JP3158541B2 - Optical article and method of manufacturing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optical article having excellent heat resistance, scratch resistance, transparency and solvent resistance.

[0002]

2. Description of the Related Art Generally, plastic materials are light in weight, and excellent in impact resistance, workability and mass productivity. Therefore, in recent years, demands for materials for optical elements such as optical filters, optical lenses and optical disks have been increasing.

[0003] Generally, plastic optical elements have drawbacks in that they have lower heat resistance and lower surface hardness than inorganic glass, and many attempts have been made to improve them. For example, Si
A method of coating an inorganic substance such as O ₂ by vacuum deposition (Japanese Patent Application Laid-Open No. 58-202031) and a method of providing a polyorganosilane hard coat film or an acrylic hard coat film on the surface of a plastic substrate (US Pat. No. 3,986) 99
7, USP 4,211,823, JP-A-57-1689.
No. 222, JP-A-59-38262, JP-A-59-51908, 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).

[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 particular, those having an inorganic thin film layer on a hard coat film had a problem in heat resistance.

An object of the present invention is to solve the above problems, and an object of the present invention is to provide a plastic optical article having excellent heat resistance, scratch resistance, transparency, and solvent resistance.

[0006]

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

[0007] (1) An organic polymer and a particulate inorganic oxide MxOy (where M represents an inorganic element,
x and y each represent a natural number) as a main component and having a thickness of 0.5 μm or more and 30 μm or less.
And a liquid crystal display substrate provided with a transparent conductive film , wherein the M / C atomic ratio in the surface layer of the cured film is less than the M / C atomic ratio at 0.2 μm from the surface layer of the cured film. 2% or more for liquid crystal displays
Substrate .

(2) An organic polymer and a particulate inorganic oxide Mx Oy (where M represents an inorganic element, x, y
Each represents a natural number) and a composition containing a hydrophilic compound is applied to form a film, and further a transparent conductive film is formed.
Method of manufacturing a substrate for a liquid crystal display according to claim Rukoto provided. The substrate used in the present invention is not particularly limited as long as it satisfies the object of the present invention. From the viewpoint of transparency, a transparent plastic material or glass gives particularly effective results. Examples of transparent plastic materials include thermoplastic resins such as polymethyl methacrylate and copolymers thereof, polycarbonate, polyester, polysulfone, and polyether sulfone, and thermosetting resins such as diethylene glycol bisallyl carbonate (CR-39), unsaturated polyester, and epoxy resin. Although a resin is appropriately used, a transparent three-dimensional crosslinked resin is more preferably used in the present invention because of its excellent heat resistance typified by thermal deformation characteristics.

As the transparent three-dimensional crosslinked resin in the present invention, a transparent three-dimensional crosslinked resin having a glass transition temperature of 130 ° C. or more can be used particularly preferably. , Heat resistance is further improved, and it is more preferably used. Here, the glass transition temperature refers to the temperature at which a polymer changes from an amorphous glass state to a rubber state. In the transition region, various properties such as elastic modulus, expansion coefficient, heat content, refractive index, and dielectric constant are used. Changes. 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 K
7121). In the case of measuring the glass transition temperature by differential scanning calorimetry, the glass transition temperature can be determined by evaluating the transparent three-dimensional resin itself or a heat-treated transparent three-dimensional resin. The glass transition temperature of an article in which a cured coating is provided on a three-dimensional resin can be regarded as the glass transition temperature of a transparent three-dimensional resin.

The mechanical properties of the transparent three-dimensionally crosslinked resin are preferably 2 when the flexural modulus is expressed as an index.
00 kg / mm ² , more preferably 330 kg / mm ²
mm ² or more. Further, the transparency of the transparent three-dimensionally crosslinked resin is preferably 60% or more, more preferably 80% or more, when the total light transmittance at the time of no coloring is represented as an index. The transparent three-dimensional crosslinked resin 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. .

