JPS60197771A - Coating composition and coating method using the same - Google Patents

Abstract

PURPOSE:To provide the titled compsn. which gives a coating film having excellent rust proofness, processability, fingerprint resistance and adhesion to paints, by dissolving or dispersing an alkoxysilane, a specified resin and a photopolymerization initiator in an org. solvent. CONSTITUTION:A lower polyfunctional compd. contg. a functional group contg. active hydrogen atoms is reacted with 0.8-1.2mol (per equivalent of said functional group) of a polyisocyanate compd. The resulting urethane prepolymer, a polybutadiene polyol contg. OH groups at both terminals of its polymer chain, a (meth)acrylate compd. contg. OH group and a thiol compd. contg. at least one thiol group per molecule are reacted together to obtain a thiol-modified urethane (meth)acrylate resin (B). 1-70wt% alkoxysilane (A) of the formula (wherein R is a 1-6C alkyl, phenyl; R' is a 1-4C alkyl; n is 0-2), 99-30wt% component B and 0.05-10wt% (based on the quantity of component B) photopolymerization initiator (C) are dissolved or dispersed in an org. solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Application of the Invention: The present invention relates to a coating composition.9 More specifically, the present invention relates to a photocurable coating composition containing an alkoxysilane and comprising a novel combination of composition components. The present invention also relates to a method of applying the composition to a substrate surface.

The coating composition is used to coat metal substrates such as stainless steel plates and galvanized steel plates with surface hardness and solvent resistance for the purpose of forming coatings with excellent rust prevention, paint adhesion, fingerprint resistance, and workability. It is applied to the surface of a plastic substrate for the purpose of forming a film with excellent properties and workability, and to the surface of a glass substrate for the purpose of forming an antifogging film.

Prior art: There have been numerous proposals for improving one or more of the properties of the coating formed by employing coating compositions and coating methods for surface treatment of various substrates. There are an endless number of them. Most of these products differ depending on their purpose, but organic polymers such as acrylic resins, epoxy resins, etc. are the main components.
After coating on the substrate, it is cured by heat or light.
Although the formed film has the advantage of being highly flexible,
It has drawbacks such as low surface hardness, poor solvent resistance, and lack of rust prevention, especially when applied to metal surfaces. In recent years, many coating compositions containing organosilicon compounds as components have been proposed as coating compositions capable of forming coatings with high surface hardness and excellent solvent resistance. The main one is a composition containing an organosilicon compound into which a substituent having a polymerizable unsaturated bond is introduced, without citing any specific literature. In these products, the organosilicon compound, which is the main ingredient, is not only expensive because it is synthesized through an extremely complicated process, but also has defects in the organosilicon compound or its composition flow line and stability. be. In order to introduce a relatively inexpensive organosilicon compound into a coating composition, JP-A-51-33128 discloses a co-partial hydrolyzate of tetraalkoxy77rane and alkylalkoxysilane, and an acrylic copolymer. Also, a coating composition in which etherified methylolmelamine is dissolved in a solvent has been proposed. The composition forms a film by heat curing after being applied to a substrate, and has high surface hardness and excellent solvent resistance, and when applied to metals, a film with excellent rust prevention properties can be obtained. There are advantages. However, this coating has a drawback that it has poor flexibility and is easily peeled off and separated by deformation processing after the coating is formed.

JP-A-59-4611 discloses a photosensitive resin consisting of a three-dimensional compact of methyl silicate treated with a prepolymer having ethylenically unsaturated bonds, a monomer, a photopolymerization initiator, and a titanium-based coupling agent. A composition is disclosed,9 and an embodiment is described in which it is applied to a substrate and photocured to form a film.

The film obtained by photocuring the composition is highly flexible,
Although it has the advantage of excellent adhesion to the substrate, it has the disadvantages of low surface hardness and poor solvent resistance.

Problems to be solved by the invention: The present invention has found that after the coated substrate has been deformed, the surface hardness is high;
The object of the present invention is to provide a coating composition that has excellent solvent resistance and corrosion resistance and forms a coating, and a method for coating a substrate using the same.

Means for solving the problem: The present invention is directed to component (B): alkoxysilanes, component (B)
: Thiol-modified urethane (meth)acrylate resin and component C): A coating composition prepared by dissolving or dispersing a photopolymerization initiator in an organic solvent, and applying the coating composition directly to a substrate to activate the This coating method is characterized by photo-curing by irradiation with light, or by photo-curing and then further heat-curing.

In the present invention, the alkoxysilane as a component has the general formula: Rn181(OR')4-n...
・・・・・・・・・・・・Tetraalkoxyfurans (in the formula, i200 o'clock), trialkoxysilanes (in the formula, n = 10 o'clock) and dialkoxysilanes represented by (1) (in the formula, n=20 o'clock), and one or more selected from the group consisting of a partial condensate of the alkoxysilane and a partial hydrolysis product of the alkoxysilane. The partial condensate of alkoxysilane is produced by reacting 1aI of the alkoxysilane represented by the general formula (1) alone or in a mixture of two or more in the presence of a lower alcohol having 1 to 4 carbon atoms and an organic acid such as acetic acid. It is a siloxane polymer obtained by condensation polymerization in a system. Further, the partial hydrolysis product of alkoxysilane is expressed by the general formula 1
It is a siloxane polymer obtained by hydrolyzing a single t or a mixture of 2 m or more of alkoxysilanes represented by 1) in the presence of an acidic or alkaline catalyst.

In the present invention, component (g) is used alone or as a mixture of two or more of the alkoxysilanes described above.

In the present invention, component (8) thiol-modified urethane (
The meth)acrylate resin contains the following components (b) and @.

It is a photocurable resin obtained by reacting 0 and 0).

