JPS61114203A - Production of composite film having antireflecting property - Google Patents

Abstract

PURPOSE:To improve an effect for preventing a reflection, a surface hardness and a heat-resisting property of the titled film by coating a specific primer composition on a substrate and curing and then coating, and curing a specific coating composition on the obtd. coated substrate followed by forming an antireflective film composed of an inorg. substance thereon. CONSTITUTION:The primer composition composed of an acrylpolyol (hydroxyl value is 10-200, NCO/OH ratio is >=0.6) and a polyfunctional org. isocyanate. The primer composition is coated on the substrate and then is cured by thermally drying. The obtd. cured primer layer is coated and cured with a coating composition contg. an org. silicon compd. and/or its hydrate shown by the formula wherein R<1> and R<2> are each an alkyl, an alkenyl, an allyl group or a hydrocarbon residue having a halogen atom, an epoxy, an amino, a mercapto, a methacryloxy or a cyano group, R<3> is 1-8C an alkyl, an alkoxyalkyl, an acyl or a phenyl group, (a) and (b) are each 0 or 1. The antireflective film composed of the inorg. compd. is formed on the obtd. cured film.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention provides excellent abrasion resistance, abrasion resistance, secondary impact resistance, chemical resistance,
The present invention relates to a composite film having excellent antireflection properties such as hot water resistance, flexibility, #I heat resistance, light resistance, and weather resistance.

[Conventional technology]

Traditionally, plastic molded products are lightweight and impact resistant.

Eyeglass lens materials that take advantage of advantages such as ease of processing.

Windshields, show windows, and cathode ray tube front panels.

It is used in many ways, including window glass. However, it has drawbacks such as insufficient surface hardness, which makes it easily scratched, dust due to static electricity adhering to it, and the surface reflection of light rays being large, making it difficult to see images and objects clearly. Furthermore, it has disadvantages such as being easily stained by household products such as ink, cosmetics, and soy sauce, and being easily attacked by chemicals such as hair spray, hair tonic, and cologne, which limits its use. Many proposals have been made to improve these drawbacks, such as improving the resin itself and further improving it by various coatings. For example, as an improvement on the resin itself, there is a recently developed polymer of diethylene glycol bisallyl carbonate called 1, "CR-39". Although this material has improved chemical resistance, heat resistance, and 9 surface hardness compared to conventional plastics, it is insufficient for use in eyeglass lenses and windshields, and further improvements are desired. ing.

On the other hand, as a coating method, for example, Japanese Patent Publication No. 5 D-28092, 50-28446゜51-2
343.51-24368. @ Kaikai 52-152425
．． 52-152427.52-154857.53-1
No. 250 discloses improvement of surface hardness by coating a hydrolyzate of tetraorthosilicate or alkyltrialkoxysilane on a substrate. I cut it.

Special Publication Showa 4159.57-42665. Japanese Unexamined Patent Publication No. 52-11
2698 uses reactive silane compounds such as epoxy groups or methacroxy groups to improve surface hardness.

Furthermore, a method for imparting dyeability is disclosed. In addition, Special Publick No. 52-'59691, 56-18625
．． No. 57-2735 discloses a composition containing fine silica particles.

On the other hand, methods using primer coating have been attempted for substrates to which it is difficult to impart adhesion, and the prior art for such primer coating includes a method using a copolymer of two different acrylic esters (Japanese Patent Publication No. 53-4020 Public notice,
JP-A-56-161871), a primer composition comprising a silane coupling agent (JP-A-54-2842);
Publication No. 9).

[Problem that the invention seeks to solve]

One of the problems with surface modification such as improving surface hardness by coating methods is that adhesion varies greatly depending on the substrate, and often does not provide fully satisfactory performance. For this reason, measures such as changing the composition or solvent are currently being taken depending on the base material. Such measures may result in an unnecessarily large number of types of coating compositions, complicating production management, and even causing product variations.On the other hand, using two compositions or changing the solvent may not provide sufficient adhesion. There are many materials.

This is also one of the major problems with surface modification by coating. In addition, all of the methods using a primer coat or an e-pulling agent according to the prior art are
14 There are problems such as insufficient aqueous properties, resulting in decreased adhesion and further adhesion deterioration during outdoor exposure tests. In addition, the types of base materials that can be effectively used with these materials are limited.