As a component of the transparent three-dimensional crosslinked resin having a glass transition temperature of 130 ° C. or more, for example, polymethacrylic acid,
Polyolefin resins represented by polymethacrylic resins such as polycarboxyphenyl methacrylamide and polystyrene resins such as poly (biphenyl) styrene, and poly (2,6-dimethyl-1,4-phenylene oxide) Polyether resin, polycarbonate resin represented by poly (oxycarbonyloxy-1,4-phenyleneisopropylidene-1,4-phenylene), poly (oxy-2,2,4,4-tetramethyl-1) , 3-cyclobutyleneoxyterephthaloyl)
Polyester resin represented by
4-phenylenesulfonyl-1,4-phenylene), poly (oxy-1,4-phenyleneisopropylidene-
Polysulfone-based resins such as 1,4-phenyleneoxy-1,4-phenylenesulfonyl-1,4-phenylene) and poly (iminoisophthaloylimino-4,
4′-biphenylene), a polyamide resin represented by
Poly (thio-1,4-phenylenesulfonyl-1,4-
(Phenylene) represented by polysulfide resin, unsaturated polyester resin, epoxy resin, melamine resin, phenol resin, diallyl phthalate resin, polyimide resin, polyphosphazene resin, etc. It is possible to obtain a transparent three-dimensionally crosslinked resin exhibiting the above-mentioned thermal characteristics by introducing a three-dimensionally crosslinked structure in the polymer group. In particular, a polyolefin-based resin is preferable from the viewpoint of transparency and moldability.
A polyolefin-based copolymer obtained by polymerizing a composition containing a polyfunctional monomer having at least one polyolefin monomer is more preferably used.

As the copolymer, 20 to 98% by weight of the monomer represented by the general formula (A) and 2
2 to 80% by weight of a polyfunctional monomer having at least one monomer, and the monomer represented by the general formula (A) and the unsaturated group
A copolymer obtained by polymerizing a composition having a total weight ratio of at least 30% by weight with a polyfunctional monomer having at least one polymer is particularly preferably used.

[0013]

Embedded image

(Wherein R ³ is hydrogen and carbon number 1-20)
Represents a substituent selected from the hydrocarbon groups of R ¹ , R ²
Represents a substituent selected from hydrogen, a methyl group and an ethyl group. ) R ¹ and R ² contained in the maleimide derivative compound represented by the general formula (A) may be the same or different.

When R ³ 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 ¹ , R ² and R ³ are substituted with various substituents such as halogeno groups such as fluorine, chlorine and bromine, cyano groups, carboxyl groups, sulfonic groups, nitro groups, hydroxy groups and alkoxy groups. May be done.

Specific examples of the compound represented by the general formula (A) include N-methylmaleimide, N-butylmaleimide, N-phenylmaleimide, No-methylphenylmaleimide, Nm-methylphenylmaleimide, and N-methylmaleimide. −
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, alkylmaleimide and cycloalkylmaleimide are particularly preferable from the viewpoint of yellowing after the heat resistance test and weather resistance, and N-iso-propylmaleimide and N-cyclohexylmaleimide are particularly preferable.
Further, considering the easiness of preparing a monomer solution at the time of cast polymerization, N-iso-propylmaleimide and N-iso-
Combinations of N-alkylmaleimides such as -cyclohexylmaleimide and N-alicyclic alkylmaleimides are also preferably used. 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, it is usually preferable to use 10 to 500 parts by weight of N-alicyclic maleimide with respect to 100 parts by weight of N-alkylmaleimide in order to exert the effect of the combined use.

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, Methyl vinyl group,
An acryl group, a methacryl group and the like can be mentioned. 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 as described above 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 heteroatom cyclic skeleton such as triallyl diisocyanurate.

The above-mentioned polyolefin-based copolymer preferably contains the monomer represented by the aforementioned general formula (A) in an amount of 20% by weight or more and 98% by weight or less.
When the amount is less than 0% by weight, there is a tendency that properties such as sufficient heat resistance, mechanical strength and optical isotropy cannot be satisfied. On the other hand, if the content exceeds 98% by weight, the degree of crosslinking tends to decrease, and it tends to be impossible to satisfy solvent resistance, low water absorption and the like. 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 must be contained in the three-dimensional crosslinked polymer at a ratio of 2% by weight or more and 80% by weight or less. 2
If the content is less than 3% by weight, three-dimensional crosslinking does not proceed sufficiently, and a decrease in heat resistance and solvent resistance tends to be observed. On the other hand, if it exceeds 80% by weight, the impact resistance and the like may be reduced, and the characteristics as a plastic may be deteriorated.

