JPS61103966A - Production of composite film - Google Patents

Abstract

PURPOSE:A base material is coated with a specific primer composition, cured, then coated thereon with a special coating composition to give a composite film having good scorching resistance, hydrothermal resistance, and further good dyeability and high adhesion. CONSTITUTION:The base material is coated with (A) a primer composition which is obtained using (i) an acrylic polyol which contains (meth)acrylate units of the formula (R is H, methyl; X is 1-12C hydrocarbon) and has a Tg lower than 375 deg.C and has a hydroxyl value of 10-20 and (ii) a polyfunctional organic isocyanate so that the NCO/OH ratio becomes more than 0.6 and cured by heating and/or drying. Then, the coated base material is coated, on the cured primer layer, with (B) a coating composition of an organosilicon compound of the formula R<1>aR<2>bSi(OR<3>)4-a-b (R<1>, R<2> are alkyl, allyl; R<3> is 1-8C alkyl, acyl) and/or its hydrolyzate and cured to give the objective composite coating films.

Description

[Detailed Description of the Invention] [Industrial Field of Application] The present invention provides abrasion resistance, abrasion resistance, impact resistance, chemical resistance,
This invention relates to a method for producing a composite film with excellent hot water resistance, flexibility, heat resistance, dyeability, weather resistance, light resistance, etc.

[Prior Art] Conventionally, plastic molded products have been used in a wide range of applications, such as eyeglass materials, windshields, show windows, cathode ray tube front panels, and window glasses, due to their advantages such as light weight, impact resistance, and ease of processing. There is. However, it is easily scratched due to insufficient surface hardness. There are drawbacks such as the tendency for dust to adhere due to static electricity. 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 tonics, and cologne, and its uses are quite limited. Many proposals have been made for improving the resin itself, as well as improvements using various coatings, as means to improve these defects. For example, as an improvement of the resin itself, a recently developed polymer of diethylene glycol bisallyl carbonate, 'CR-
There is a 39”.

Although this material has significantly improved chemical resistance, heat resistance, and surface hardness compared to conventional plastics, it is insufficient for use in eyeglass lenses and windshield glass, and further improvements are desired. ing.

On the other hand, as a coating method, for example,
43.51-24368, JP-A-52-152425.
52-152427.52-154837.53-12
No. 30 discloses improvement in surface hardness by coating a substrate with a hydrolyzate of tetraorthosilicate or alkyltrialkoxysilane. Furthermore, Japanese Patent Publication No. 53-15743.56-28930 discloses a method of improving surface hardness and imparting dyeability by using a reactive silane compound such as a silane group. Also, Special Publication No. 52-39691.

No. 56-18625.57-2735 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 prior art techniques for such primer coating include methods using copolymers of various acrylic esters (Japanese Patent Publication No. 53-4020 Public notice,
JP-A-56-161871), Brimer Imer composition comprising a silane coupling agent (JP-A-54-284)
Publication No. 29).

[Problems to be Solved by the Invention] One of the problems in surface modification, such as improving surface hardness, by coating methods is that adhesion varies greatly depending on the substrate, and often does not provide sufficiently 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 unnecessarily increase the variety of coating compositions, complicate production management, and even cause product variations. On the other hand, there are many substrates for which sufficient adhesion cannot be imparted by changing the composition or solvent, and this is also one of the major problems in surface modification by coating.

In addition, the conventional methods using a brimer coat or a coupling agent have problems such as insufficient water resistance, reduced adhesion, and deterioration of adhesion during outdoor exposure tests. In addition, the types of base materials that can be effectively used with these are limited, and it is important to provide a versatile primer for materials such as glass, ceramics, metals, plastics, and base materials coated with various paints. have not been successful.

Additionally, glass, ceramics, etc. have higher hardness, weather resistance, and chemical resistance than plastics, and take advantage of these advantages to be used in a wide variety of fields.

However, it has drawbacks such as no dyeing property and 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.

[Means for Solving the Problems] As a result of intensive studies to solve the first problem, the present inventors have arrived at the present invention described below.