It has not been possible to provide a versatile primer for materials such as glass, ceramics, metals, plastics, and substrates coated with various paints.

In addition, glass, ceramics, etc. have higher hardness, weather resistance, and chemical resistance than plastics, and are used in a wide variety of fields by taking advantage of these advantages.

However, these techniques have no staining properties.

It has drawbacks such as high surface reflectance, and its uses are quite limited. Although many proposals have been made regarding methods using coatings or primers similar to those described above as means for improving these drawbacks, the reality is that nothing that is fully satisfactory has been achieved.

In addition, in order to improve both the surface hardness and antireflection properties of plastics, 810. coated by vacuum evaporation.

Furthermore, a method of coating a multilayer antireflection film thereon is disclosed (Japanese Patent Laid-Open No. 115101/1983).

Furthermore (Japanese Patent Publication No. 59-48702. Japanese Patent Application Publication No. 59-783
01.4? Japanese Patent Publication No. 59-78304) discloses a method in which a polyorganosilane hard coat film or a cured epoxy resin film is applied to the surface of a plastic substrate, and then an antireflection film made of an inorganic substance is coated.

The technology disclosed in JP-A-56-113101 has high hardness and antireflection properties, but it also has poor adhesion and ITi'
This is a major problem as it reduces I thermal properties, 1T11 impact properties, IiI hydrothermal properties, and Ilj'I weatherability.

Japanese Patent Publication No. 59-48702. Although the techniques disclosed in JP-A-59-78501 and JP-A-59-78304 have anti-reflection properties, they do not adhere well to the base material, resulting in deep and thick scratches during use. It has a major drawback: it cracks, and it is also easily attacked by water, alcohol, etc.

There are major problems with hot water resistant adhesion, weather resistant adhesion, etc.

[Means for solving problems]

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have arrived at the present invention described below.

That is, the present invention.

(a) A primer composition consisting of an acrylic polyol and a polyfunctional organic isocyanate compound is applied onto the base material.

(However, acrylic polyols have an OH value of 10 or more -1,2
(2) The primer composition is cured by heating and/or drying.

(c) General formula R, Rb5i (
OR) A coating composition comprising an organosilicon compound represented by 4-ab and/or a hydrolyzate thereof is coated and cured.

(R and R are each an alkyl group, an alkenyl group, an allyl group, a halogen group, or an epoxy group.

A hydrocarbon group having an amine group, a mercapto group, a methacryloxy group, or a cyan group; R is an alkyl group having 1 to 8 carbon atoms; an alkoxyalkyl group;

Acyl group, phenyl group, a and b are o or 1
2) A method for producing a composite film, characterized in that a single-layer or multi-layer anti-reflection film made of an inorganic material is further provided thereon.

The acrylic polyol contained in the primer composition of the present invention is hydroxyethyl acrylate.

Hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, polypropylene glycol monoacrylate.

Polypropylene glycol monomethacrylate.

V It is a copolymer of (meth)acrylates having a hydroxyl group such as glyceromonomethacrylate and other unsaturated compounds. Other copolymerizable unsaturated monomers include various alkyl (meth)acrylates represented by the following general formulas.

CO, B (where A is hydrogen or methyl group, B has 1 to 12 carbon atoms)
Specific examples of such compounds include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate), 1so-butyl acrylate, 1uo
-butyl methacrylate-1-, n-butyl acrylate,
Examples include alkyl (meth)acrylates such as n-butyl methacrylate. In particular, for the purpose of improving durability such as hot water resistance, Tg of homopolymer is 37.
The following monomers are preferably used at 5°.

Furthermore, organic carboxylic acids having unsaturated groups such as acrylic acid, methacrylic acid, and itaconic acid.

2-Hydroxyethyl acryloyl phosphate.

Examples include vinyl compounds having aromatic substituents such as 2-hydroxyethyl methacryloyl phosphate, styrene, chlorostyrene, and ethylstyrene.

In the acrylic polyol, not only one type of (meth)acrylate having an OH group but also two or more types can be used. Furthermore, as for other monomers that are copolymerizable components with the monomer having an OH group, it is also possible to use not only one type but also two or more types. Furthermore, using an acid component such as acrylic acid or methacrylic acid as a copolymerization component in the above monomers is effective for the reaction between the OH group in the acrylic polyol and isocyanate, and the amount of copolymerization is preferably The amount is 0.1 to 5 parts by weight, more preferably 0.2 to 6 parts by weight.