Further, in the above-mentioned polyolefin-based copolymer, improvement of mechanical strength, improvement of optical isotropy, increase of refractive index, reduction of water absorption, improvement of dyeability, improvement of heat resistance, improvement of impact resistance, etc. For the purpose, 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 an aromatic vinyl monomer include styrene, α-methylstyrene, p-methylstyrene, p-tert-butylstyrene, vinyltoluene, 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.

The total content of the monomer represented by the general formula (A) and the polyfunctional monomer having two or more unsaturated groups in the polyolefin copolymer is 30% by weight in the three-dimensional crosslinked resin. %, More preferably 40% by weight or more. That is, if it is less than 30% by weight, transparency, heat resistance, chemical resistance, impact resistance, and the like tend to be insufficient.

The transparent three-dimensional crosslinked resin in the present invention includes:
It is also useful to add various ultraviolet absorbers, antioxidants, and antistatic agents for the purpose of improving light resistance, oxidation deterioration resistance, and antistatic properties. In particular, it is preferable to copolymerize a monomer having an ultraviolet absorbing property or an antioxidant property, since these properties can be improved without lowering chemical resistance and heat resistance. Preferred examples of such a monomer include a benzophenone ultraviolet absorber having an unsaturated double bond, a phenylbenzoate 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 it exceeds 20% by weight, heat resistance, mechanical strength, and the like tend to be reduced.

The method for polymerizing the transparent three-dimensionally crosslinked resin of the present invention is not particularly limited, and it can be polymerized by a generally known method. When the transparent three-dimensional crosslinked resin is a polyolefin-based copolymer, polymerization can be performed by maintaining the above monomer mixture under a predetermined temperature condition in the presence or absence of a radical-generating initiator. Various methods such as bulk polymerization, solution polymerization, suspension polymerization, and cast polymerization can be used. The degree of polymerization of the transparent three-dimensionally crosslinked resin of the present invention is not particularly limited, but the higher the degree of polymerization, the higher the degree of polymerization is preferably 90% or more in consideration of post-processing such as solution coating such as a cured film, vacuum deposition, and sputtering. preferable.

The method for molding the transparent three-dimensionally crosslinked resin of the present invention is not particularly limited, but an effective molding method includes a cast polymerization method.

The plastic optical article of the present invention comprises an organic polymer and a particulate inorganic oxide M _x O _y on the substrate.
(Here, M represents an inorganic element, and x and y each represent a natural number.) In this case, an organic polymer is a fine particle inorganic oxide and There is no particular limitation as long as they have compatibility. Specific examples of usable organic polymers include acrylic resins, silicone resins, polyurethane resins, epoxy resins, melamine resins, polyolefin resins, celluloses, polyvinyl alcohol resins, urea resins, nylon resins, and polycarbonate resins. Base resin and the like. These resins can be used alone or in combination of two or more, and can be three-dimensionally cross-linked using various curing agents, cross-linking agents and the like. Particularly for applications where surface hardness is important, it is preferable to use a curable resin. For example, a single resin or a composite resin such as an acrylic resin, a silicone resin, an epoxy resin, a polyurethane resin, and a melamine resin is preferably used. Is done. When various properties 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 more preferably, it is represented by the following general formula (B). Examples thereof include polymers obtained from an organosilicon compound or a hydrolyzate thereof.

