparent resin component having a glass transition temperature of 160 ° C. or higher include (i) polymethacrylic acid resins such as polymethacrylic acid and polycarboxyphenylmethacrylamide, and polystyrene resins such as poly (biphenyl) styrene. Polyolefin resin represented by
(ii) Polyether resin represented by poly (2,6-dimethyl-1,4-phenylene oxide), (iii) poly (oxycarbonyloxy-1,4-phenylene isopropylidene-1,4-phenylene) Polycarbonate resin represented by (iv) poly (oxy-2,2,4,4)
-Tetramethyl-1,3-cyclobutyleneoxyterephthaloyl) represented by a polyester resin, (v) poly (oxy-1,4-phenylenesulfonyl-1,4-phenyleneoxy-1,4-phenylenesulfonyl) -1,
(4) Polysulfone-based resin typified by 4-phenylene), and (vi) poly (iminoisophthaloyluimino-4,4 ')
-A polyamide resin represented by (biphenylene), (vi
i) poly (thio-1,4-phenylenesulfonyl-1,
4-phenylene) represented by polysulfide resin,
(viii) unsaturated polyester resin, (ix) epoxy resin, (x) melamine resin, (xi) phenol resin, (xi)
Examples thereof include i) diallyl phthalate resin, (xiii) polyimide resin, and (xiv) polyphosphazene resin.

By introducing a cross-linking structure into these polymer groups,
It is also possible to obtain a transparent crosslinked resin exhibiting the above-mentioned thermal characteristics, and in consideration of shape retention at high temperature, a transparent crosslinked resin is preferably used. Particularly, from the viewpoint of transparency and moldability, a polyolefin resin is preferable, and a polyolefin copolymer obtained by polymerizing a composition containing a polyfunctional monomer having two or more unsaturated groups is more preferable. Used. As the copolymer, 20 to 98% by weight of a maleimide-based monomer represented by the general formula (A), and 2 to 80% by weight of a polyfunctional monomer having two or more unsaturated groups.
The total weight ratio of the monomer represented by the formula (A) and the polyfunctional monomer having two or more unsaturated groups is 30.
A copolymer obtained by polymerizing the composition in an amount of not less than wt% is preferably used.

[0012]

[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 hydrogen and a hydrocarbon group having 1 to 20 carbon atoms.

R ¹ and R ² may be the same or different from each other. When R ³ is a hydrocarbon group, specific examples include (i) a linear alkyl group such as a methyl group, an ethyl group, a propyl group, an octyl group and an octadecyl group, (ii) an isopropyl group, a sec-butyl group, te
branched alkyl groups such as rt-butyl group, isopentyl group, (iii) cyclohexyl group, alicyclic hydrocarbon group such as methylcyclohexyl group, (iv) phenyl group, aryl group such as methylphenyl group, (v) benzyl group Base,
Examples thereof include an aralkyl group such as a phenethyl group. R ¹ , R ² and R ³ are halogeno groups (fluorine, chlorine, bromine, etc.), cyano groups, carboxyl groups,
It may be substituted with various substituents such as a sulfonic acid group, a nitro group, a hydroxy group and an alkoxy group.

Specific examples of the compound represented by the general formula (A) include N-methylmaleimide, N-butylmaleimide, N-phenylmaleimide, N-o-methylphenylmaleimide, Nm-methylphenylmaleimide and N-methylmaleimide. −
p-Methylphenylmaleimide, N-o-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, N-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, Np-methoxyphenyl Maleimide, N
-O-chlorophenyl maleimide, Nm-chlorophenyl maleimide, Np-chlorophenyl maleimide,
Examples thereof include N-o-carboxyphenylmaleimide, Np-carboxyphenylmaleimide, Np-nitrophenylmaleimide, N-ethylmaleimide, N-cyclohexylmaleimide and N-isopropylmaleimide.

These monomers may be used alone or as a mixture of two or more. From the viewpoint of yellowing and weather resistance after the heat resistance test, among these maleimide compounds, alkylmaleimide and cycloalkylmaleimide are preferable, and N-iso-propylmaleimide and N-cyclohexylmaleimide are particularly preferable. Furthermore, from the viewpoint of ease of preparation of a monomer solution at the time of cast polymerization and satisfying the above characteristics, N-
Most preferred is the combination of N-alkylmaleimide and N-alicyclic alkylmaleimide, such as the combination of iso-propylmaleimide and N-cyclohexylmaleimide. The ratio of N-alkylmaleimide and N-alicyclic alkylmaleimide at the time of combined use should be appropriately determined experimentally depending on the type and amount of the polyfunctional monomer having two or more unsaturated groups. However, in order to exert the combined effect, N-
It is preferable to use the N-alicyclic maleimide in an amount of 10 to 500 parts by weight based on 100 parts by weight of the alkyl maleimide.