Acrylic polyols can be produced by known methods9 and are usually produced using an azo compound such as azobisisobutyronitrile or a peroxide compound such as penzoylno(-oxide) as a polymerization initiator. A dropwise solution polymerization method in which a monomer and an initiator are dropped into a solvent such as toluene, xylene, butyl acetate, or ethyl acetate is preferably used.Furthermore, a solution consisting of a monomer and an initiator is poured into an ampoule or between a casting plate. It is also fully possible to use the polymer by dissolving it in a suitable solvent after obtaining it by a cast polymerization method in which the resin is sandwiched and polymerized by heating.

The molecular weight of the acrylic polyol of the present invention is not particularly limited, but the average molecular weight is determined from the viewpoints of ease of preparing the primer composition, stability of the paint, wettability during coating, amount of unreacted residue after heat curing, etc. 2000-10
00,000, more preferably 6,000 to 100,000.

Furthermore, the OH value contained in the acrylic polyol of the present invention is 1
It is 0-200, more preferably 20-100. That is, if the OH value is smaller than this, crosslinking will not proceed sufficiently, resulting in poor solvent resistance.

Problems arise with adhesion. Moreover, if it is larger than this, there are problems with water resistance, weather resistance, etc.

The OH value of the acrylic polyol is defined below.

Add 5 ml of the following acetylation reagent to 1 g of sample.

Heat at 95-100°0 for 1 hour. Then 1ml of water
Add and shake well. Heat for an additional 10 minutes, allow to cool, and wash with 5 ml of ethyl alcohol. Thereafter, the phenolphthalein solution is used as an indicator for titration with N/2 potassium hydroxide ethyl alcohol solution. The number of mg of potassium hydroxide required at this time is called the OH value.

Acetylating agent: 25 g of acetic anhydride in 100 volumetric flasks
ml, add pyridine to make the total volume 100ml,
Shake the solution thoroughly.

The other component contained in the primer composition of the present invention, a polyfunctional organic isocyanate compound, is a compound having two or more isocyanate groups in one molecule, which reacts with the acrylic polyol and is compatible with various substrates. It forms strong adhesive properties.

Such polyfunctional organic incyanates are not particularly limited to these, but preferably N00% is 2% to 7%.
Preferably used are organic compounds having two or more incyanate groups in one molecule. Here N00%
is the NGO content expressed by the following formula.

However, the number of Neo functional groups in Niokki means the number of NGO groups contained in the 84 molecules.

Specific examples of polyfunctional organic isocyanates include the following.

a As a diisocyanate.

Hexamethylene diisocyanate.

Inphoron di incyanate.

2,2.4-) Limethylhexamethylene diincyanate.

Dicyclohexylmethane diisocyanate.

Lysine diisocyanate methyl ester.

Xylylene diisocyanate.

Bis(incyanatomethyl)cyclohexane.

Tolylene diisocyanate.

4.47-Cyphenylmethane diisocyanate.

Hydrogenated xylylene diisocyanate is an example of polyfunctional incyanate having six or more functional groups.

Biuret conjugate of hexamethylene diisocyanate,
Or incyanurate conjugate.

A reaction adduct of hexamethylene diisocyanate and trimethylolpropane.

2-incyanate ethyl-2,6-cyincyanate hexanoate.

1,6.11-Undecane triincyanate.

A reaction adduct of isophorone diisocyanate and trimethylolpropane.

A reaction adduct of xylylene diisocyanate and trimethylolpropane.

There is a reaction adduct of bis(incyanatomethyl)cyclohexane and trimethylolpropane.

Among the above isocyanate compounds, particularly preferred are hexamethylene diisocyanate, a biuret-forming reaction product of hexamethylene diisocyanate, and hydrogenated xylylene diisocyanate.

The thermosetting acrylic urethane polymer, which is the primer composition of the present invention, is made of the above-mentioned acrylic polyol and a metal material having a bifunctional or higher isocyanate group, and contains OH contained in the acrylic polyol and a compound having an incyanate group. The ratio of NGOs included in (
N COlo H ratio) is 06 or higher.

More preferably, it is used in a range of 0.8 to 20.