That is, the present invention provides: (1) a brimer comprising an acrylic polyol and a polyfunctional organic isocyanate compound containing at least one type of acrylate or methacrylate represented by the general formula CH2=C02X having a TO of 375°K or less in a homopolymer on a base material; Apply the composition (where R is H or CH3, and X has 1 to 1 carbon atoms).
12 hydrocarbon groups, and even OH of acrylic polyol
The value is 10 or more and 200 or less, and the NC010H ratio is 0.6
(Here, R
1 and R2 are each an alkyl group, an alkenyl group, an allyl group,
or a hydrocarbon group having a halogen group, an epoxy group, an Amim L mercapto group, a methacryloxy group, or a cyano group, R3 is an alkyl group having 1 to 8 carbon atoms, an alkoxyalkyl group, an acyl group, a phenyl group, and a and b
is O or 1).

The acrylic polyols contained in the brimer composition of the present invention include droxyethyl acrylate, hydroxyethyl methacrylate, human oxypropyl acrylate, hydroxypropyl methacrylate, polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, polypropylene glycol monoacrylate, polyethylene glycol Tg in (meth)acrylates and homopolymers having hydroxyl groups such as monomethacrylate and glycerol monomethacrylate
It is a copolymer containing at least one type of acrylate or methacrylate represented by the general formula % where the temperature is 375°K or less. Here, R is H or CH3, and X is a hydrocarbon group having 1 to 12 carbon atoms. Specific examples of such acrylic monomers include methyl acrylate, ethyl acrylate, ethyl methacrylate, and is.

-butyl acrylate, 1so-butyl methacrylate, n-butyl acrylate, n-butyl methacrylate, lauryl methacrylate, and phenyl (meth)acrylates. Furthermore, other copolymerizable monomers include (meth)acrylic compounds having acidic groups such as acrylic acid, methacrylic acid, 2-hydroxyethyl acryloyl phosphate, 2-hydroxyethyl methacryloyl phosphate, and itaconic acid, or styrene and chloride. Examples include aromatic vinyl compounds such as styrene and ethylstyrene. It is quite possible to use one or more of these in addition.

Note that the use of acrylate and/or methacrylate whose general formula in the homopolymer has To exceeding 3756 K and which is represented by CH2-C O2X, such as methyl methacrylate, etc., as a copolymerization component may reduce hot water resistance. This causes problems such as poor adhesion.

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 which are copolymerizable components with the hexamer having OHM, it is also possible to use not only one type but also two or more types. Furthermore, among the above monomers, acrylic acid or methacrylic acid,
It is effective to use an acid component such as 2- and do-Oxyethyl methacrylic acid component as a copolymerization component for the reaction between the OH group in the acrylic polyol and the isocyanate, and the copolymerization ω is 0.1 to The amount is 5 parts by weight, more preferably 0.2 to 3 parts by weight.

On the other hand, acrylic polyols consisting solely of (meth)acrylic monomers having hydroxyl groups have poor water resistance and have the problem of peeling of the film or reduction of hardness when immersed in hot water.

Acrylic polyols can be produced by known methods, and are usually produced using an azo compound such as azobisisobutyronitrile or a peroxide compound such as benzoyl peroxide as a polymerization initiator.

As the polymerization method, a dropping 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. It is also fully possible to obtain the solution by a cast polymerization method in which a solution consisting of a monomer and an initiator is sandwiched between ampoules or casting plates and polymerized by heating, and then used by dissolving it in a suitable solvent.

The molecular weight of the acrylic polyol of the present invention is not particularly limited, but the average molecular weight is 2000~10
00,000, more preferably 3,000 to 100,000.

In addition, the 08 valence 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 lower than this, crosslinking will not proceed sufficiently, causing problems in solvent resistance and adhesiveness. 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 mα of the following acetylation reagent to 1 g of sample, and
Heat at 100°C for 1 hour. Then, add 1 mα of water and shake well. Roughly heat for 10 minutes, allow to cool, and then wash with 5 ml of ethyl alcohol.