[0029] ^{_{R 4 a R 5 b SiX 4}} -ab (B) ( wherein, R ⁴ is an organic group having 1 to 10 carbon atoms, R ⁵
Is a hydrocarbon group having 1 to 6 carbon atoms or a halogenated hydrocarbon group having 1 to 6 carbon atoms, 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 methyl silicate, ethyl silicate, n-propyl silicate, iso-propyl silicate, n-butyl silicate, sec-butyl silicate, and t-butyl silicate.
Tetraalkoxysilanes such as butyl silicate, and hydrolysates thereof, further, methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane, methyltriacetoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxy Silane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane,
Vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, 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-glycidoxypropyltrimethoxyethoxysilane, 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) ethyltrimethoxyethoxysilane, β- (3, 4-epoxycyclohexyl) ethyltriphenoxysilane, γ- (3,4-epoxycyclohexyl) propyltrimethoxysilane, γ- (3,4-
Trialkoxysilane, triacyloxysilane, or triphenoxy such as epoxycyclohexyl) propyltriethoxysilane, δ- (3,4-epoxycyclohexyl) butyltrimethoxysilane, δ- (3,4-epoxycyclohexyl) butyltriemethoxysilane Silanes or hydrolysates thereof and 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-glycidoxyethylmethyl Dimethoxysilane, α-glycidoxyethylmethyldiethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylmethyldiethoxysilane α-glycidoxypropylmethyldimethoxysilane, α-glycidoxypropylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane Silane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethylmethoxyethoxysilane, γ-glycid Xypropylmethyldiphenoxysilane, γ-glycidoxypropylmethyldiacetoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylvinyldimethoxy Silanes, dialkoxysilanes such as γ-glycidoxypropylvinyldiethoxysilane, γ-glycidoxypropylphenyldimethoxysilane, γ-glycidoxypropylphenyldiethoxysilane, diphenoxysilane or diacyloxysilanes or a hydrolyzate thereof Decomposition products are an example.

These organosilicon compounds may be used alone or in combination.
It is also possible to add more than one species. 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.

These organosilicon compounds are 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 (B) from the viewpoint of accelerating curing.

At the time of the hydrolysis, it is possible to carry out the hydrolysis without a solvent since alcohol and the like are generated. However, after the organic silicon compound and the solvent are mixed 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 above composition is usually preferably diluted in a volatile solvent and applied as a liquid composition, but the composition applied as a solvent is not particularly limited. Is not impaired, and should be determined in consideration of the stability of the composition, wettability to a substrate, volatility, and the like. Further, the solvent may be used as a mixture of not only one kind but also two or more kinds. These solvents include alcohols, esters, ethers, ketones, halogenated hydrocarbons, aromatic hydrocarbons such as toluene and xylene, and solvents such as aprotic polar solvents.

The cured film used in the present invention contains, as an essential component, a particulate inorganic oxide M _x O _{y in} addition to the above-mentioned organic polymer. The following is preferred. If the amount exceeds 80% by weight, problems such as poor adhesion to the plastic substrate, cracks in the coating itself, and reduced impact resistance tend to occur. Such a particulate inorganic oxide is not particularly limited as long as it does not impair transparency in the state of a coated film, but a particularly preferred example from the viewpoint of workability and imparting transparency is a sol dispersed in a colloidal form. As more specific examples, silica sol (SiO ₂ ), titania sol (T
iO ₂ ), antimony oxide sol (Sb ₂ O ₅ or Sb
₂ O ₃ ), alumina sol (Al ₂ O ₃ ), zirconia sol (ZrO ₂ ) and the like. The particle size of the particulate inorganic oxide used in the present invention is not particularly limited, but for the purpose of the present invention, preferably has an average particle size of 1 to 200.
mμ, more preferably 5 to 100 mμ, more preferably 20
〜80 mμ is used. Average particle size is 200m
When a material having a particle diameter exceeding μ is used, the resulting film tends to be poor in transparency and highly cloudy. There is no problem even if various surfactants or amines are added to improve the dispersibility of the particulate inorganic oxide.