Component υ): A lower polyfunctional compound having a plurality of functional groups having active hydrogen, and 0.8 to 1.0% per equivalent amount of functional group.
The urethane prepolymer component (g) obtained by reacting with 2 moles of a polyisocyanate compound has hydroxyl groups at both ends of the polymer chain. Mixture component (F') with a compound having at least one thiol group: a (meth)acrylate compound having a hydroxyl group in one molecule; a thiol-modified urethane (of the thiol compound component having at least one thiol group in one molecule); The meth)acrylate resin is crosslinked by irradiation with actinic rays in the presence of a photopolymerization initiator using the double bonds of the (meth)acrylate group and polybutadiene, and is then crosslinked with a radical polymerization initiator or a radical. It is crosslinked by thermosetting in the presence of a polymerization initiator and a curing accelerator to form a tough film.

In the present invention, the photopolymerization initiator (Q) is added to photocure the thiol-modified urethane (meth)acrylate resin of the component (-), and any known photopolymerization initiator may be used. can be used.

In the present invention, the coating composition comprises an organosilicon compound as the above-mentioned component and a thiol-modified urethane (meth) as the component.
The ll amount ratio converted to solid content with acrylate resin is 1=
99-70:30. The photoinitiator of component (Q) is the component (B
) of thiol-modified urethane (meth)acrylate resin is dissolved or dispersed in an organic solvent, and if desired, a photopolymerization accelerator, radical polymerization initiator, curing Additives such as accelerators, stabilizers, glass-forming agents, and organometallic compounds other than silicon compounds are added.

In the present invention, the coating composition that can be applied to a substrate includes:
It is photocured by irradiating ultraviolet rays of 200 to 500E1111 as actinic rays, and then heated to a temperature of 80 to 300°C by 0.5
A desired film is formed on the substrate by heat treatment and thermosetting for ~120 minutes.

Function: As a result of extensive research by the inventor, Hiromu, the present invention provides a photocurable composition comprising the above-described component (B), a thiol-modified urethane (meth)acrylate resin, and component (C), a photopolymerization initiator. The film formed by applying and photocuring to a substrate has excellent film performance, and by adding the alkoxysilane of component η) to the component (B), the film formed by photocuring. This work was completed after discovering that the performance of the coating was improved, and that the coating performance was significantly improved by heat-treating the formed coating. That is, the composition for contacting of the present invention has both photocurability and thermocurability.

In the present invention, the thiol-modified urethane of component (B) (
The (meth)acrylate group in the meth)acrylate resin and the double bond of the polybutadiene are crosslinked to form a film. The film thus formed has excellent adhesion to the substrate and is flexible, so that the substrate can be subjected to deformation processing such as bending and welding. Then, by heat-treating the substrate on which the photocured coating has been formed, crosslinking progresses further, resulting in a product with high surface hardness, excellent solvent resistance and corrosion resistance, and especially when applied to gold bullion substrates, it has excellent rust prevention properties. A film is formed. Although the line of the crosslinking process due to heat treatment is not certain, the active hydroxyl groups, thiol groups, etc. derived from the thiol-modified urethane (meth)acrylate resin of component (B) present in the film formed by photocuring mutually and Ingredients (6
) is more likely to be crosslinked using alkoxysilanes as a crosslinking agent.

In the present invention, general formula (1) Rn8 l (OR' ) @ used as the alkoxysilane of component (g)
Specific examples of compounds represented by +n include tetramethoxysilane, tetraethoxysilane, tetraisogloboxysilane, tetramethoxysilane, dimethoxysilane, and dimethoxydiisopropoxy, where the number in the formula is 0. silane, methyltrimethoxysilane, methyltriethoxysilane in which jetoxydiisopropyl is 1;
Trialkoxysilane derivatives in which R is an alkyl group having 1 to 6 carbon atoms or a phenyl group, such as methyltriisopropoxydisilane, ethyltriisopropoxysilane, ethyltributoxysilane, phenyltriethoxysilane, and i is 2, such as dimethyldimethoxysilane, dimethyljethoxysilane, diethyldiisopropoxysilane, diethyldibutoxysilane, etc. Dialkoxysilane in which R is the same type as an alkyl group having 1 to 6 carbon atoms, a phenyl group, etc. Derivatives may be mentioned.

Partially condensed flow line used in component), the above general formula +13
The alkoxysilane 01ai represented by 01ai alone or a mixture of two or more can be partially reacted with a lower alcohol such as methanol, ethanol, boopanol, butanol, etc. under reflux of the alcohol in a system in the presence of an organic acid such as acetic acid. Obtained as a condensed siloxane polymer.

In addition, the partial hydrolysis product used in component) is obtained by adding one or more alkoxysilanes represented by the general formula (1) alone or in a mixture of two or more in an organic solvent.
By reacting with water in the presence of an acidic or alkaline catalyst, a siloxane polymer is obtained by dealkylation of the alkyl group represented by R' in the general formula (1). Acidic catalysts used in the hydrolysis reaction include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphorous acid, and boric acid; lower organic acids such as acetic acid, propionic acid, Schereric acid, fumaric acid, maleic acid, and succinic acid; Two or more types of mixed acids can be exemplified.

In the present invention, component (B) thiol-modified urethane (
As described above, the meth)acrylate resin contains components p), (
6), 0 and 1G) are reacted.

Ingredient (b) is a lower polyfunctional compound having a plurality of functional groups having active hydrogen, and 0.0% per equivalent of the functional group of the compound.
8 to 1.2 moles of polyisocyanate compound and 25 to 1.2 moles of polyisocyanate compound.
This is a urethane prepolymer having the same number of incyanate groups as the active hydrogen number of the lower polyfunctional compound obtained by reacting at a temperature of 100° C. for at least 30 minutes.