Then, using phenolphthalein solution as an indicator, N/
Titrate with potassium dihydroxide ethyl alcohol solution. The number of mg of potassium hydroxide required at this time is called the OH value.

Acetylating agent: 25Q acetic anhydride in a 100m volumetric flask
Add pyridine to make the total volume 100 mα, and shake thoroughly.

The polyfunctional organic isocyanate compound, which is the other component contained in the brimer composition of the present invention, is a compound having two or more isocyanate groups in one molecule, which reacts with the acrylic polyol and is compatible with various base materials. Specific examples of adhesives that form strong adhesive properties include the following.

Examples of diisocyanates include hexamethylene diisocyanate, isophorone diisocyanate, 2.2.4-trimethylhexyl diisocyanate, dicyclohexylmethane diisocyanate, lysine diisocyanate methyl ester, xylylene diisocyanate, bis(isocyanatomethyl)cyclohexane, tolylene diisocyanate, 4.4 '-diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, and trifunctional or higher polyfunctional isocyanates include biuret conjugate of hexamethylene diisocyanate,
Or an isocyanurate conjugate, a reaction adduct of hexamethylene diisocyanate and trimethylolpropane, 2-isocyanatoethyl-2,6-ditucyanatehexanoate, 1.6.11-undecane triisocyanate, isophorone diisocyanate and trimethylol There is a reaction adduct with propane, a reaction adduct with xylylene diisocyanate and trimethylolpropane, and a reaction adduct with bis(isocyanatomethyl)cyclohexane and trimethylolpropane.

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

The thermosetting acrylic urethane polymer that is the primer composition of the present invention is composed of the acrylic polyol and a compound having a difunctional or higher isocyanate group, and the OH contained in the acrylic polyol and the compound having an isocyanate group are contained in the acrylic polyol. The ratio of NGOs contained in (NGO10H ratio) is 0.6 to 1 or more, more preferably 0.8 to 2ON.

In other words, if it is smaller than this, crosslinking will be insufficient,
As a result, problems arise in water resistance, chemical resistance, sweat resistance, 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 NGO10H 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 with a boiling point of 180° C. or lower is preferably used from the viewpoint of primer pot life and 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 (halogenated) hydrocarbons such as benzene, chlorobenzene, toluene, and xylene, acetone,
Ketones such as methyl ethyl ketone and methyl isobutyl ketone, esters such as ethyl formate, 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, and cyclohexane;
halogenated hydrocarbons, acetate, such as trichlorethylene and tetrachloroethane.

Examples include nitrile, 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 curing catalysts such as various tertiary amine compounds and quaternary ammonium salts to 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 primer layer may be any value as long as it achieves the object of the present invention, but the smoothness of the primer layer, the maintenance of adhesive strength,
From the viewpoint of water resistance, weather resistance, surface hardening, etc., the thickness is preferably applied between 0.01 micron and 20 micron.

The primer composition is applied to various types of long materials and then cured by heating and/or drying.

Heating or drying conditions should be determined based on productivity, the coating composition to be applied on one layer of primer, and application conditions, but preferably applied conditions are air temperature to 150°C, 1. minutes to 240
It is a minute. In particular, when considering problems such as dust adhesion, preferably the temperature is 40° C. to 120° C. for 5 minutes to 120 minutes. If the primer layer is not cured, the primer layer will be eluted during application of the coating composition applied on the primer layer, and not only will sufficient adhesive curing not be achieved, but problems such as whitening of the coating film will occur.

The present invention provides general 1
2.