The dispersed state of the inorganic oxide M _x O _y fine particles in the cured film is important because it affects the heat resistance when an inorganic thin film or the like is provided on the cured film. When the fine particles of the inorganic oxide M _x O _y are present densely near the surface of the cured film, it is possible to prevent the inorganic thin film provided on the cured film from peeling or cracking. In the present invention, as an index of the dispersion state of the inorganic oxide M _x O _y fine particles in the cured film, a comparison of the concentration of the particulate inorganic oxide on the surface of the cured film and inside the cured film is used. The concentration of the particulate inorganic oxide in the surface layer of the cured film is usually determined by using ESCA (electron spectroscopy for chemica).
l analysis). This is a method of irradiating a sample surface with X-rays and obtaining information on the elemental composition in the sample from the kinetic energy and the amount of photoelectrons emitted by the photoelectric effect. In this technique, the composition of the surface layer can be analyzed by changing the angle between the sample surface and the X-ray source, and the ratio of the inorganic atom M contained in the inorganic oxide to the carbon atom contained in the organic polymer, M / C atom The number ratio indicates the concentration of the particulate inorganic oxide on the surface of the cured film. Usually, when the sample surface is irradiated with X-rays, the M / C atomic ratio at about 30 Å from the surface layer is measured. In the present invention, “M / C in the surface layer of the cured film”
The "atomic ratio" is measured by irradiating the sample surface with X-rays as described above.

The concentration of the particulate inorganic oxide in the cured film was also evaluated by ESCA and the like.
It is displayed in the ratio of the number of C atoms. In the present invention, the concentration evaluation inside the film is performed at a position of 0.2 μm from the surface layer, that is, after physically removing a 0.2 μm thick portion from the surface layer, performing the ESCA evaluation in the same manner as described above, while performing sputter etching. Method of performing ESCA evaluation (evaluation of element composition change from surface to depth direction, depth-profiling
Evaluation) and the like are appropriately used. M of surface layer of cured film
When the / C atomic ratio is 2% or more, more preferably 5% or more of the M / C atomic ratio at 0.2 μm from the surface layer of the cured film, the heat resistance when an inorganic thin film or the like is provided on the cured film Excellent.

Various curing agents can be used in combination with the coating composition used in forming a cured film in the present invention for the purpose of accelerating curing and curing at low temperatures. 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 include various metal complex compounds, metal alkoxides, various salts such as alkali metal organic carboxylate and carbonate, and radical polymerization initiators such as peroxides and 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 film 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 . In the formula, X represents OL (L represents a lower alkyl group), and Y represents a general formula M ¹ COCH ₂ COM.
² (M ¹ and M ² are both lower alkyl groups) and a ligand derived from the compound represented by the general formula M ³ COCH ₂ C
OOM ⁴ (M ³ and M ⁴ are each a lower alkyl group) is at least one selected from ligands derived from compounds represented by the following formula, 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.

Some of the cured films of the present invention can be dyed with various dyes, especially disperse dyes. In the case of dyed products, various transition metal compounds or their transition metals 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 molded product, the type of the diluting solvent and the types of other components, but the solubility and the whiteness of the coating film should be determined. 0.001 in
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, and if the amount is more than 10% by weight, clouding of the coating film may occur. In addition, 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 cured film, but it is included in the film as a chelate compound in order to obtain a greater effect Is preferred.

The coating composition used in the formation of the cured film of the present invention may have various surfactants for the purpose of improving the flow during application, improving the smoothness of the cured film and reducing the coefficient of friction 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.

Further, an inorganic oxide other than the finely divided inorganic oxide may be added to the coating composition used in forming the cured 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 (I).

M ⁵ (OR) _m (I) (where R is an alkyl group, an acyl group, or an alkoxyalkyl group, and m has the same value as the number of charges of the metal M ⁵ ).
Silicon as M ^5, titanium, zirconium, antimony,
Examples include tantalum, germanium, and aluminum. It is also possible to add an ultraviolet absorber for the purpose of further improving the weather resistance, and an antioxidant as a method for improving heat deterioration.

The cured film of the present invention can be obtained by curing a coating composition containing the components of the cured film, 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 transparent three-dimensional crosslinked resin.
0-250 ° C.

As a method for producing a cured film contained in the optical article of the present invention, a method of applying a coating composition obtained by adding a hydrophilic compound in addition to the above-mentioned components is preferably used. As the hydrophilic compound, a polar compound such as a hydroxyl group-containing compound and an amino group-containing compound is used, and the amount of the compound is preferably 0.1% by weight or more and 10% by weight or less based on the solid content of the cured film. More preferably, the content is 0.5% by weight or more and 5% by weight or less. If the amount is less than this range, the effect is small, and if it exceeds this range, it is not preferable in terms of transparency and surface hardness.