The polyfunctional monomer having two or more unsaturated groups is a monomer having two or more unsaturated functional groups copolymerizable with the maleimide. Examples of the copolymerizable functional group include a vinyl group, a methyl vinyl group, an acryl group, a methacryl group and the like. Further, a monomer having two or more different functional groups copolymerizable in one molecule is also included in the polyfunctional monomer.

Specific preferred examples of the polyfunctional monomer having two or more unsaturated groups include (i) ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate and triethylene glycol di (meth).
Acrylate, glycerol (di / tri) (meth) acrylate, trimethylolpropane (di / tri) (meth) acrylate, pentaerythritol (di / tri /
Di-, tri-, tetra- (meth) acrylates of polyhydric alcohols such as tetra) (meth) acrylate, (ii)
aromatic polyfunctional monomers such as p-divinylbenzene and o-divinylbenzene, (iii) esters such as (meth) acrylic acid vinyl ester and (meth) acrylic acid allyl ester, (iv) butadiene, hexadiene, pentadiene, etc. Examples thereof include dienes, (v) monomers having a phosphazene skeleton in which a polymerized polyfunctional group is introduced from dichlorophosphazene as a raw material, and (vi) polyfunctional monomers having a heteroatom cyclic skeleton such as triallyl isocyanurate.

In the above polyolefin-based copolymer composition, the monomer represented by the above general formula (A) is contained in an amount of 20 to 9
It is preferably contained in an amount of 8% by weight. Content is 20
If it is less than wt%, sufficient heat resistance, mechanical strength, optical isotropy and other properties may not be satisfied. On the other hand, when it exceeds 98% by weight, the degree of cross-linking is lowered, and the solvent resistance and the low water absorption may be insufficient. The content is more preferably 30 to 80% by weight, further preferably 40 to 60% by weight.

The polyfunctional monomer having two or more unsaturated groups is preferably contained in the crosslinked polymer composition in an amount of 2 to 80% by weight. If less than 2% by weight,
Crosslinking does not proceed sufficiently and heat resistance, solvent resistance, etc. tend to be reduced. Moreover, if it exceeds 80% by weight,
Impact resistance and the like tend to decrease, and the properties as plastic tend to decrease.

In the above polyolefin-based copolymer composition, the mechanical strength is improved, the optical isotropy is improved, the refractive index is increased,
Various copolymerizable monomers are preferably used in combination for the purpose of lowering water absorption, improving dyeability, improving heat resistance, improving impact resistance. Examples of the monomers that can be used in combination include aromatic vinyl-based monomers, olefin-based vinyl monomers, (meth) acrylic acid and its ester-based monomers, and polyvalent carboxylic acid anhydrides. Specific examples of such an aromatic vinyl-based monomer include styrene, α-methylstyrene, p-methylstyrene, p-tert-butylstyrene, vinyltoluene, chlorostyrene and bromostyrene. Usually, styrene, α-methylstyrene and p- are used because of their performance and industrial availability.
Methylstyrene is used. Other vinyl monomers include (i) vinyl cyanide monomers such as acrylonitrile and methacrylonitrile, (ii) methyl methacrylate, methyl acrylate, cyclohexyl methacrylate, t-butyl methacrylate. Preferred examples include (meth) acrylic acid (ester) -based monomers such as benzyl methacrylate, acrylic acid and methacrylic acid, and (iii) maleic anhydride.

The total content of the monomer represented by the general formula (A) and the polyfunctional monomer having two or more unsaturated groups in the above polyolefin-based copolymer composition is It is preferably 30% by weight or more, and more preferably 40% by weight or more. If it is less than 30% by weight, the polymer may have insufficient transparency, heat resistance, chemical resistance, impact resistance and the like.

It is also useful to add various ultraviolet absorbers, antioxidants and antistatic agents to the transparent resin of the present invention for the purpose of improving light resistance, oxidation resistance and antistatic property. In particular, it is preferable to copolymerize a monomer having an ultraviolet absorbing property or an antioxidant property, because it is possible to improve their performance without lowering the chemical resistance and heat resistance. Preferred examples of such a monomer include a benzophenone-based UV absorber having an unsaturated double bond, a phenylbenzoate-based UV absorber having an unsaturated double bond, and a (meth) acrylic monomer having a hindered amino group as a substituent. Is mentioned. These copolymerization monomers are preferably used in the range of 0.5 to 20% by weight. If it is less than 0.5% by weight, the effect of addition is not observed, and if it exceeds 20% by weight, heat resistance and mechanical strength tend to be lowered.