Organic arrow represented by the formula RRS+(OR3)
It is obtained by coating and curing a coating composition consisting of a Tokuichi silicon compound and/or its hydrolyzate. (Here, R1 and R2 are each an alkyl group, an alkenyl group, an allyl group, or a hydrocarbon group having a halogen group, an epoxy group, an amino group, a mercapto group, a methacryloxy group, or a cyano group, and R3 has 1 to 1 carbon atoms. (8) is an alkyl group, an alkoxyalkyl group, or an acyl group, and is a and bLtO or 1.) Specific representative examples of these organosilicon compounds include:
Tetraalkoxysilanes such as methyl silicate, ethyl silicate, n-propyl silicate, i-propyl silicate, n-butyl silicate, 5ea-butyl silicate and t-butyl silicate, and their hydrolysates, as well as methyltrimethoxysilane, Methyltriethoxysilane, methyltrimethoxyethoxysilane, methyltriacetoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxy Silane, phenyltrimethoxysilane,
Phenyltriethoxysilane, phenyltriacetoxysilane, γ-riO-loprobiltrimethoxysilane, γ-
-O-lopropyltriethoxysilane, γ-O-lopropyltriacetoxysilane, 3,3.3-trifluoropropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ- Amisobrobyltriethoxysilane, γ
-Mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, N-β(aminoethyl)-γ-aminopropyltrimethoxysilane, β-cyanoethyltriethoxysilane, methyltriphenoxysilane, chloromethyltrimethoxysilane, Chloromethyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyloxysilane, β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, α-glycidoxypropyltrimethoxy Silane, α-glycidoxypropyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane,
γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltribroboxysilane, γ-glycidoxypropyltributoxysilane, γ-glycidoxy Probyltrimethoxysilane, γ-glycidoxypropyltrifenoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-glycidoxybutyltrimethoxysilane, 2silane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-
Glycidoxybutyltriethoxysilane, δ-glycidoxybutyltrimethoxysilane, δ-glycidoxybutyltriethoxysilane, (3,4-epoxycyclohexyl)methyltrimethoxysilane, (3,4-epoxycyclohexyl)methyl Triethoxysilane, β-(
3゜4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltripropoxysilane, β-(3,4-epoxycyclohexyl)ethyltripropoxysilane
-Epoxycyclohexyl)ethyltriptoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxyethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriphenoxysilane, γ-(3,
4-Epoxycyclohexyl)butyltriethoxysilane, γ-(3,4-epoxycyclohexyl)propyltriethoxysilane, δ-(3,4-epoxycyclohexyl)butyltrimethoxysilane, δ-(3,4-epoxycyclohexyl) Trihair, Ruco-xy, triazyloxy or triphenoxysilanes such as butyltriethoxysilane or their hydrolysates, dimethyldiacetoxysilane, phenylmethyldimethoxysilane, dimethyljethoxysilane, phenylmethyljethoxysilane, γ- Rirolopropylmethyldimethoxysilane, γ-chloropropylmethyljethoxysilane, dimethyldiacetoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyljethoxysilane, γ-mercapdobutylmethyldimethoxysilane Sisilane, γ-aminopropylmethyljethoxysilane, methylvinyldimethoxysilane, methylvinyljethoxysilane, glycidoxymethyldimethoxysilane, glycidoxymethyljethoxysilane, α-glycidoxyethylmethyldimethoxysilane, α -Glycidoxyethylmethyldiediethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycidoxib O
Bylmethyljethoxysilane, β-glycidoxybumerobylmethyldiXtoxysilane, β-glycidoxypropylmethyljethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane Silane, γ-glycidoxypropylmethyldibroboxysilane, γ-glycidoxy70virmethyldibutoxysilane, γ-glycidoxypropylmethyldimethoxyethoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ - Glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylphenyldimethoxysilane, γ-glycidoxypropylphenylvinyldimethoxysilane, γ-glycidoxypropylphenyldimethoxycisyloxysilane or its hydrate An example is decomposition products.

It is also possible to add one type or two 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 are preferably used after being hydrolyzed in order to lower the curing temperature and further promote curing.

Hydrolysis is produced by adding and stirring pure water or an acidic aqueous solution such as hydrochloric acid, acetic acid, or sulfuric acid. Furthermore, pure water or acidic aqueous solution.

It is also possible to easily control the degree of hydrolysis by adjusting the amount added. During hydrolysis, it is particularly preferable to add pure water or an acidic aqueous solution in an amount equal to or more than 3 times the mole of the alkoxy group, 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 possible to mix the organosilicon compound and a solvent before hydrolysis. It is possible to remove an appropriate amount and use it, or it is also possible to add an appropriate solvent afterwards.