In other words, if it is smaller than this, crosslinking will be insufficient,
As a result, lTl4 water resistant, II chemical resistant, sweat resistant.

Problems arise with weather resistance, etc. Furthermore, problems such as whitening occur when the coating composition is applied onto the primer layer.

On the other hand, although there is no performance problem no matter how large the NC010H ratio is, it is preferably 20 or less from the viewpoint of safety and health. The primer composition used in the present invention is usually dissolved in an organic solvent before use. Although the type of solvent is not particularly limited, an aprotic solvent having a boiling point of 180° C. or lower is preferably used in view of the pot life of the primer and the ease of curing and drying. However, from the viewpoint of coating workability, it is of course possible to use a solvent with a higher boiling point in combination. Specific examples of preferably used solvents include aromatic (halokenated) hydrocarbons such as benzene, chlorobenzene, toluene, and xylene, acetone,
Methyl ethyl ketone.

Ketones such as methyl isobutyl ketone, formic acid fk,
Esters such as ethyl acetate and butyl acetate.

Cyclic ethers such as tetrahydrofuran and dioxane, diethylene glycol dimethyl ether.

Aliphatic ethers such as ethyl ether, hydrocarbons such as hexane, heptane, petroleum ether, cyclohexane, chloroform, dichloroethane.

Examples include halogenated hydrocarbons such as trichloroethane, trichlorethylene, and tetrachloroethane, acetonitrile, dimethylformamide, and carbon tetrachloride. These solvents can be used not only alone, but also as a mixture of two or more.

It is also possible to add various tertiary amine compounds, quaternary ammonium salts, and curing catalysts such as dibutyltin dilaurate to the primer composition of the present invention for the purpose of accelerating curing or low-temperature curing.

The solid content of the primer composition of the present invention or the thickness of the brimer layer may be any value as long as it achieves the objectives of the present invention, but the smoothness of the primer layer, the maintenance of adhesive strength,
From the viewpoints of II water-based, weather-resistant 9 surface hardness, etc., it is preferably applied between 0.01 micron and 20 micron.

The primer composition is applied to various substrates and then cured by heating and/or drying.

Heating or drying conditions should be determined based on productivity, the coating composition applied to the primer layer, coating conditions, etc., but preferably applied conditions include a temperature range from room temperature to 150°C. 1 minute to 2
The duration is 40 minutes. Especially when considering problems such as dust adhesion, the temperature is 40°0 to 120°0 for 5 minutes to 120°.
The preferred condition is 1 minute. If the primer layer is not cured, the primer layer will dissolve when the coating composition is applied onto the primer layer.

Not only does it not exhibit a sufficient adhesive effect, but it also causes problems such as whitening of the paint film.

The present invention provides a compound of the general formula RR5 on the cured primer layer.
Organosiliconization a b represented by i(OR)
It is obtained by coating and curing a coating composition comprising a 4-ab metal object and/or a hydrolyzate thereof.

(R and R are each an alkyl group, an alkenyl group, an allyl group, or a halogen group having a carbon number of 1 to 12, an epoxy group, a glycidoxy group, an amino group, a mercapto group,
a hydrocarbon group having a methacryloxy group or a cyano group; R is an alkyl group, an alkoxyalkyl group, or an acyl group having 1 to 8 carbon atoms; a and b are 0 or 1; ) Specific representative examples of these organosilicon compounds include methyl silicate and ethyl silicate.

n-propyl silicate, 1-propyl silicate, n
-butyl silicate), 5ea-butyl silicate, and t-butyl silicate, and their hydrolysates, as well as methyltrimethoxysilane, methyltriethoxysilane, and methyltrimethoxyethoxysilane.

Methyltriacetoxysilane, methyltriptoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane.

Vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane.

Phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltriacetoxysilane, 3,3.5-)lifluoroprobyltri Methoxysilane, γ-methacryloxyglobiltrimethoxysilane,
γ-Aminepropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptogropyltriethoxysilane, N-β(aminoethyl)-γ-aminopropyltrimethoxysilane, β -cyanoethyltriethoxysilane, methyltriphenoxysilane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane,
Glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, β-glycidoxyethyltrimethoxysilane, β-glycid xyethyltriethoxysilane, α-glycidoxyprobyltrimethoxysilane, α-glycidoxyglobiltriethoxysilane, β-glycidoxyglobiltrimethoxysilane, β-glycidoxyprobyltriethoxysilane, γ- Glycidoxyglopyltrimethoxysilane, γ-glycidoxyprobyltriethoxysilane, γ-glycidoxybrobyl triglopoxysilane, γ-glycidoxypropyl tributoxysilane, γ
- glycidoxypropyltrimethoxyethoxysilane,
γ-glycidoxypropyltrifenoxysilane, α-
Glycidoxybutyltrimethoxysilane, a-glycidoxybutyltriethoxysilane, β-glycidoxybutyltrimethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ- Glycidoxybutyltriethoxysilane, δ
-glycidoxybutyltrimethoxy one 1- silane, δ-glycidoxybutyltriethoxysilane,
(3,4-epoxycyclohexyl)methyltrimethoxysilane, (3,4-epoxycyclohexyl)methyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl) ) Ethyltriethoxysilane, β
-(!1.4-Epoxycyclohexyl)ethyltripropoxysilane.

β-(3,4-epoxycyclohexyl)ethyltributoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxyethoxysilane.

β-(ro,4-epoxycyclohexyl)ethyltriphenoxysilane, γ-(6,4-epoxycyclohexyl)propyltrimethoxysilane, T-(ro,4-epoxycyclohexyl)propyltriethoxysilane, β
-(6,4-epoxycyclohexyl)butyltrimethoxysilane, β-(3,4-epoxycyclohexyl)
Trialkoxysilanes such as butyltriethoxysilane, triazyloxysilane or triphenoxysilanes or their hydrolyzed polymers and dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyljethoxysilane, phenylmethyljethoxysilane, γ-chloropropyl Methyldimethoxysilane, γ-chloropropylmethyljethoxysilane.

Dimethyldiacetoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyljethoxysilane.

γ-Mercaptopropylmethyldimethoxysilane.

γ-Mercaptoglobil methyldiethoxysilane.

γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyljethoxysilane, methylvinyldimethoxysilane, methylvinyljethoxysilane, glycidoxymethylmethyldimethoxysilane, glycidoxymethylmethyljethoxysilane, α-glycidoxy Ethylmethyldimethoxysilane, α-glycidoxyethylmethyljethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylmethyljethoxysilane, α-glycidoxyglovylmethyldimethoxysilane, α-glycidoxyethylmethyldimethoxysilane, Sidoxypropylmethyljethoxysilane, β-glycidoxypromepylmethyldiquitoxysilane, β-glycidoxypropylmethyljethoxysilane, γ-glycidoxyglovylmethyldimethoxysilane, γ-glycidoxypropylmethyl Jetoxysilane, γ-glycidoxypropylmethyldibroboxysilane.

γ-Glycidoxyglobylmethyldibutoxysilane, γ
-glycidoxypropylmethyldimethoxyethoxysilane, γ-glycidoxyglopylmethyldiphenoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxyglopylethyldiethoxysilane,
γ-glycidoxyglobylethyldipropoxysilane,
γ-glycidoxypropylbinyldimethoxysilane, γ
- Glycidoxyglopyruvinyljethoxysilane.

γ-glycidoxyglobylphenyldimethoxysilane,
γ-glycidoxyglobylphenyldiethoxysilane,
Examples include dialkoxysilanes, diacyloxysilanes, and hydrolysates thereof.

It is also possible to add one or more types of these organosilicon compounds. Particularly for the purpose of imparting dyeability, it is preferable to use organosilicon compounds containing epoxy groups.

These organosilicon compounds lower the curing temperature.

In order to further progress the curing, it is preferable to use it after hydrolysis.

Hydrolysis is produced by adding pure water or an acidic aqueous solution such as hydrochloric acid, acetic acid, or sulfuric acid and stirring. Furthermore, the degree of hydrolysis can be easily controlled by adjusting the amount of pure water or acidic aqueous solution added. During hydrolysis, it is particularly preferable to add pure water or acidic aqueous solution in an amount equal to or more than 6 times the mole of the alkoxy group, but not more than 6 times the mole, from the viewpoint of accelerating curing.

During hydrolysis, alcohol and other substances are produced, so it is possible to hydrolyze without a solvent, but in order to make the hydrolysis more uniform, it is preferable to mix the organosilicon compound and a solvent before hydrolysis. is also possible. Further, depending on the purpose, it is possible to use the alcohol after hydrolysis after being appropriately removed by heating and/or under reduced pressure, and it is also possible to add an appropriate solvent after that.