The method for polymerizing the transparent resin is not particularly limited, and it can be polymerized by a generally known method. When the transparent resin is a polyolefin-based copolymer, it can be polymerized by keeping the above-mentioned monomer mixture under a predetermined temperature condition in the presence or absence of a radical initiator. The degree of polymerization of the transparent resin of the present invention is not particularly limited, but a higher polymerization rate is preferable, and in consideration of solution coating such as transparent cured film and post-processing such as vacuum deposition, the polymerization rate is 90% or more. preferable. The polymerization temperature is preferably in the 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 also no particular limitation on the method for molding the transparent resin, but bulk polymerization, solution polymerization,
Various methods such as suspension polymerization and cast polymerization can be used. An effective molding method is a cast polymerization method. In consideration of mechanical properties, the thickness of the transparent resin substrate is preferably 0.1 to 10 mm,
More preferably, it is 0.1 to 0.8 mm.

The cured coating containing inorganic fine particles in the present invention is a coating containing an organic polymer in addition to the inorganic fine particles. Specific examples of the organic polymer that constitutes the cured film include acrylic resins, silicone resins, polyurethane resins, epoxy resins, melamine resins, polyolefin resins, celluloses, polyvinyl alcohol resins, urea resins, nylon resins. , Polycarbonate resins, and the like. These resins can be used alone or in combination of two or more kinds, and can be three-dimensionally crosslinked by using various curing agents, crosslinking agents and the like. Especially for applications where surface hardness is important, a curable resin is preferable, and for example, an acrylic resin, a silicone resin, an epoxy resin, a polyurethane resin, a melamine resin is preferably used alone or in combination. To be done. When various characteristics such as surface hardness, heat resistance, chemical resistance, and transparency are taken into consideration, it is preferable to use a silicone resin as the organic polymer, and an organosilicon compound represented by the following general formula (B) or It is more preferable to use a polymer obtained from the hydrolyzate.

R ⁴ aR ⁵ b SiX ⁴ _ab (B) wherein R ⁴ is an organic group having 1 to 10 carbon atoms, and R ⁵ 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.

Examples of the organosilicon compound represented by the general formula (B) include (i) methyl silicate, ethyl silicate, n-propyl silicate, iso-propyl silicate, n-butyl silicate, sec-butyl silicate, and t. -Tetraalkoxysilanes such as butyl silicate and hydrolysates thereof, (ii) methyltrimethoxysilane, methyltriethoxysilane, methyltriacetoxysilane, methyltripropoxysilane,
Methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ-
Chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltriacetoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ
-Aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, N-β- (aminoethyl) -γ-
Aminopropyltrimethoxysilane, β-cyanoethyltriethoxysilane, methyltriphenoxysilane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, glycidoxymethyltrimethoxysilane,
Glycidoxymethyltriethoxysilane, α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, 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) ethyltriethoxy Silane, β-
(3,4-Epoxycyclohexyl) ethyltripropoxysilane, β- (3,4-epoxycyclohexyl)
Ethyltributoxysilane, β- (3,4-epoxycyclohexyl) ethyltriphenoxysilane, γ-
(3,4-epoxycyclohexyl) propyltrimethoxysilane, γ- (3,4-epoxycyclohexyl)
Propyltriethoxysilane, δ- (3,4-epoxycyclohexyl) butyltrimethoxysilane, δ-
Trialkoxysilanes such as (3,4-epoxycyclohexyl) butyltriemethoxysilane, triacyloxysilanes, or triphenoxysilanes or hydrolysates thereof, and (iii) dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane. , Phenylmethyldiethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ- Mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-
Aminopropylmethyldiethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, glycidoxymethylmethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, α-glycidoxyethylmethyldimethoxysilane, α-glycidoxy Ethylmethyldiethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylmethyldiethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycidoxypropylmethyldiethoxysilane, β- Glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypro Pyrmethyldipropoxysilane, γ-glycidoxypropylmethyldiptoxysilane, γ-glycidoxypropylmethylmethoxyethoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropylmethyldiacetoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylvinyldimethoxysilane, γ-glycidoxypropylvinyldiethoxysilane, γ-glycidoxypropylphenyldimethoxysilane Examples thereof include silane, dialkoxysilane such as γ-glycidoxypropylphenyldiethoxysilane, diphenoxysilane, diacyloxysilanes and hydrolysates thereof.

These organosilicon compounds may be used alone or in combination.
It is possible to add more than one species. In particular, for the purpose of imparting dyeability, it is preferable to use an organosilicon compound containing an epoxy group or a glycidoxy group, which gives a high added value.

The film-forming component containing a silicone resin as a main component is not limited to a silicone resin, but an acrylic resin, a polyurethane resin, an epoxy resin, as long as the surface hardness is satisfied without impairing transparency. It is possible to add a melamine resin, a polyolefin resin, a cellulose, a polyvinyl alcohol resin, a urea resin, a nylon resin, a polycarbonate resin, or the like.