The lower polyfunctional compound is usually a lower polyfunctional compound having a molecular weight of 200 or less, preferably having 3 to 4 Fi functional groups, such as glycerin, 1.2.6-hexandriol, 1.1@1. -) Limeterorp four breads 1.・
These are l@l-trimethylolethane, triethanolamine, triisoglopanolamine, and pentaerythritol. These compounds include la [alone or #i
Used as a mixture of two or more. On the other hand, polyisocyanate compounds can include a wide variety of polyisocyanate compounds, either alone or as a mixture of isomers, or in combination.
Mixtures of more than one species can be used, as well as polyincanate polymers and mixtures of these polymers.

As polyincyanate compounds, 2,4-triledgeanate, 4-methoxy-1,3-phenylene diisocyanate, 4-isopropyl-1,3-phenylene diisocyanate, 4-chloro-1-3-phenylene diisocyanate, 4-butoxy -1,3-phenylene diisocyanate, 2,4-diisocyanate diphenyl ether, mesitylene diisocyanate, 4,4'-methylene-bis(phenylisocyanate), ditolylene diisocyanate, 1,5-naphthalene diisocyanate,
benzine diisocyanate, 0-dibenzine diisocyanate, 4,4'-dibenzyl diisocyanate,
l,4-tetramethylene diisocyanate, l,6-hexamethylene diisocyanate), 1@10-decamethylene diisocyanate, l,4-cyclohesilyl diisocyanate, medium silylene diisocyanate, 4"4'-
Trimers and pentamers of polyisocyanates such as methylene biscyclohexyl isocyanate, 1.5 tetrahydronaphthalene diisocyanate and isophorone diisocyanate, tolylene diisocyanate, and trimer of isophorone diisocyanate (manufactured by Hürz AG, West Germany)
Polyisocyanate polymers such as

As the polyincyanate compound, an isomer mixture of 80% 2-4-tolylene diisocyanate and 20% 2,6-tolylene diisocyanate is preferably used.

The polybutadiene polyol having hydroxyl groups at both ends of the polymer chain used as component (b) has a number average molecular weight of 50.
0 to IO,000. As a specific example, Nippon Ichida Co., Ltd.'s product name Nl880-PBG-1000, N
l580-PIG-2000, Nl880-PBG-3
000, Po1y BD manufactured by Arc (MuaCO) Co., Ltd.
-R-45M, Poly BD-R-45BT%
Poly BD-CB-15, Poly BD-CN-
15. Philips product name Butar@g HT
, the product name Hyaar-HTB% by Gutdrich, and the product name T@1og·n HT by General Tire Company.

It is also possible to use a polybutadiene polyol having a hydroxyl group, which is hydrogenated using a Raney catalyst or a medium-stabilized nickel catalyst.

In addition, the compounds having two or more hydroxyl groups in one molecule, which are used by partially mixing with polybutadiene polyol in component (g), include polyether diol, polyester diol, and polyacryl diol, and the mixing ratio is polyether diol, polyester diol, and polyacryl diol. Butadiene polyol is used at 60% or more.

Typical polyether diols are those obtained by polymerizing alkylene oxide, such as polyethylene glycol and polytetrapyrene glycol having a molecular weight of 200 to 5,000.

In addition, as an alkylene glycol, neopentyl glycol, l.4-butanediol, l.6-hexanediol, or a polyester diol obtained by combining N41!1 lactones such as caprolactone in the presence of a polyhydric alcohol with a molecular weight of 500 Examples include 1 in 3,000.

The (meth)acrylate resin having a hydroxyl group in one molecule used as component F)) has the following general formula (21 (wherein, X is hydrogen, halogen or lower alkyl group, and R is -f
CH2+. Mara is I1 (-CH2CHO-)-nCH2-1i is an integer from θ to 2o, R2 is hydrogen, lower alkyl, the ratio is -CH2Cl,
R5 is hydrogen, lower alkyl or -CH20R5, R
p and R9 are hydrogen, a lower alkyl group, or a lower alkyl group containing halogen. ) is a hydroxyalkyl (meth)acrylate represented by For example, 2-hydroxyethyl methacrylate,
2-hydroxyethyl acrylate, 3-chloro 2-hydro dipropyl acrylate, 3-butoxy 2-hydroxypropyl acrylate, 3-butoxy 2-hydroxypropyl methacrylate, 2-hydroxypentyl acrylate, 2- and droxypentyl methacrylate, etc. can be mentioned. Acrylate is more preferably used than methacrylate from the viewpoint of photocuring speed.

In addition, as a (meth)acrylate having a hydroxyl group,
Compounds modified with dibasic acids such as phthalic anhydride, alkylene oxides such as propylene oxide, and having at least one hydroxyl group may also be used. As an example of this, 2-
Hydroxyethyl methacrylate-phthalic anhydride-propylene oxide (1/1/1 molar ratio) reactants may be mentioned. Thiol compounds containing at least one thiol group per molecule used as component C) are: General formula R6
-(SH)n (where R6 is an a-valent organic residue having no reactive unsaturated bond with the 8■ group, and n is an integer from 1 to 4) with a molecular weight of 80 to methyl-2 -propanethiol, 2-butanethiol, 2-methyl-1-propanethiol, l-butanethiol, l-pentanethiol, l-hexanethiol, 1-hebutanethiol,
Thiols such as L, 2-cotanedithiol, 2,2-propanedithiol, benzenethiol, P-benzenedithiol, pyridine-2-thiol, thiophene-2-thiol, thioglycolic acid, α-mercaptopropionic acid, β- Thiols derived by the esterification reaction of mercaptopropionic acid and monoalcohol or polyhydric alcohol, aliphatic and aromatic J') thiols such as alcohol ethanedithiol, propanedithiol, hexamethylenedithiol, xylylenedithiol, etc.
Polythio-types derived by replacing the halogen atom of the shrimp halohydrin adduct of alcohol with a mercaptan group.
Examples include sulfuric acid reactants of 1'-1' compounds. In addition, thiourea, α-mercaptobenzothiazole, etc. can be used. These thiols may be used alone or in combination of two kinds. It can be used as a mixture of the above.