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. Depending on the purpose, it is also possible to accelerate the hydrolysis reaction and heat it above room temperature to further advance reactions such as precondensation, or to lower the hydrolysis temperature to below room temperature to suppress precondensation. Needless to say, it is also possible to do so.

Curing of the coating composition of the present invention can be achieved by preheating and/or drying the composition, UV irradiation, or electron beam irradiation, but various curing agents may be used to accelerate curing and enable low-temperature curing. Can be used together. 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 acid anhydrides, nitrogen-containing organic compounds, and various gold Ii!
Examples include complex compounds, metal alkoxides, and various salts such as alkali metal organic carboxylates and carbonates. 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 viewpoint of the stability of the coating material and the presence or absence of coloring of the coating film after coating.

The aluminum chelate compound mentioned here has the general formula A
It is an aluminum chelate compound represented by IXnY3-n.

However, in the formula, X is OL (L is a lower alkyl group), Y is the general formula MI
GOCI-12C0M2 (Ml, M2 yesfWf
:+Lower alkyl group)
and n is 0.1 or 2.

The general formula AIXπY3- is particularly useful as a curing agent in the present invention.
As the aluminum chelate compound represented by n, various compounds can be mentioned, but the solubility in the composition, stability,
Particularly preferred from the viewpoint of effectiveness as a curing catalyst are aluminum acetylacetonate, aluminum bisethylaceto 7acetate monoacetylacetonate, aluminum di-n-butoxide monoethylacetoacetate, and aluminum di-130-propoxy. Do-monomethyl acetoacetate 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 aI friction coefficient of the coating film surface. In particular, block or graft copolymers of dimethylsiloxane and alkylene oxide, and fluorine-based surfactants are 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 heat deterioration resistance.

Various inorganic oxides can be used to further improve surface hardness, improve antistatic properties, increase the refractive index of coating films, and improve weather resistance. Silica sols, which are colloidal dispersions of high molecular weight silicic anhydrides in organic solvents such as water and/or alcohols, are preferably used.

Curing of the coating composition of the present invention is mainly carried out by heat treatment, but the heating temperature can be used over a much wider range than in the case of conventional thermosetting resin compositions, and 50 to 250'C is sufficient. Good results are obtained.

The object to be coated to which the present invention is applied may be any material as long as the purpose of the present invention is required, but from the viewpoint that it is possible to impart strong adhesive properties, glass, thermosetting resins, adhesive coated materials, etc. Thermoplastic resins, which are difficult to control, give particularly effective results.

The above plastic materials include polymethyl methacrylate and its copolymers, polycarbonate, diethylene glycol bisallyl carbonate (OR-39),
Polyesters, especially polyethylene terephthalate, and unsaturated polyesters, acrylonitrile (halogenated) styrene copolymers, vinyl chloride, polyurethane, epoxy resins, di(meth)acrylate polymers of (halogenated) bisphenol A and their copolymers, (halogenated) ) Tane-modified di(meth)acrylate polymers of bisphenol A and copolymers thereof are preferred.

Among these, it is preferably used for halogen-containing organic polymers that generally have poor weather resistance.

Moreover, it can also be preferably used for glass.

As the means for applying the primer composition of the present invention and the coating composition to be applied on the seven primer layers, commonly used coating methods such as brush coating, dip coating, roll coating, spray coating, and flow coating can be easily used. It is possible.

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. A useful application method of the composite film of the present invention is to coat the composite film of the present invention with metal oxide, inorganic oxide, etc. by vapor deposition, etc., for heat ray reflection, antireflection, mirror processing, etc.

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 parts and percentages in the examples are based on weight.

Example 1 (1) Preparation of primer composition Xylene/butyl acetate (50150 weight ratio) of a quaternary copolymer (OH value = 50) consisting of styrene/butyl acrylate/hydroxyethyl methacrylate/2-hydroxyethyl methacryloyl phosphate and a biuret conjugate of hexamethylene diisocyanate (
NGO content %: 16.5%) 1.22/1 NGO1
A primer composition was obtained by adding at a 0H ratio and diluting the solid content to 10% with a methyl isobutyl ketone/ethyl acetate (50150 weight ratio) solvent.