Examples of the hydroxyl group-containing compound include alkylene glycol compounds such as ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, phenyl cellosolve (ethylene glycol monophenyl ether) and diethylene glycol monomethyl ether, and benzyl. Alcohols such as alcohols and aromatic alcohols such as phenethyl alcohol; and amino group-containing compounds include polar solvents such as alkanolamines such as triethanolamine and tertiary amines such as tripropylamine and tributylamine. It is preferably used in terms of dispersibility of the polymer.

As a means for applying the coating applied on the transparent three-dimensionally crosslinked resin of the present invention, commonly used coating methods such as brush coating, dip coating, roll coating, spray coating, spin coating and flow coating can be easily used. Can be used.

In applying the coating composition of the present invention, various pretreatments for improving cleaning, adhesion, water resistance, etc. are also effective means. 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,
Examples include neon, argon, freon, water vapor, ammonia, carbon monoxide, chlorine, nitric oxide, nitrogen dioxide and the like. These can be used alone or in combination of two or more. Among the above, preferred gases include those containing oxygen, and may be gases that exist in nature 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 thickness of the cured film in the present invention is preferably 0.5 μm or more and 30 μm or less from the viewpoint of maintaining the adhesive strength and hardness. Particularly preferably, it is 1.0 μm or more and 10 μm or less. Also, when applying the coating,
It is used by diluting it with various solvents for workability and film thickness control. Examples of the diluting solvent include water, alcohols, esters, ethers, halogenated hydrocarbons, dimethylformamide, dimethylsulfoxide, etc. It can be used, and if necessary, a mixed solvent can be used.

The optical article obtained by the present invention is excellent in transparency, heat resistance, light resistance, weather resistance, impact resistance, glazing, chemical resistance, optical isotropy, etc. For optical lenses such as camera lenses, video camera lenses, goggle lenses, and contact lenses, as well as various displays such as liquid crystal display substrates, liquid crystal display light guide plates, electrochromic substrates, and electroluminescent substrates. It is applied to substrate materials such as windows for front, side, rear, and roof of automobiles and aircrafts, and to optical disc substrates because of its excellent optical isotropy. In particular, when a transparent conductive film such as ITO is formed on the optical article of the present invention, its conductivity is maintained for a long time even at a high temperature, so that it can be used as a heat-resistant transparent conductive film substrate, and TN (Twist) Nema
tic) type and STN (Super TwistNema)
(tic) type liquid crystal display and the like.

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

Various properties of the optical article were measured as follows.

(A) Transparency The total light transmittance was measured using a digital SM-3 color computer (manufactured by Suga Test Instruments Co., Ltd.).

(B) Surface Resistance The surface resistance (ohm / □) was measured using a surface resistance meter MCP-TESTER FP (manufactured by Mitsubishi Yuka).

(C) Moisture / heat resistance After leaving an optical article having an inorganic thin film on its surface layer for 100 hours in a thermo-hygrostat controlled at 60 ° C./95% RH, the presence or absence of cracks in the inorganic thin film is visually judged. did. The judgment was made as follows.

：: good ×: crack generation Example 1 (1) Preparation of transparent three-dimensional cross-linked resin 26.5 g of isopropylmaleimide 18.5 g of styrene 5.0 g of azobisisobutyronitrile 0.05 g of azobisisobutyronitrile was mixed and dissolved. It was cast molded by cast polymerization. Cast polymerization was performed as follows.

The size 150 mm × 150 mm and the thickness 5 mm 2
The outer peripheral portions of the two glass plates were adhered with a soft vinyl chloride gasket, and assembled so that the distance between the two glass plates was 2 mm. The monomer mixture is poured into the assembled glass plate, and polymerized at 70 ° C. for 8 hours and at 100 ° C. for 1 hour to form a transparent casting plate (hereinafter referred to as a casting plate (I)). Obtained.

The glass transition temperature of this casting plate (I) is 18
The temperature was 0 ° C., and the total light transmittance was 90%. Furthermore, flexural modulus 398kg / mm ^2, it represents the strength 9 kg / mm ^2, were those also solvent resistance good.