The thiol-modified urethane (meth)acrylate resin of component (B) is produced by a method in which the reaction product of component ρ) and component (g) described above is reacted with component 0 and then component 0), component p) and component A method of reacting component 0 and then component C) with the reaction product of component (6), and component (g) and component (6).
) can be synthesized by any of the following methods: reacting the reaction product with component (D) and then component (g).

The thiol-modified urethane (meth)acrylate resin of component (B) is based on 1 equivalent of hydroxyl groups in the polybutadiene polyol of component (6) or a mixture of polybutadiene polyol and a compound having two or more hydroxyl groups in one molecule. On the other hand,
Urethane prepolymer with 1 to 4 mol of component ([)), 0.02 to 0.6 mol of component (G) per 1% of component
, and the reaction product of component (g) and linear component ρ), component (6), and component C) relative to 1 equivalent of isocyanate residue in the reaction product of component (g) and component (g).
It is obtained by reacting 0.8 to 1.2 equivalents of the hydroxyl group of the (meth)acrylate compound having a hydroxyl group (g).

If the amount of polybutadiene polyol in component () is too large compared to the urethane prepolymer of component (ρ), the viscosity will increase and there is a risk of gelation. This is undesirable because strength and chemical properties are lost. If the amount of the thiol compound introduced as component 0) is less than 0.02 mol per 1 mol of component (g), there will be little effect on the physical properties of the film, and if it exceeds 0.6 mol, the resin will deteriorate. This is not preferable because the viscosity increases and the stability of the resin and the flexibility of the cured film deteriorate.

Furthermore, the component (g) for 1 equivalent of incyanate residue
If the amount of hydroxyl groups in the (meth)acrylate compound is less than 0.8 degrees, the photocurability of the resulting resin will decrease, and if it exceeds 1.2 degrees, the cured product will have poor properties, which is not preferred.

In the present invention, the photopolymerization initiator of component 9 is the component 0.
) Any thiol-modified urethane (meth)acrylate resin that can initiate polymerization when irradiated with actinic rays can be used. Its representative compounds are benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether,
Benzoin isobutyl ether, benzoin acetate, benzophenone, 2-/lorbenzophenone, 4-methoxybenzophenone, 4,4'-dimethylbenzophenone,
4-bromobenzophenone, 2.2',4.4'-tetrachlorobenzophenone, 2-chloro-4'-methylbenzophenone, 3-methylbenzophenone, 4-1-butylbenzophenone, benzyl, benzylic acid, benzyl dimethyl ketal, Diacetyl, methylene r, acetophenone, 2.2-jethoxyacetophenone, 9.
10-7 enanthrenequinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, diphenyl disulfide, dithiocarbamate, α-chloromethylnaphthalene, anthracene, iron chloride, l,4-naphthoquinone, etc. be. Particularly preferred are benzyl dimethyl ketal, 2,2-jethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, penzoin isopropyl ether, benzoisobutyl ether 2-ethylanthraquinone and thiosanthone. These photopolymerization initiators may be used alone or in combination of two or more.

In the present invention, the coating composition contains 1 to 70% of component (5) based on the total amount of the alkoxysilane as component (6) and the thiol-modified urethane (meth)acrylate resin as component (B) in terms of solid content. % by weight, preferably 5 to 25 layers of alcosilanes converted to 8% 02, and 0.05 to 1O of the photopolymerization initiator of component c> relative to component (B).
It is prepared by dissolving or dispersing a composition having a weight of preferably 0.1 to 5 in an organic solvent.

Component (6) improves the surface hardness, solvent resistance, and corrosion resistance of the coating obtained by curing, which is expected by adding the component (the component is less than 1 weight with respect to the total amount of Bl). If the improvement is insufficient and the Tol exceeds 70% by weight, the adhesion of the film obtained by photocuring to the substrate will decrease and the deformability of the substrate after photocuring will deteriorate, which is not preferable.

There are no particular restrictions on the organic solvent to be used, but there are
, -) and tc> are preferably used. As a solvent for (component), lower alcohols such as methanol, ethanol, isopropanol, a-butanol, methyl acetate, ethyl acetate, esters of butyl acetate, acetone, ketones such as methyl ethyl ketone, acetylacetone, polyhydric Examples include alcohols, their ethers, and mixed solvents of two or more of these. , aliphatic hydrocarbons such as mineral spirits, ethyl acetate,
Esters such as butyl acetate, carbon tetrachloride, 111111
Examples include halogenated hydrocarbons such as 1-trichloroethane, perchlorethylene, chlorobenzene, and dichlorobenzene, and mixed solvents of 2 m or more of these. Preferably, an ester such as butyl acetate that dissolves components (T), (B) and 0 together and a lower alcohol that is a solvent for components (B) and (Q) are combined. A mixed solvent with hydrogen is used.

In the present invention, various additives can be added to the coating composition as desired. Additives include photopolymerization accelerators, radical polymerization initiators, curing accelerators used in combination with radical polymerization initiators, stabilizers (polymerization inhibitors), glass forming agents, organometallic compounds other than silicon compounds, pigments, etc. can be mentioned.