The organosilicon compound lowers the curing temperature,
In order to further accelerate the curing, it is preferable to use it after hydrolysis. Hydrolysis can be obtained by adding pure water or an acidic aqueous solution such as hydrochloric acid, acetic acid or sulfuric acid, and stirring. The degree of hydrolysis can be easily controlled by adjusting the amount of pure water or acidic aqueous solution added. Upon hydrolysis, it is preferable to add pure water or an acidic aqueous solution in an amount of equimolar or more and 3 times or less the molar amount of the hydrolyzable group contained in the compound represented by the general formula (B) from the viewpoint of accelerating the curing.

At the time of hydrolysis, alcohol or the like is generated, so that it can be hydrolyzed without a solvent.
Further, for the purpose of carrying out the hydrolysis more uniformly, it is also possible to carry out the hydrolysis after mixing the organosilicon compound and the solvent. In addition, depending on the purpose, it is also possible to remove an appropriate amount of the hydrolyzed alcohol and the like under heating and / or reduced pressure, and then to use it, and then to add an appropriate solvent.

The above composition is usually preferably diluted with a volatile solvent and applied as a liquid composition. The solvent to be applied is not particularly limited, but it is required that the surface properties of the object to be coated are not impaired in use. Furthermore, stability of the composition, wettability to the substrate,
The solvent should be determined in consideration of volatility and the like. Further, the solvent can be used not only as one kind but also as a mixture of two or more kinds. Examples of the solvent include alcohols, esters, ethers, ketones, halogenated hydrocarbons, aromatic hydrocarbons such as toluene and xylene, and aprotic polar solvents.

The hardened film has improved surface hardness, controlled refractive index, improved mechanical strength, improved thermal properties, improved durability of metal oxide film and transparent conductive film provided on the cured film. Inorganic fine particles are added for the purpose. The inorganic fine particles are not particularly limited as long as they do not impair the transparency in the film state. A particularly preferable example from the viewpoint of improving workability and imparting transparency is a sol dispersed in a colloidal form. As a more specific example, silica sol,
Examples thereof include antimony oxide sol, titania sol, alumina sol, zirconia sol, and tungsten oxide sol.

The amount of the inorganic fine particles added is not particularly limited, but in order to make the effect more remarkable, 1 is added to the transparent film.
It is preferable that the content is not less than 80% by weight and not less than 80% by weight. If the amount is less than 1% by weight, it is difficult to recognize the effect of addition, and if the amount exceeds 80% by weight, the adhesion with the transparent resin may be poor and the coating film itself may be cracked to cause a problem such as a decrease in impact resistance. There are cases.

The particle size of the inorganic fine particles is not particularly limited, but is preferably 1 to 300 mμ, more preferably 5 to 5.
Those having a thickness of 100 mμ and 20 to 80 mμ are used. If the average particle size exceeds 300 mμ, the resulting coating tends to be poor in transparency and turbid. Further, in order to improve the dispersibility of the particulate inorganic material,
Various fine particle surface treatments may be carried out, and addition of various surfactants, amines, etc. causes no problem.

Various curing agents may be used in combination in the coating composition used for forming the cured film for the purpose of accelerating curing and curing at low temperature. 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,
Examples thereof include various metal complex compounds, metal alkoxides, various salts such as alkali metal organic carboxylates and carbonates, peroxides, and 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 aluminum chelate compound is particularly useful from the viewpoint of the stability of the coating composition and the presence or absence of coloring of the coating film after coating.

The aluminum chelate compound referred to herein is, for example, an aluminum chelate compound represented by the general formula AlX _n Y _3-n . However, X in the formula is O
L (L represents a lower alkyl group), Y is a general formula M ¹ CO
A ligand derived from a compound represented by CH ₂ COM ² (M ¹ and M ² are both lower alkyl groups) and a compound represented by the general formula M
^It is at least one selected from the ligands derived from the compound represented by ³ COCH ₂ COOM ⁴ (M ³ and M ⁴ are both lower alkyl groups), and n is 0, 1 or 2.

As the aluminum chelate compound represented by the general formula AlXnY3-n, various compounds can be mentioned, but from the viewpoints of solubility in the composition, stability, effect as a curing catalyst and the like, particularly preferable ones are: Aluminum acetylacetonate, aluminum bisethylacetoacetate monoacetylacetonate, aluminum-di-n-butoxide-monoethylacetoacetate, aluminum-di-iso-propoxide-monomethylacetoacetate and the like. It is also possible to use a mixture of two or more of these.