Examples of these solvents include alcohols, esters, ethers, ketones, halogenated hydrocarbons, and aromatic hydrocarbons such as toluene and xylene. Moreover, these solvents can also be used as a mixed solvent of two or more types as required. Furthermore, depending on the purpose, it is possible to accelerate the hydrolysis reaction and further advance reactions such as precondensation by heating above room temperature, or to suppress precondensation, the hydrolysis temperature can be lowered to below room temperature. However, this can be achieved only by heating and/or drying the raw composition, irradiating it with ultraviolet rays or irradiating it with an electron beam.

Various curing agents can be used in combination for the purpose of accelerating curing and enabling low-temperature curing. As the curing agent, various epoxy resin curing agents or various organosilicon resin curing agents are used.

Specific examples of these curing agents include various organic acids and their acid anhydrides, nitrogen-containing organic compounds, various metal complex compounds, and metal alkoxides.

Further examples include various salts such as organic carboxylates and carbonates of alkali metals. It is also possible to use a mixture of two or more of these curing agents. Among these curing agents, the aluminum chelate compounds shown below are particularly useful for the purpose of the present invention from the viewpoints of stability of the coating material, coloring of the coating film after coating, and the like.

What is the aluminum chelate compound mentioned here?

The general formula Al: (Y)
It is a n 5 yant compound.

and n is 0, 1 or 2.

The general formula AIX is particularly useful as a curing agent in the present invention!
As the aluminum chelate compound nR-n, various compounds can be mentioned, but aluminum acetylacetonate is particularly preferable from the viewpoint of solubility in a composition, stability, effect as a curing catalyst, etc. , aluminum bisethyl acetoacetate monoacetylacetonate, aluminum di-n-butoxide
Monoethyl acetoacetate, aluminum chelate 1s
o-propoxide-monomethylacetoacetate and the like.

It is also possible to use a mixture of two or more of these.

It is also possible to use various surfactants in the coating composition of the present invention for the purpose of improving the flow during application, improving the smoothness of the coating film, and lowering the coefficient of friction on the coating film surface. Yes, especially block or graft copolymers of dimethylsiloxane and alkylene oxide,
Furthermore, fluorine-based surfactants are also effective. In addition, dyes and pigments and fillers can be dispersed, organic polymers can be dissolved, and paint films can be colored, coating properties, adhesion to substrates, etc.
It is also easily possible to improve its practicality as a coating agent, such as by improving its physical properties.

Furthermore, it is easily possible to add an ultraviolet absorber for the purpose of improving weather resistance, and an antioxidant to improve side heat deterioration.

Furthermore, various inorganic oxides can be added for the purpose of further improving surface hardness, improving antistatic properties, improving the refractive index of the coating film, and improving fFI weatherability. Silica sol, which is a colloidal dispersion of high molecular weight silicic anhydride in an organic solvent such as water and/or alcohol, is preferably used. In particular, it is preferably added in an amount of 5 to 65 weight percent to improve adhesion to the antireflection film.

The coating composition of the present invention is mainly cured by heat treatment, but the heating temperature can be used in a much wider range than in the case of conventional thermosetting resin compositions, and a temperature of 50 to 250°C is sufficiently favorable. Get results.

The object to be coated to which the present invention is applied is as follows.

Any material may be used if the purpose of the present invention is required, but 1. Glass, thermosetting resins, and thermoplastic resins that are difficult to provide adhesive properties are particularly effective from the viewpoint of providing strong attachment properties. give.

The above plastic materials include polymethyl methacrylate and its copolymers, polycarbonate, diethylene glycol bisallyl carbonate (CR-39),
Polyesters, especially polyethylene terephthalate, and unsaturated polyesters.

Acrylonitrile (halogenated) styrene copolymer, vinyl chloride, polyurethane, epoxy resin.

Preferred are di(meth)acrylate polymers of (halogenated) bisphenol A and copolymers thereof, urethane-modified di(meth)acrylate polymers of (halogenated) bisphenol A, and copolymers thereof. Among these, it is effective for thermosetting resins and is particularly preferably used for halogen-containing organic polymers that have poor weather resistance.

It can also be preferably used for glass.