(2) Applying and curing the primer composition (1)
0.) of hexamethylene diisocyanate per 1 mole of the hydroxyl group-containing compound obtained by esterifying the primer composition obtained by esterifying 1 mole of acrylic acid to 2 moles of ethylene oxide adduct of tetrabromobisphenol A.
70 parts of a monomer containing a polyfunctional acrylate monomer and 30 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 rate 1).
0 cm/g+in). The coated board is 9
It was heat-cured at 3°C for 1 hour.

(3) Preparation of coating composition (a) Preparation of silane hydrolyzate γ-glycidoxypropylmethyljethoxysilane 10
6.8Q was cooled to 10℃ and without stirring, 0.05
15.5 g of a normal aqueous hydrochloric acid solution was gradually added dropwise, and after the addition was completed, stirring was continued for an additional hour at room temperature to obtain a silane hydrolyzate.

(b) Preparation of coating composition The silane hydrolyzate is coated with an epoxy resin coating.
,.

Bicoat 827”, Shell Chemical Co., Ltd. product) 50Q1
Diacetone alcohol 59g, benzyl alcohol 29g
．． 5G, acetylacetone 23.3Q, and silicone surfactant 1.5Q were added and mixed, and methanol-dispersed colloidal silica (average particle size 12±1 mu, solid content 3
0%) 416°90 and 12°5 g of aluminum acetylacetonate were added and stirred thoroughly to prepare a coating composition.

(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. 4 at 93℃ after application
A composite film was obtained by heating and curing for a period of time.

(5) Test Results The performance of the base material 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 #0OOOO steel wool and judge the extent of scratches. The criteria are: A: Strong<*No scratches even when rubbed.

B: Pretty strong! If you rub it, it will get a little scratched.

C: Even weak friction causes scratches.

D: Easily scratched with nails.

(B) On the coated surface of the adhesive base material, use a steel knife to make goggles that reach the 11-sided substrate on the coated film. 100 pieces of mini cellophane adhesive tape (product name: "Cellotape Panichiban Co., Ltd. product") was strongly applied and rapidly peeled off in a 90-degree direction, and the presence or absence of paint film peeling was examined.

(C) Appearance The transparency and degree of coloration of the substrate having the obtained composite film were observed with the naked eye.

(D) Hot water resistance After immersion in hot water at 90°C, an adhesion test was conducted in the same manner as in (B) above.

Comparative Examples 1-2 The same procedures as in Example 1 were carried out except that the acrylic polyol in the primer composition was changed to the composition shown in Table 1. The OH values of the acrylic polyols used are shown in Table 1. The test results are shown in Table 1.

Table 1 ST: Styrene BA Nibutyl acrylate HEMA: Hydroxyethyl methacrylate HEMP:
2- and droxyethyl methacryloyl phosphate MM
A: Methyl methacrylate EA: Ethyl acrylate to H niacrylic acid BMA: n-butyl methacrylate [Effects of the invention] (1) High surface hardness and less likely to be scratched.

(2) Can be dyed with disperse dyes.

(3) Excellent water resistance, especially hot water resistance.

(4) Good adhesion with vapor deposited films such as non-1m oxides.

<5) Effective in improving the heat resistance of deposited films such as inorganic oxides.

Claims (1)

[Claims] (a) Tg of the homopolymer on the base material is 375°K
A primer composition consisting of an acrylic polyol containing at least one type of acrylate or methacrylate represented by the following general formula ▲ mathematical formula, chemical formula, table, etc. ▼ and a polyfunctional organic isocyanate compound (where R is H or CH_3, X has 1 or more carbon atoms
12 hydrocarbon groups, and even OH of acrylic polyol
The value is 10 or more and 200 or less, and the NCO/OH ratio is 0.6.
(b) The primer composition is cured by heating and/or drying, (c) The general formula R^1_aR^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, 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, and a and b is 0 or 1).