Various kinds of surfactants are added to the coating composition used for forming the cured film for the purpose of improving the flow at the time of application and improving the smoothness of the transparent film to reduce the friction coefficient of the film surface. It is also possible to do so. As the surfactant, a block or graft copolymer of dimethylpolysiloxane and alkylene oxide, and a fluorine-based surfactant are particularly effective.

Inorganic oxides other than the inorganic fine particles can be added to the coating composition used for forming the cured coating film, as long as the coating performance and transparency are not significantly reduced. By using these additives in combination, various properties such as adhesion to a substrate, chemical resistance, surface hardness, and durability can be improved. Examples of the inorganic material that can be added include metal alkoxides represented by the following general formula (C), chelate compounds, and / or hydrolysates thereof.

M (OR) m (C) Here, M is silicon, titanium, zircon, antimony, tantalum, germanium, aluminum or the like. R is an alkyl group, an acyl group, or an alkoxyalkyl group. m is the same value as the number of charges of the metal M.

It is also possible to add an ultraviolet absorber for the purpose of improving the light resistance and an antioxidant for the purpose of improving the heat deterioration.

The cured film is obtained by curing the above coating composition, and the curing is carried out by heat treatment. The heating temperature is appropriately selected in consideration of the composition of the coating composition and the heat resistance of the transparent crosslinked resin, but is preferably 50 to 250 ° C.

As a method of applying a film on the transparent resin,
Conventional coating methods such as brush coating, dip coating, roll coating, spray coating, spin coating and flow coating can be easily used.

In applying the coating composition,
It is also an effective means to perform various pretreatments for the purpose of improving cleaning, adhesion and water resistance. Particularly preferably used pretreatments include activated gas treatment, chemical treatment, and ultraviolet treatment. These pretreatments are
It is also sufficiently possible to carry out the combined use either continuously or stepwise.

The activated gas treatment is a treatment with ions, electrons or excited gas produced under normal pressure or reduced pressure. As a method of generating these activated gases, for example, corona discharge, direct current under reduced pressure,
There are low frequency, high frequency or high voltage discharge by microwave. The gas used here is not particularly limited, but specific examples include oxygen, nitrogen, hydrogen, carbon dioxide, sulfur dioxide, helium, neon, argon, freon, water vapor, ammonia, carbon monoxide, Examples include chlorine, nitric oxide, and nitrogen dioxide. These can be used as a mixture of two or more kinds. Among the above, preferable gases include those containing oxygen, and those existing in nature such as air may be used. More preferably, pure oxygen gas is effective for improving adhesion.
Further, it is possible to raise the temperature of the substrate to be treated during the treatment.

Specific examples of the chemical treatment include (i) alkali treatment with caustic soda, (ii) acid treatment with hydrochloric acid, sulfuric acid, potassium permanganate, potassium dichromate, etc., and (iii) organic solvent treatment. To be

The film thickness of the cured film is not particularly limited, but from the viewpoint of maintaining the adhesive strength, hardness, etc.
It is preferably between 1 and 50μ. Particularly preferably 0.3 to 1
0 μ. In addition, in coating the coating, the coating composition is diluted with various solvents for the purpose of workability and adjustment of the coating thickness. As the diluting solvent, for example, water, alcohols, esters, ethers, halogenated hydrocarbons, dimethylformamide, dimethylsulfoxide and the like can be variously used according to the purpose, and it is also possible to use a mixed solvent as necessary. . A polar solvent such as water, alcohol, dimethylformamide, ethylene glycol, diethylene glycol, triethylene glycol, benzyl alcohol, phenethyl alcohol, or phenyl cellosolve is preferably used from the viewpoint of dispersibility of the particulate inorganic oxide.

The transparency of the transparent resin having a cured coating is preferably 60% or more, more preferably 80% or more, when the total light transmittance is used as an index. For applications where optical isotropy is important, the birefringence is preferably 30 nm or less.
It is more preferably 5 nm or less.

The metal oxide film formed by the high frequency discharge sputtering method provided on the cured coating containing the inorganic fine particles in the present invention uses a dielectric or an insulator metal oxide as a sputtering target and an inert gas. The film is formed under an atmosphere and / or an activated gas atmosphere. As the metal oxide film, for example, Si, Zr, T
Examples thereof include metal oxides composed of i, Y, Yb, Mg, Ta, Ce, Hf, etc. From the viewpoint of improving cost, transparency, gas barrier property, and durability of the transparent conductive film provided on the metal oxide film. Oxides of metals selected from Si, Al and Ti are preferable. As the sputtering gas, an inert gas such as He, Ne, Ar, Kr, Xe, or Rn is used, but Ar is particularly preferably used from the viewpoints of cost, availability, and sputtering rate. Further, O ₂ , N ₂ , CO, CO ₂ or the like is used as the activating gas, and O ₂ is preferably used from the viewpoint of compensating for O ₂ deficiency during sputtering when forming the metal oxide film. The O ₂ concentration (partial pressure with respect to the inert gas) is appropriately selected depending on the type of cured film containing inorganic fine particles, the substrate temperature, the target material, the sputtering rate, and the input power, but is generally 0.1 to 10%. is there. In the present invention, it is preferably 5% or less, more preferably 1% or less, from the viewpoint of reducing plasma damage to the cured film containing the inorganic fine particles.