As means for applying the primer composition of the present invention and the coating composition to be applied onto the primer layer, commonly used coating methods such as brush coating, dip coating, roll coating, spray coating, and flow coating can be easily used. .

When applying the primer of the present invention, various chemical treatments or physical treatments can be performed for the purpose of further improving wettability and adhesion to the substrate.

In particular, plasma treatment using oxygen gas is effective as a pretreatment for various plastics.

Further, the means for applying the primer composition and the coating composition may be the same or may be different.

Substances for forming a single-layer or multi-layer antireflection film by coating and curing an organic polysiloxane composition on the above-mentioned primer are 9 essentially inorganic substances with high hardness, such as metals, metals, etc. Alternatively, semimetal oxides, fluorides, silicides, borides, carbides, nitrides, sulfides, etc. are selected.

Examples include ytterbium. As fluoride,
Examples include MgP, etc. Si as a metal nitride
, N, etc.

A method for forming a single-layer or multi-layer anti-reflection film made of the above-mentioned substances is a vacuum evaporation method.

Examples include sputtering method, ion blating method, and ion beam assist method. Also.

In order to further improve the adhesion between the coating composition and the antireflective film, various methods (corona discharge, direct current under reduced pressure,
Surface treatments using low frequency, high frequency, or high voltage discharge using microwaves are effective.

In particular, treatment with low-temperature plasma obtained by high-frequency discharge under reduced pressure is preferably used from the viewpoint of reproducibility and productivity. Surface treatment using these activated gases or ionized gases is vacuum evaporation.

It is advantageous to perform ion blating and the like in the same chamber to improve adhesion.

Since the composite film obtained by the present invention has a high hardness surface with secondary properties in addition to antireflection properties, it can be preferably used not only for corrective lenses but also for lenses of cameras and binoculars, as well as front panels of various displays. .

In order to clarify the gist of the present invention, Examples are given below.
The present invention is not limited to these examples. Note that the number of copies and numbers in the examples are based on weight.

Examples 1-5. Comparative Example 1 (1) Preparation of primer composition Xylene/butyl acetate (50150 weight ratio) of a quaternary copolymer (OH value = 50) consisting of styrene/phthyl acrylate/hydroxyethyl methacrylate/acrylic acid
5 (biuret conjugate of 11% solution and hexamethylene diisocyanate (NGO content = 4: 16.5%)
were added in the NC0ZOH ratio shown in Table 1, respectively, and methyl isobutyl ketone/ethyl acetate (50,750 weight ratio) was added.
A primer composition was obtained by diluting the solid content to 10% with a solvent.

(2) Applying and curing the primer composition (1)
), hexamethylene diisocyanate was added to 1 mole of the hydroxyl group-containing compound obtained by bonding 1 mole of acrylic acid to 2 moles of ethylene oxide adduct of tetrabromobisphenol A by esterification.
70 parts of a monomer containing a polyfunctional acrylate monomer and 60 parts of styrene were cast-polymerized using isopropyl peroxide as a polymerization initiator, and the surface was further treated with oxygen plasma using the immersion method (pulling speed I).
Coating was performed at C1s+/min). The coated board is 9
It was heated and cured at 6°0 for 1 hour.

(3) Preparation of coating composition (a) Preparation of silane hydrolyzate γ-glycidoxypropylmethyljethoxysilane 10
Cool 6.8 g to 10°0 while stirring.

155 g of 005 normal hydrochloric acid aqueous solution was gradually added dropwise.

After the dropwise addition was completed, stirring was continued for an additional hour at room temperature to obtain a silane hydrolyzate.

(b) Preparation of coating composition - Filter 4 - To the silane hydrolyzate, 50 g of epoxy resin ("Epicoat 827", manufactured by Shell Chemical Co., Ltd.), 59 g of diacetone alcohol, and 29.5 g of benzene alcohol were added.
g, acetylacetone 23.3 g, and silicone surfactant 158 g were added and mixed, and methanol-dispersed colloidal silica (average particle diameter 12±1 mμ, solid content 3
0%) and 12.5 g of aluminum acetylacetonate) were added.

After thorough stirring, a coating composition was prepared.

(4) Coating and Curing The coating composition obtained in (2) above was coated onto the base material coated and cured in the same manner as the primer composition using the coating composition described above. After coating, it was heated and cured at 93°0 for 4 hours to obtain a composite film.