Addition of a photopolymerization accelerator accelerates the curing rate compared to photocuring, particularly ultraviolet curing, and significantly reduces the polymerization inhibiting effect of oxygen and the like, and is therefore preferably used in combination with a photopolymerization initiator. There are amines as such photopolymerization accelerators,
For example, primary amines such as butylamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, monoethanolamine; diethylamine, dimethylaniline, dimethylvala-toluidine, pyridine, N,N'-dimethylcyclohexylamine, jetanolamine , triethanolamine, Michler's ketone, and other secondary amines and tertiary amines.

As the radical polymerization initiator, diacyl peroxides such as benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, octanoyl peroxide, lauroyl peroxide, dialkyl peroxides,
For example, di-tertiary butyl peroxide, dicumyl peroxide, peroxy esters such as tertiary butyl hachenzoe),! 3-butyl peracetate, di-tert-butyl perphthalate, 2,5-dimethyl-2,5-
di(benzoylperoxy)hexane, etc., ketone peroxides such as methyl ethyl ketone peroxide, cyclopentyl peroxide, hydroperoxides such as tertiary butylhydroperoxide, cumene hydroperoxide, Preferably, α-phenylethyl hydroperoxide, cyclohexenyl hydroperoxide, etc., and mixtures thereof are additives and have no foaming properties, and the amount used is based on the total resin content.
0.1-10% by weight, preferably α5 to 5% by weight.

In addition, examples of curing accelerators used in combination with the radical polymerization initiator include metal soaps such as cobalt naphthenate, manganese naphthenate, copper naphthenate, iron naphthenate, and cobalt oleate; cobalt chloride, manganese acetate, etc. aquatic metal salts; strong reducing agents such as ascorbic acid and araboascorbic acid; thiocyanates such as ammonium thiocyanate and potassium thiocyanate; thiourea, tetramethylthiourea, ditolylthiourea, ethylenethiourea, 2-mercaptobenzo Thioureas such as thiazole and 2-mercaptobenzindazole are effective.

Dimethylaniline, diethylaniline, triethylamine, triethanolamine, octylamine, butylamine, diethylenetriamine, triethylenetetramine, pentaethylenehexamine, tetraethylenepentamine, anisidine, pyrrolidine, toluidine, 2.2
Amines such as '-bipyridyl-4°4'-cyanodiphenylmethane, pendidine, and triphenylenetetramine have a strong effect of promoting radical generation.

The amount of curing accelerator added is 0.001 to 3 based on the total resin content.
If it is less than 0%, there is no effect, and if it is too much, the main agent will be diluted and the adhesive strength will decrease.

It is even better to use a combination of several curing accelerators.

It exhibits the ability to accelerate curing. The radical polymerization initiator and curing accelerator may be dissolved in the (meth)acrylate, or may be dissolved in trichlorethylene, chlorophor A% vinegar &:r-
It may be used alone or after being dissolved in a mixed solution of chill, ethanol, ingropanol, acetone, methyl ethyl ketone, ether, methyl chloroform, water and the like.

Among the curing accelerators, metal soaps such as cobalt naphthenate, manganese naphthenate, copper naphthenate, iron naphthenate, and cobalt oleate can also be added alone as a curing agent.

In order to prevent early crosslinking of the thiol-modified urethane (meth)acrylate resin of component (B) during heat treatment and storage, it is desirable to incorporate a stabilizer (polymerization inhibitor). Examples of the stabilizer include di-t-butyl-p-cresol, hydroquinone monomethyl ether, hyrogallol, quinone, hydroquinone, t-butylcatechol, hydroquinone monobenzyl ether, methyl hydroquinone, aruquinone, phenol, hydroquinone monopropyl ether, Examples include phenothiazine and nitrobenzene. These stabilizers prevent premature crosslinking during formulation or storage of the coating composition.

It forms a glass by heating with alkoxysilanes, and it does not necessarily form a glass when it is added to the composition of the present invention for coating. , improves the surface hardness and corrosion resistance of the formed coating, especially the alkali resistance. As glass forming agents, phosphoric acids, phosphorus compounds such as dialkoxide conductors, boron compounds such as boric acids, boron alkoxide conductors, arsenic acids, arsenic compounds such as arsenic alkoxide derivatives, antimonic acids, antimony alkoxide derivatives, etc. antimony compounds such as carbon derivatives, organic gallium compounds, zinc compounds such as zinc carboxylates, zinc alkoxides, etc.
Lead compounds such as lead carboxylates and lead alkoxides, and mixtures thereof can be used in addition.

Organometallic compounds other than silicon compounds also have the effect of improving the properties of the formed film, similar to the glass forming agent. As these organometallic compounds, titanium, tantalum, aluminum, alkoxides of zirconium, chelated products, acylated products, and mixtures thereof can be preferably used.

Pigments can be added for the purpose of forming a transparent colored film. For example, CIBA-GEIGY's M
icrolith Bln@4G-T, Crom
ophtal Orange 2G #Miaro11
th Gre@n GT etc. can be used.

In the present invention, the coating composition described above is applied to various substrates to a uniform thickness, and after drying and removing the solvent as necessary, actinic light is irradiated to form a photocured film on different surfaces of the substrate. . As a light source for photocuring, it is possible to activate the photopolymerization initiator of component 0 and the photopolymerization accelerator optionally added.
~500nm.

A high-pressure mercury lamp that generates ultraviolet rays, a high-pressure mercury lamp,
Carbon arc lamps etc. can be used. There are no particular restrictions on the method of applying the composition to the substrate, and methods that provide a uniform coating thickness, such as dipping and pulling up, spraying, and roll coating, are preferably employed.

The film formed by photocuring has sufficient properties as a protective film for various substrates covered with it, but it also has 8
Heat treatment at a temperature of 0 to 300°C for 0.5 to 120 minutes advances thermal curing, improving coating properties, especially surface hardness,
A film with significantly improved solvent resistance and corrosion resistance, especially when encapsulated on a metal substrate, is formed. In addition, when forming a coating for the purpose of IT corrosion, rust prevention, etc. on the deformed surface of a metal substrate such as a stainless steel copper plate or a galvanized steel plate, after coating the flat substrate with a coating composition and photo-curing, A desired film can be formed by carrying out a desired deformation process and then thermally curing.