The film thickness of the metal oxide film is not particularly limited, but is preferably 50 to 2000 angstroms, more preferably 100 to 1200 angstroms from the viewpoints of film formation time, gas barrier property imparting, and durability of the transparent conductive film. .

As a method of forming a transparent conductive film containing an ITO (Indium Tin Oxide) film as a main component on the metal oxide film obtained as described above, a vacuum deposition method is used. A method such as an ion plating method, a high frequency discharge method, a direct current method or a sputtering method such as a magnetron method can be used. High transparency,
The substrate temperature during film formation is appropriately selected depending on the transparent resin material, the type of the cured film, and the like from the viewpoint of improving conductivity, adhesiveness, heat resistance, and chemical resistance. Further, the composition ratio of ITO should be determined by the surface resistance value, specific resistance, transparency and the like required for the transparent conductive film, but from the viewpoint of improving conductivity and imparting transparency, the content of SnO ₂ is 25 wt. % Or less, and in order to further improve the conductivity, it is preferable to use a high-density ITO target in which the ITO target is close to the true density of ITO. The film thickness of the ITO film is not particularly limited, but it is preferable to be appropriately selected from the range of 150 to 5000 angstrom in consideration of the conductivity and the film formation time. Since the plastic optical article obtained as described above has excellent conductivity, transparency, heat resistance, chemical resistance and durability, it can be used for electric parts circuit materials such as capacitors and resistors, electrophotography and static electricity. Materials for copying such as electronic recording, liquid crystal displays, electrochromic displays, electroluminescent displays, touch panel signal input transparent electrodes, solar cells, photoelectric amplifiers such as optical amplifiers, antistatic, electromagnetic wave shielding It can be used for various applications such as applications, surface heating elements, and sensors.

The plastic optical article of the present invention is preferably used as a substrate for a liquid crystal display, and TN
(Twisted Nematic type), STN (Super Twisted Nema)
tic type, ferroelectric liquid crystal) FLC (Ferroelectric Liquid)
Simple matrix type such as Cristal type, MIM (Meta
l-Insulator-Metal) type, TFT (Thin-Film Transist
Although it is applicable to active matrix type liquid crystal displays such as or) type, it is preferably used for simple matrix type liquid crystal displays because the manufacturing process is relatively simple.

When the plastic optical article of the present invention is used as a substrate for a liquid crystal display, it has a structure in which a liquid crystal is sandwiched by the plastic optical article. That is, in the conventional liquid crystal display using a glass substrate, the plastic optical article of the present invention replaces the glass substrate. Specifically, the liquid crystal layer is sandwiched between the plastic optical article of the present invention and a substrate provided with an insulating film and an alignment film thereon if necessary.
A deflection plate is provided outside the substrate holding the liquid crystal layer.
A liquid crystal display further includes a retardation plate, a light reflection plate, or the like, if necessary.

As a method for producing a liquid crystal display using the plastic optical article 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 Japan Society for the Promotion of Science, 142nd Edition, published by Nikkan Kogyo Shimbun, 19
89) p. 531], after cleaning the substrate, transparent conductive film formation, transparent conductive film fine processing (resist coating, development, etching, resist cleaning removal), alignment film formation, rubbing treatment, cleaning, sealing agent printing, substrate bonding, A liquid crystal display device is obtained by sequentially performing steps such as heating / pressurization, vacuum degassing, liquid crystal injection, injection port sealing, liquid crystal cell division, and sticking of a deflector / light reflector. In these liquid crystal display manufacturing steps, the manufacturing conditions should be set in consideration of various properties such as heat resistance and mechanical properties of the liquid crystal display substrate using the plastic optical article.

[0056]

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

Various characteristics of the transparent resin were measured as follows.

The total light transmittance was measured according to ASTM D-648, and the solvent resistance was evaluated by visually observing the gloss change at that time by rubbing the surface with gauze impregnated with acetone. Further, the glass transition temperature was measured using a Mettler TA3000 (measured at 2nd run).

The plastic optical article provided with a cured coating, a metal oxide film, and a transparent conductive film was measured as follows.

(A) Appearance It was visually observed.