(2) Preparation of Coating Composition (a) Preparation of γ-Glycidoxypropylmethyldiethoxysilane Hydrolyzate γ-glycidoxypropylmethyldiethoxysilane was placed in a reactor equipped with a rotor. Charge 1 g and adjust the liquid temperature to 10
C. and 13.2 g of a 0.05 N hydrochloric acid aqueous solution was gradually added dropwise while stirring with a magnetic stirrer. After completion of the dropwise addition, the cooling was stopped to obtain a hydrolyzate of γ-glycidoxypropylmethyldiethoxysilane.

(B) Preparation of paint 59.5 g of diacetone alcohol was added to the silane hydrolyzate.
g, benzyl alcohol 29.7 g, n-propyl alcohol 178.1 g, acetylacetone 23.7 g, silicon-based surfactant 1.3 g, bisphenol A type epoxy resin (trade name Epicoat 8 manufactured by Yuka Shell Epoxy Co., Ltd.)
27) 64.0 g was added and mixed, and further, a colloidal silica sol (trade name: OSCAL-113, manufactured by Catalyst Chemical Industry Co., Ltd.)
5, 426.5 g of average particle diameter (50 μm), 8.5 g of triethanolamine, and 12.8 g of aluminum acetylacetonate were added, and the mixture was sufficiently stirred to obtain a coating composition.

(3) Preparation of plastic optical article The casting plate (I) obtained in the above (1) was added to the above (2).
The coating composition prepared in the above was dip-coated at a pulling rate of 20 cm / min, pre-cured at 100 ° C./10 min, and further heated at 150 ° C./0.5 hr to form a casting plate (I). Was provided with a cured film. The Si / C of the surface layer of the obtained cured film was measured by ESCA analysis. The Si / C was also measured by ESCA analysis on the surface layer of the cured film after cutting 0.2 μm from the surface layer. Table 1 shows the measured values.

(4) Formation of Inorganic Thin Film Using a transparent plate having a cured film provided on the casting plate (I), SiO ₂ 300 was formed on the surface by sputtering.
A transparent conductive film made of Å and 1,000 Å of ITO (mixed oxide of indium and tin) was formed.

Table 1 shows properties of the obtained optical article.

Example 2 An optical article was prepared in the same manner as in Example 1 except that triethanolamine was changed to triethylene glycol in the preparation of the coating material of Example 1. The Si / C of the surface layer of the obtained cured film was measured by ESCA analysis. The Si / C was also measured by ESCA analysis on the surface layer of the cured film after cutting 0.2 μm from the surface layer. Table 1 shows the measured values and various characteristics.

Example 3 An optical article was prepared in the same manner as in Example 1 except that the preparation of the coating composition of Example 1 was changed to the following composition. The Sb / C of the surface layer of the obtained cured film was determined by ESCA
It was determined by analysis. In addition, Sb / C was also converted to ESCA for the surface layer of the cured film after cutting 0.2 μm from the surface layer.
It was determined by analysis. Table 1 shows the measured values and various characteristics.

(1) Preparation of coating composition (a) Preparation of γ-glycidoxypropyltrimethoxysilane hydrolyzate In a reactor equipped with a rotor, 95.3 g of γ-glycidoxypropyltrimethoxysilane was added. Charge, maintain the liquid temperature at 10 ° C, and stir with a magnetic stirrer for 0.0
21.8 g of a 1N aqueous hydrochloric acid solution is gradually added dropwise. After dropping, cooling was stopped to obtain a hydrolyzate of γ-glycidoxypropyltrimethoxysilane.

(B) Preparation of paint The above silane hydrolyzate was added to 216 g of methanol, 216 g of dimethylformamide, and 0.5 part of a silicone surfactant.
g, bisphenol-A type epoxy resin, made by Yuka Shell Epoxy Co., Ltd., and 67.5 g of Epicoat 827 (trade name, manufactured by Nissan Chemical Industries, Inc., antimony sol A-2550, average). 270 g, particle size 50 mμ), triethanolamine 5.4
g and 13.5 g of aluminum acetylacetonate were added, and the mixture was sufficiently stirred to obtain a coating composition.