Implementation Ga; Below, the present invention will be explained in more detail with reference to Examples.

However, the scope of the present invention is not limited in any way by the following examples.

Note that parts and - in the examples are based on weight unless otherwise specified.

11) Component (A) Preparation of alkoxysilanes [A-
11 tetraethoxysilane was designated as [A-11].

[A-2] Ethyltriethoxysilane was designated as (A-2).

(A-3) Tetraethoxysilane: 186 parts, ethanol = 64 parts in a reaction vessel equipped with a stirrer and a reflux condenser
3 parts of acetic acid and 206 parts of acetic acid were added, and further 0.3 parts of 35% hydrochloric acid was added, heated with stirring, and maintained for 45 hours while refluxing the solvent to complete the reaction. After adjusting the amount of solvent so that the concentration of the produced organosilicon compound (partial condensate) in terms of 8102 is 5%, 5102-2.
P2O5 corresponding to 5% was added and dissolved to obtain [A-3].

[A-4) Attach a dropping tube to the reaction vessel used in (A-33) above, and add methyltriethoxysilane to the reaction vessel:
200 parts, tetraethoxysilane = 250 parts, ethanol: 2500 parts and 20% hydrochloric acid: 1.5 parts,
After stirring and mixing, the mixture was heated to 70°C, and 150 parts of water was added dropwise from a dropping tube.

The reaction temperature was maintained at 70° C. during the dropwise addition of water. After the dropwise addition of water was completed, the temperature was maintained at 70° C. for an additional 5 hours to complete the reaction. Organosilicium compound produced (partial hydrolysis product)
The amount of solvent was adjusted so that the 5to2 concentration was 4.75%, and it was designated as A-41.

(A-5) Into the reaction vessel used in (A-3) above, 11 fS parts of tetrabutoxysilane, 163 parts of ethanol, 0.15 parts of 20% hydrochloric acid and 22 parts of water were charged,
The reaction was completed by heating to 70° C. and maintaining the temperature for 4 hours while stirring. After cooling to room temperature, 3.3 parts of nat-2-butoxytitanium was added and dissolved, and the resulting organosilicon compound (partial hydrolysis product) had a 5to2 concentration of 7.
The amount of solvent was adjusted so as to give A-5).

[A-6] To 100 parts of ITolD solution prepared by diluting isopropyl triisostearoyl titanate (Ajinomoto Co., Ltd.: Plenaku) TT8) with toluene, add a three-dimensional condensate of methyl silicate (Nikko Fine Products Co., Ltd.: M8P) to 100 parts of ITolD solution. -8 "8102 Particulates"): 50
After addition and mixing, toluene was removed by volatilization under heating and reduced pressure to obtain (A-a). [Mu-6] was a titanium-based coupling agent: M8F-8, a three-dimensional condensate of methyl silicate to which 2% TTS was attached.

(For comparison) (2) Component (B) Preparation of thiol-modified urethane (meth)acrylate resin [8-1] In a reaction vessel equipped with a stirrer, nitrogen gas blowing tube, dropping funnel, thermometer, and reflux condenser tube, @l”
Tolylene diisocyanate 24 consisting of 60 parts of l-trimethylolpropane, 80% of 2,4-tolylene diisocyanate and 20% of 2,6-tolylene diisocyanate
0 parts and 120 parts of n-butyl acetate were added, and after purging with nitrogen, the mixture was gradually heated while stirring and allowed to react at 80°C for 2 hours. Next, 470 parts of polybutadiene diol having a number average molecular weight of 2,000, a hydroxyl value of 50 (KOHW/f1 and below) and in which 91.716 of the butadiene units in the polymer chain are 1.2-bonds (t-) Chef 3 A mixture of 0 parts of ethyl acetate, 90 parts of ethyl acetate, 90 parts of n-butyl acetate, and 90 parts of ethylene glycol monoether ether acetate (BS) was well dissolved and added dropwise into the reaction vessel over about 2 hours. After the dropwise addition was completed, the reaction was continued at 80°C for 2 hours while passing a small amount of nitrogen gas into the reaction vessel. The polyisocyanate compound thus obtained is a pale yellow transparent solution containing 2.4% free isocyanate;
The viscosity was - (20°C, foam viscometer, same below). Next, switch the introduced nitrogen gas to dry air and, while struggling a little, add 2-hydroxyethyl acrylate from the dropping funnel. 116 parts were added dropwise over 2 hours, and after the addition was completed, the reaction was continued for an additional 3.5 hours at 80°C to form urethane/J.
J) 771-1 No-k spider%/f) Next, 2-ethylhexyl (3
-Mercaptopropione))) was added dropwise for 30 minutes using a dropping funnel, and then an aging reaction was further performed at 50 to 60°C for 2 hours to obtain a thiol-modified urethane (meth)acrylate resin CB-11.

(B-2) (Urethane (meth)acrylate resin (i) obtained in B-13 After dropping 3 parts of ethylene glycol dimercabutoglobionate into 0 parts of ZQ using a dropping funnel for 30 minutes, The reaction was carried out at 60°C for 2 hours to obtain thiol-modified urethane (meth)acrylate resin (
8-2) was obtained.

(Number average molecular weight used in a-31 [a-1] 2.
After thoroughly dissolving 470 parts of 1.2-bonded polybutadiene diol of 000 in 370 parts of toluene, 4.7 parts of benzoyl peroxide was added, and while maintaining the reaction temperature at 50 to 60°C, 2 53.2 parts of -ethylhexyl (3-mercaptopropionate) was added dropwise for 30 minutes, and after the addition was completed, the reaction was carried out at 50 to 60°C for 2 hours to obtain a thiol-modified reaction solution.