(5) Preparation of anti-reflection film A mixture of inorganic substances ZrO,/SiOs, Z
rO,.

S】0. were coated in multiple layers in this order using a vacuum evaporation method, with the optical film thickness set to λ/4 (λ is the wavelength in the visible range).

The reflection interference color of the obtained composite film was green, and the total light transmittance was 98 cm.

(6) Test Results The performance of the substrate having the obtained composite membrane was tested according to the following method. The results are shown in Table 1.

(A) Steel wool hardness Rub the painted surface with 4oooo steel wool.

Assess the degree of injury. What are the criteria?

A...It won't get scratched even if it is rubbed strongly.

B... If you rub it quite strongly, it will get a little scratched.

C: Even weak friction causes damage.

D: Easily scratched with nails.

(B) On the coating surface of the adhesive base material, use a steel knife to make 100 10-square goblets that reach the substrate.

Cellophane adhesive tape (trade name: "Cellotape", manufactured by Nichiban Co., Ltd.) was strongly applied and rapidly peeled off in a 90 degree direction to examine whether or not the paint film had peeled off.

(C) Appearance The substrate having the obtained composite film was visually observed for transparency and degree of coloration.

(D) 1T11 Hydrothermal After immersion in hot water at 80°C for 2 hours, an adhesion test was conducted in the same manner as in (B) above.

When the base material having the obtained composite film was subjected to an outdoor exposure test, it had good adhesion even after one month. Further, even when left in an oven at 80°0 for 2 hours, no change was observed and it had excellent heat resistance. In this example, the anti-reflective film was similarly formed after dyeing with a disperse dye bath consisting of six colors of red, blue, and yellow before forming the anti-reflective film.

The test results showed that the steel hardness was B, and the adhesion, heat resistance, and hot water resistance were all good. Furthermore, when an outdoor exposure test was conducted, good adhesion was observed even after one month.

A similar test was conducted in Example 1 without applying the primer composition, and the steel wool hardness was B, indicating good adhesion.

Although both heat resistance and lit hydrothermal resistance were good, poor adhesion occurred during a one week outdoor exposure test.

Example 4 The same procedure as in Example 1 was carried out except that the polyfunctional isocyanate in the primer composition was changed. Incyanates used are shown in Table 2.

The test results are shown in Table 2.

Example 5 The same procedure as in Example 1 was carried out except that the acrylic polyol in the primer composition was changed. The OH values of the acrylic polyols used are shown in Table 6. The test results are shown in Table 6.

Comparative Example 2 The same procedure as in Example 1 was carried out except that the primer composition and coating composition were not applied.

The total light transmittance of the obtained composite film was 98%, but the reflection interference color was reddish-purple.

The test results showed that the steel wool hardness was C and the adhesion was poor. Note that the hot water resistance was poor with cracks occurring on the entire surface of the antireflection film.

Table 1 Table 2 [Effects of the Invention] The composite film having the antireflection film obtained by the present invention has the following effects.

(1) It has a high antireflection effect.

(2) A composite film with good adhesion and high surface hardness can be obtained.

(3) Excellent heat resistance, #4 hydrothermal resistance, secondary impact resistance, light resistance, and weather resistance.

Claims (1)

[Claims] (a) A primer composition consisting of an acrylic polyol and a polyfunctional organic isocyanate compound is applied onto a substrate, (however, the acrylic polyol has an OH value of 10 or more, 20
0 or less, and the NCO/OH ratio is 0.6 or more) (b) The primer composition is cured by heating and/or drying, and (c) the general formula R^1_aR^ is formed on the cured primer layer. 2_bSi(OR^3)_4_-_a_
A coating composition consisting of an organosilicon compound and/or its hydrolyzate represented by −_b is coated and cured, (where R^1 and R^2 are each an alkyl group, an alkenyl group, an allyl group, or a halogen group, A hydrocarbon group having an epoxy group, a glycidoxy group, an amino group, a mercapto group, a methacryloxy group or a cyano group, R^3 is an alkyl group having 1 to 8 carbon atoms, an alkoxyalkyl group, an acyl group, a phenyl group, (a and b are 0 or 1) (d) A method for producing a composite film, characterized in that a single-layer or multi-layer antireflection film made of an inorganic substance is further provided thereon.