Comparative Example 1 An optical article was prepared in the same manner as in Example 1 except that triethanolamine was not added in the preparation of the coating material of Example 1. The Si / C of the surface layer of the obtained cured film was converted to ES
Measured by CA analysis. Further, the surface layer of the cured film after cutting 0.2 μm from the surface layer was also subjected to Si / C ES.
Measured by CA analysis. Table 1 shows the measured values and various characteristics.

[0073]

[Table 1]

[0074]

The optical article obtained by the present invention has the following effects.

1. When an inorganic thin film such as a transparent conductive film is provided on the surface, a thin film having excellent heat resistance and wet heat resistance can be obtained.

2. Excellent heat resistance.

3. High surface hardness and excellent scratch resistance.

4. Excellent transparency.

5. Excellent solvent resistance and chemical resistance.

6. Excellent durability such as light resistance and weather resistance.

Continuation of the front page (56) References JP-A-2-189316 (JP, A) JP-A-64-79208 (JP, A) JP-A-62-232415 (JP, A) JP-A-3-121108 (JP) JP-A-3-2290 (JP, A) JP-A-2-189380 (JP, A) JP-A-2-5308 (JP, A) JP-A-3-91795 (JP, A) JP 63-280790 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) G02B 1/00-1/12

Claims (9)

(57) [Claims] An organic polymer and a particulate inorganic oxide MxOy (where M represents an inorganic element, x, y)
Each represents a natural number).
m or more, the cured coatings and permeability having a thickness of no more than 30μm
In the liquid crystal display substrate provided with the bright conductive film , the M / C atomic ratio in the surface layer of the cured film is at least 2% of the M / C atomic ratio at 0.2 μm from the surface layer of the cured film. Characteristic LCD substrate . 2. The substrate for a liquid crystal display according to claim 1, wherein the inorganic oxide is silicon dioxide. 3. The substrate for a liquid crystal display according to claim 1, wherein the substrate is made of a transparent three-dimensionally crosslinked resin having a glass transition temperature of 130 ° C. or higher. 4. The transparent three-dimensional crosslinked resin comprises a monomer represented by the general formula (A) in an amount of 20% by weight or more and 98% by weight or less and a polyfunctional monomer having two or more unsaturated groups. Over 8% by weight
0% by weight or less, and the total weight ratio of the monomer represented by the general formula (A) and the polyfunctional monomer having two or more unsaturated groups is 30% by weight or more. The copolymer according to claim 3, which is a copolymer obtained by polymerizing the composition.
Substrate for liquid crystal display . Embedded image (In the formula, R3 represents a substituent selected from hydrogen and a hydrocarbon group having 1 to 20 carbon atoms. R1 and R2 represent a substituent selected from hydrogen, a methyl group and an ethyl group.) 5. The liquid crystal device according to claim 1, wherein the organic polymer is an organic silicon compound represented by the following general formula (B) or a polymer obtained from a hydrolyzate thereof.
Display substrate . R4 a R5 b SiX4-ab (B) (where R4 is an organic group having 1 to 10 carbon atoms;
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. ) 6. An organic polymer, a particulate inorganic oxide Mx Oy (where M represents an inorganic element, and x and y each represent a natural number) and a hydrophilic compound are added on a substrate in an amount of 0.1 to 10 %. 1
0% by weight of the composition to form a coating ,
Liquid crystal, characterized in Rukoto a transparent conductive film on Display
Method for manufacturing substrate for a . 7. A method of manufacturing a liquid crystal display substrate <br/> according to claim 6, wherein the hydrophilic compound is a hydroxyl group-containing compound. 8. The liquid crystal display according to claim 6, wherein the hydrophilic compound is an alkylene glycol compound.
A method for manufacturing a play substrate . 9. A coating having a thickness of not less than 0.5 μm and not more than 30 μm, wherein the M / C atomic ratio in the surface layer of the coating is 2% of the M / C atomic ratio at 0.2 μm from the surface of the coating.
10. The method according to claim 6, wherein
A method for manufacturing a substrate for a liquid crystal display .