Then, add 111161-)') to another reaction vessel in advance.
Add 60 parts of methylolpropane, 240 parts of tolylene diisocyanate, and 120 parts of ropetyl acetate, i1
After the substitution, the reaction was carried out at 80°C for 2 hours while stirring, and 90% of ethyl acetate was added to the resulting reaction solution.
90 parts of n-butyl acetate and 90 parts of ethylene glycol monoethyl ether acetate were added and dissolved well, and the total amount of the above thiol-modified reaction solution was added to a reaction vessel containing the urethane prepolio reaction solution obtained. 2wf
Good to drip over time. After the dropwise addition was completed, the reaction was continued at 80°C for 2 hours while passing a small amount of nitrogen gas into the reaction vessel. Next, while changing the introduced nitrogen gas to dry air and passing a small amount, 116 parts of 2- and droxyethyl acrylate were added dropwise from the dropping funnel over 2 hours, and after the addition was completed, the reaction was further carried out at 80°C for 3.5 hours. A thiol-modified urethane (meth)acrylate resin (B-3) was obtained.

[8-41CB-1] In a reaction vessel similar to
60 parts% of trimethylolpropane 240 parts of tolylene diisocyanate used in CB-1) and 300 parts of n-butyl acetate were added, and after nitrogen substitution, the mixture was gradually heated with stirring and reacted at 80°C for 2 hours.

Next, the number average molecular weight is 1,500 and the hydroxyl value is 66.
6. 91.796 of the butashev unit of the polymer chain is l・2
A mixed solution of 175.4 parts of polybutadiene diol consisting of - bonds and 73.6 parts of propylene glycol having a number average molecular weight of 700 dissolved in 249 parts of a-butyl acetate was added dropwise over about 2 hours. . After the dropwise addition was completed, the reaction was continued at 80° C. for 4 hours while passing a small amount of nitrogen gas into the reaction vessel.

Next, 20.2 parts of ethylene glycol dimerkabutoglopionate (ethylene glycol dimerkabutoglopionate) was added dropwise for 30 minutes using a dropping funnel, and the reaction was further carried out at 50 to 60°C for 2 hours. Next, switch the introduced nitrogen gas to dry air and pass a small amount of nitrogen gas,
-Hydroxyethyl acrylate) was added dropwise for 2 hours using a dropping funnel, and the reaction was further carried out at 50 to 60°C for 2 hours to obtain a thiol-modified urethane (meth)acrylate resin [B-4].

[8-5) In a reaction vessel similar to [8-1], add 1 toluene.
00%, Inphorone diisocyanate Gokeitai (Hul)
95 parts of IPDI-T xylene, Cellosolve acetate 70% solution (manufactured by S. Co., Ltd.) were added and dissolved.

Next, after adding 0.2 parts of dibutyltin dilaure, the number average molecular weight was 1,500. Polybutadiene diol with a hydroxyl value of 66.6 and 91.796 butadiene units in the polymer chain consisting of l/2-bonds 75 ftBt-toluene 7
A solution of 5 parts was added dropwise over about 2 hours. After completing the dropping, while passing a small amount of nitrogen gas into the reaction vessel,
The reaction was continued for 4 hours at 80°C. Next, ethylene glycol dimercaptope. 1 o$-)), l'5WtmT
o-) After dropping K-73 (1-M', further at 50-60°C
The reaction was carried out for 2 hours. Next, the introduced nitrogen gas was changed to dry air, and 22 parts of 2-hydroxyether acrylate was added dropwise for 2 hours using the dropping funnel, after which the nitrogen gas was changed to dry air.
Further, the reaction was carried out at 50 to 60°C for 2 hours to form a thiol-modified urethane (meth)acrylate resin [B-5] (B-6).
) Butyl acrylate = 40 parts, 2-human p-xyethyl methacrylate: lO@, and azopisisobutyrilonitrile: 0.5 parts together with ethanol: 300 parts (
Pour into the reaction vessel used in B-1), under nitrogen atmosphere, 7
The mixture was stirred and maintained at a temperature of 0° C. for 5 hours for polymerization. After the reaction is complete, unreacted monomers are extracted and removed using petroleum ether.B
-63.

(For comparison) [8-7] Vinyl ester resin: 100 parts 6-
Heme Sandiol diacrylate: Dissolved in 70 parts B
-7). (For comparison) (3) Preparation of coating composition Various combinations of alkoxysilanes as the above-prepared components and thiol-modified urethane (meth)acrylate resin as component (B), and further photopolymerization of component C) [& benzyl methyl ketal as an agent and n as a diluting solvent.
- A coating composition was prepared by dissolving in a l=1 mixed solvent of butanol and xylene.

Table 1 shows the supported compositions prepared by adjusting the rumor, I+-1!6I.

However, parts and - in Table 1 are based on weight.
It is a table.

(4) Coating and film test The coating composition prepared above was applied to various substrates to a uniform thickness by dipping or roll coating.
One fabric surface was irradiated with ultraviolet rays from a distance of tM using a 3KW mercury lamp to form a photocured film.

Next, the substrate on which the photocured film was formed was heat-treated to form a thermoset film.

The following film test was conducted on the photocured film and thermoset film thus formed.

The film formation conditions and film test results are shown in Table 2.

(a) Film thickness measurement: Measured using a thin film step measuring device.

(b) Surface hardness: Pencil hardness was measured according to JIS-G-3320. The hardness of a pencil was determined by observing with a 20x magnifying glass and determining the hardness of a pencil without scratching.