(B) Surface resistance Loresta MCP-TESTER-FP (manufactured by Mitsubishi Petrochemical Co., Ltd.) was used and measured at room temperature. (C) Adhesiveness Put 100 pieces of crevices reaching the base material of 1 mm on the surface of the transparent conductive film with a steel knife, and strongly stick cellophane adhesive tape (trade name "Cellotape", manufactured by Nichiban Co., Ltd.),
It was rapidly peeled off in the direction of 90 degrees, and the presence or absence of peeling of the coating film was examined.

(D) Heat resistance After heating in an oven set to 180 ° C. for 2 hours and cooling to room temperature, the appearance of the plastic optical article was visually observed.

(E) Chemical resistance A plastic optical article is dipped in a 3% caustic soda aqueous solution at 40 ° C. for 5 minutes, washed with running water for 5 minutes, replaced with purified water, drained with gauze, and visually observed. I observed.

Example 1 (1) Preparation of transparent resin Isopropylmaleimide 26.5 g, styrene 18.5
g, divinylbenzene 5.0 g, and azobisisobutyronitrile 0.05 g were mixed and dissolved, and cast molding was performed by cast polymerization. Cast polymerization was performed as follows.

Size 300 mm × 300 mm, thickness 5 m
A soft vinyl chloride gasket was attached to the outer peripheral portion of the two glass plates of m, and the two glass plates were assembled so that the distance between the two glass plates was 0.4 mm. Inject the monomer mixture into the assembled glass plate, and heat at 70 ° C. for 8 hours and 100 ° C. for 1 hour.
Further, polymerization was carried out at 150 ° C. for 1 hour to obtain a molded plate (I) made of a resin having a crosslinked structure.

The glass transition temperature of this molded plate (I) is 18
It was 0 ° C., and the total light transmittance was 90%. Furthermore, flexural modulus at room temperature is 398kg / mm ^2, the flexural strength was 9 kg / mm ^2, the solvent resistance was good.

(2) Formation of cured coating containing inorganic fine particles 95.3 g of γ-glycidoxypropyltrimethoxysilane was charged into a reactor equipped with a rotor, the liquid temperature was kept at 10 ° C., and a magnetic stirrer was used. 0.0 with stirring
21.8 g of 1N hydrochloric acid aqueous solution was gradually added dropwise. After completion of dropping, cooling was stopped to obtain a hydrolyzate of γ-glycidoxypropyltrimethoxysilane.

Methanol 216 was added to this silane hydrolyzate.
g, dimethylformamide 216 g, silicon-based surfactant 0.5 g, bisphenol A type epoxy resin (Yukaka Shell Epoxy Co., trade name Epicoat 827) 67.
5 g was added and mixed, and further 270 g of colloidal antimony pentoxide sol (average particle size 50 mμ) and 13.5 g of aluminum acetylacetonate were added and sufficiently stirred to obtain a coating composition (I).

Coating composition (I) on molded plate (I)
Was applied by dip coating, then pre-cured at 100 ° C. for 10 minutes, and further heated at 110 ° C. for 4 hours to form a cured coating containing inorganic fine particles on the molded plate (I).

(3) Formation of Metal Oxide Film On the molded plate having the cured coating containing the inorganic fine particles obtained in (2) above, SiO _{2 of the} metal oxide is deposited by RF discharge sputtering under the following conditions. A 600 angstrom film was formed.

Sputtering conditions Target material: SiO ₂ sputtering introduction gas: Ar Sputtering film forming vacuum degree: 3.5 × 10 ⁻³ Torr Input power: 1.5 kw Substrate temperature: 120 ° C. Sputtering rate: 50 Å /
Min (4) I on the metal oxide film obtained by the above (3)
A transparent conductive film containing TO as a main component was formed into a film having a thickness of about 1000 Å by the DC magnetron sputtering method under the following conditions.

Sputtering conditions Target material: ITO (SnO ₂ 10
wt%) Sputtering introduction gas: Ar and O ₂ Sputtering film forming vacuum degree: 2.0 × 10 ⁻³ Torr Input power: 1.5 kw Substrate temperature: 120 ° C. Sputtering rate: 100 Å / min The characteristics are shown in Table 1.

Example 2 The same procedure as in Example 1 was carried out except that the transparent resin was prepared and the cured coating containing the inorganic fine particles was changed as follows. Various characteristics of the obtained optical article are shown in Table 1.

(1) Preparation of transparent resin 23.5 g of isopropylmaleimide, 5.0 g of cyclohexylmaleimide, 15.5 g of styrene, 6.0 g of divinylbenzene, and 0.1 g of azobisisobutyronitrile were mixed and dissolved, and cast polymerization was carried out. It was cast-molded by. Cast polymerization was performed as follows.