(e) Workability: After bending the nuclide substrate 360 degrees using a bending tester with a diameter of 2 mφ, 5-thihydrochloric acid:
3 in a mixed solution of 97CC and 30% H2O2 aqueous solution.
The sample was immersed for 0 seconds, and the bent portion was observed using a 100x magnifying glass.

If there are any cracks in the coating or peeling is not observed),
Those in which cracks were observed in the coating were evaluated as (B), and those in which the coating peeled off were evaluated as (C).

(d) Rust prevention: NaCL: 289μ, Mg80 omitted: 7f on the nine-nuclide substrate processed in the above (b).
After spraying artificial seawater with a composition of /l and ygct2:s tyt, and drying using an infrared comb lamp, the sample was left in a desiccator maintained at a relative humidity of 50% (25°C) for 6 days. Those with no rust observed were classified as (body), those with dotted rust on the processed parts were classified as (B), and those with brass dots all over were classified as (Q).

(・) Solvent resistance: Methyl ethyl ketone 11-m on the coating
After lowering and leaving it for 1 minute, the surface I11 in the direction of JlI was inspected. A case where no abnormality was observed on the coating surface was judged as (4), a case where a slight trace was observed was judged as (B), and a case where a clear mark was observed was judged as a mouth.

(f) Adhesion: A Cellotape e goblin peeling test was conducted according to JIS D-0202.

(100/loo), 99”
-91/100 was determined as (B), and 90 or more'/100 was determined as 0.

Effect of the invention: In the present invention, the composition to be contacted includes alkoxysilanes (component) and thiol-modified urethane (meth) as component
It contains an acrylate resin and a photopolymerization initiator of component (q), and by photocuring the coating film of the composition, each of the components acts synergistically, and as shown in the examples, various coating performances are improved. Forms an excellent film.In particular, a film with excellent surface hardness and rust prevention properties is formed compared to the system containing no alkoxysilanes (Comparative Example 3).In addition, component (B)
By selecting a thiol-modified urethane (meth)acrylate resin as the material, a coating with excellent workability can be obtained despite its high surface hardness.

Furthermore, by thermally curing the coating formed by photocuring, it is possible to form a coating with extremely high surface hardness without deteriorating the various properties of the coating formed by photocuring. It has excellent bending workability despite being as high as 2 to 3H.

In addition, as another embodiment, as shown in Examples 1O and 12, the substrate on which the photocured film was formed was subjected to various processing such as curve processing, and then thermally cured, whereby alkoxysilanes were thermally cured. Fit! A coating having a surface hardness equivalent to that of Comparative Example 2 and having excellent rust prevention, solvent resistance, adhesion, etc. can be formed on the processed surface. This means that by forming a photo-cured film on the surface of stainless steel or galvanized iron plate, applying various processes to it, and then heat-curing it, a film with excellent film performance can be applied to the narrow surface of the workpiece. It is possible to form. Furthermore, by adding a pigment to the composition to be coated in advance, a transparent colored film can be formed, and it is possible to coat the surface of the final processed product using a rough plate material.

The present invention provides a composition for punching that can form a photocured film having excellent film performance and a thermoset film after photocuring treatment, and a method for applying the same.The fields of application thereof are metal surface treatment, metal surface treatment, Its industrial significance is extremely large, as it is used in many industrial fields such as plastic p-bending treatment and glass surface treatment.

Claims (1)

[Claims] 1. Component ■: alkoxysilanes, component (B): thiol-modified urethane (meth)acrylate resin and component (
q: Coating composition 2 prepared by dissolving or linearly dispersing a photopolymerization initiator in an organic solvent, the alkoxysilanes in the components have the general formula;
1) One member selected from the group consisting of tetraalkoxysilanes, trialkoxysilanes, and dialkoxysilanes represented by the above, and partial condensates of the alphoxysilanes and hydrolysis products of the alkoxysilanes, or 2a or more, the thiol-modified urethane (meth)acrylate resin of component (B) is the following components (b), @), (n and O).
Component (b): Cretane Grepolymer component obtained by reacting a lower polyfunctional compound having a plurality of functional groups having active hydrogen with 0.8 to 1.2 mol of a polyisocyanate compound per equivalent of the functional group. (g) A mixture of a polybutadiene polyol having hydroxyl groups at both ends of the double composite steel or a compound having two or more hydroxyl groups in one molecule of the polybutadiene polyol and a compound having two or more hydroxyl groups in one molecule (0:1) meth)acrylate compound component 0): a photocurable resin obtained by reacting a thiol compound having at least one thiol group per molecule; ) and the thiol-modified urethane (meth)acrylate resin of component (8) in a weight ratio of 1:99 to 70:30, and the photopolymerization initiator of component (q) was added. The amount is 0.05 to 1 of the thiol-modified urethane (meth)acrylate resin of component (B).
Coating composition 5 according to claim 1, which has a weight of 0 weight, optionally a photopolymerization accelerator, a radical polymerization initiator,
Claim 1 containing one or more additives such as a curing accelerator, a stabilizer, a glass forming agent, an organic gold compound (excluding silicon compounds), and a pigment. Coating composition 6 described above, component <x): alkoxysilanes, component (B): thiol-modified urethane (meth)acrylate resin, and component (q: photopolymerization initiator dissolved or dispersed in an organic solvent) Coating method 7, characterized in that the coating composition is applied to the surface of the substrate and photocured by irradiation with actinic rays, or further thermally cured after photocuring. Method 8 of claim 6, which is ultraviolet rays of 500 fl m, heat curing at a temperature of 80 to 300 ° C.
The method 9 according to claim 6, which is carried out by heating for a minute, and the method according to claim 6, in which the heat curing process is carried out after deformation processing of the photocured coated substrate.