Size 300 mm × 300 mm, thickness 5 m
A soft vinyl chloride gasket was attached to the outer peripheral portion of the two glass plates of m, and the two glass plates were assembled so that the distance between the two glass plates was 0.4 mm. Inject the monomer mixture into the assembled glass plate, and heat at 70 ° C. for 8 hours and 100 ° C. for 1 hour.
Further, polymerization was carried out at 150 ° C. for 1 hour to obtain a molded plate (II) made of a resin having a crosslinked structure.

The glass transition temperature of this molded plate (II) is 1
The temperature was 80 ° C., and the total light transmittance was 90%. Also,
The flexural modulus at room temperature was 398 kg / mm ² , the flexural strength was 9 kg / mm ² , and the solvent resistance was good.

(2) Formation of Hardened Film Containing Inorganic Fine Particles 91.1 g of γ-glycidoxypropylmethyldimethoxysilane was charged into a reactor equipped with a rotor and the liquid temperature was adjusted to 10
While being kept at 0 ° C., 13.2 g of a 0.05 N hydrochloric acid aqueous solution was gradually added dropwise while stirring with a magnetics stirrer. After completion of dropping, cooling was stopped to obtain a hydrolyzate of γ-glycidoxypropylmethyldimethoxysilane.

To this silane hydrolyzate, 178.1 g of n-propyl alcohol, 29.7 g of benzyl alcohol,
59.5 g of diacetone alcohol, 28.7 g of acetylacetone, 1.3 g of a surfactant, 64.0 g of bisphenol A type epoxy resin (trade name Epicoat 827, manufactured by Yuka Shell Epoxy Co., Ltd.) were added and mixed, and further colloidal silica sol. (Average particle size 50 mμ) 426.5 g, aluminum acetylacetonate 7.5 g, and triethylene glycol 8.5 g were added, and after sufficiently stirring, a coating composition (II) was obtained.

The coating composition (I
I) was applied by dip coating, then pre-cured at 100 ° C. for 10 minutes, and further heated at 110 ° C. for 4 hours to form a cured coating containing inorganic fine particles on the molded plate (II).

[0080] Example 3 Example of SiO ₂ metal oxide in 2 high-frequency discharge sputtering conditions of the sputtering introducing gases Ar and O ₂
(O ₂ partial pressure: 2.5%), except that the procedure was the same.

Table 1 shows various characteristics of the obtained optical article.

Comparative Example 1 The same procedure as in Example 1 was carried out except that the method of forming the metal oxide film in Example 1 was changed to the DC magnetron sputtering method.

Sputtering Conditions Target Material: Si Sputtering Gas: Ar and O ₂ (O ₂ Partial Pressure 2.5%) Sputtering Deposition Vacuum Degree: 1.0 × 10 ⁻³ Torr Input Power: 0.3 kw Substrate Temperature: 120 ° C. Sputtering rate: 10 Å / min. Various properties of the obtained optical article are shown in Table 1.

Comparative Example 2 The same procedure as in Example 1 was carried out except that the cured coating containing inorganic fine particles was not provided. Table 1 shows various properties of the obtained optical article.

[0085]

[Table 1]

[0086]

According to the present invention, excellent conductivity and transparency,
Moreover, a plastic optical article having excellent heat resistance, durability, and chemical resistance can be provided.

Claims (10)

[Claims] 1. A plastic optical article in which the following A, B, C and D are laminated in this order. A: transparent resin B: cured film containing inorganic fine particles C: metal oxide film formed by high frequency discharge sputtering method D: transparent conductive film containing indium and tin mixed oxides as main components 2. The plastic optical article according to claim 1, wherein the transparent resin is a resin having a glass transition temperature of 160 ° C. or higher. 3. The plastic optical article according to claim 1, wherein the transparent resin is a crosslinked resin. 4. The metal oxide film has a thickness of 50 to 2000 angstroms.
Alternatively, the plastic optical article according to the item 3. 5. The transparent conductive film has a thickness of 100 to 5000 angstroms.
The plastic optical article according to 2, 3, or 4. 6. The plastic optical article according to claim 1, wherein the metal oxide film is made of an oxide of a metal selected from Si, Al and Ti. 7. The cured coating containing inorganic fine particles is a siloxane-based cured coating containing one or more fine particles selected from silica, antimony oxide, titania, alumina, zirconia and tungsten oxide having an average particle diameter of 1 to 300 mμ. The plastic optical article according to claim 1. 8. The transparent resin contains a maleimide-based monomer in an amount of 20 to 20.
The plastic optical article according to claim 1, 2 or 3, which is a resin obtained by copolymerizing 98% by weight. 9. The plastic optical article according to claim 1, wherein the metal oxide film is a film formed in an inert gas atmosphere having an oxygen concentration of 1% or less. 10. The plastic optical article according to claim 9, wherein the inert gas is Ar gas.