JPS6049667B2 - Coating composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel coating compositions, and more particularly to:
The purpose of the present invention is to provide a novel coating composition that is crosslinked and cured by heat or radiation energy to provide a coating with excellent physical properties.

Many coating compositions that can be cross-linked and cured by radiation are known, but since the main coating components of these conventional coating compositions are relatively low molecular weight monomers and oligomers, the adhesion of the formed coating is difficult. It has insufficient flexibility, flexibility, impact resistance, etc., and it is also difficult to completely polymerize all monomers and oligomers.

As a result of intensive research to solve the above-mentioned drawbacks of the prior art, the inventors of the present invention have found that the above-mentioned drawbacks of the prior art have been solved by using a multifunctional polymer with a specific composition as the main film-forming component. The present invention was completed based on this knowledge.

That is, the present invention provides a monohydroxy or monoamino compound (2) having an α/β monoethylenically unsaturated carbonyl group, a polyhydroxy or polyamino compound (B) having an α/β monoethylenically unsaturated carbonyl group, and a polyhydroxy or polyamino compound (B) having a molecular weight of There is a coating composition containing a reaction product obtained from a terminal polyhydroxy or polyamino oligomer (C) of about 1,000 to 4,000 and a polysisocyanate compound as the main film-forming components.

To explain the present invention in more detail, the compound (2) used in the present invention includes an α,β-ethylenically unsaturated carboxylic acid such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, and itaconic acid, and a diol compound; It is obtained by reacting a polyfunctional compound such as a polyol compound or a monoamino polyalcohol compound so that one hydroxyl group or amino group remains. For example, a preferable example is 2-hydroxyethyl (meth). ) acrylate, 2
-Hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, etc.

These compounds (4) form the terminal functional groups of the polyfunctional polymer which is the film-forming component used in the present invention.
Compound (B) is added to (1) trifunctional or more functional polyol or aminopolyol so that two functional groups remain.
A method of reacting a β-monoethylenically unsaturated carboxylic acid or a derivative thereof, (2) a method of reacting a glycidyl group with a primary monoamine compound, a compound having two hydroxyl groups, a secondary amino group, a carboxyl group, a phenolic hydroxyl group, etc. It can be obtained by reacting an α●β monoethylenically unsaturated carbonyl compound having one γ-halogen or β-hydroxy-n-propyl group.

In the method (1) above, it is preferable to use polyols such as glycerin, trimethylolpropane, pentaerythritol, diethanolamine, and dipropanolamine.

In the method (2) above, ethylene glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, dimers, trimers, polymers thereof, neopentyl glycol, ethylene oxide of bisphenol A, or a propylene oxide addition product, polyethylene adipate. Diols such as glycol, polybutylene adipate glycol, polybutadiene glycol; Amino alcohols such as N-methylethanolamine, N-propylethanolamine, N-methylpropanolamine, N-ethylpropanolamine: hexylamine, rauramine, aniline, etc. 1st of
grade amines; those using bisphenols such as bisphenol A are preferable, and as the unsaturated carbonyl compound to be reacted with these, glycidyl (meth)acrylate and γ-chloroβ-hydroxy-n-propyl (meth)acrylate are preferable. It is something. As another method, a diglycidyl compound or a di(γ-halo β-hydroxy-n-propyl) compound obtained by reacting epihalohydrin with the above diol or other (meth)
It may also be used as a compound (B) obtained by reacting an unsaturated carboxylic acid such as acrylic acid.

The oligomer (C) has a hydroxyl group or an amino group at the end of the polymer chain, and for example, the polymer chain includes 1,2- or 1,4-polybutadiene, polyisoprene, polychloroprene, butadiene-styrene copolymer, Styrene-isoprene copolymer, butadiene-acrylonitrile copolymer, or their partial or fully hydrogenated products; polyethylene, polypropylene, polybutylene, ethylene-propylene copolymer, etc.; polystyrene, etc.; polymethyl acrylate, etc.; polyethylene oxide, polypropylene oxide, ethylene oxa Idopropylene oxide copolymer, polytetramethylene ether, etc.: polyethylene adipate, polybutylene adipate, polyethylene butylene adipate, polyε-caprolactone, polybutylene terephthalate, addition product of bisphenol A and propylene oxide and adipic acid, terephthalic acid, isophthalic acid. Polyesters with acids, etc.; polyamides with dimer acids and alkylene diamines such as ethylene diamine and hexamethylene diamine; polyurethanes made with polyamide diols and diisocyanates with dicarboxylic acids such as azelaic acid and sebacic acid and hexamethylene diamine, etc. These polymer chains may be in any form such as homopolymers, random copolymers, graft copolymers, block copolymers, etc.

Such polymer chains have an average molecular weight of about 1000 to 4
000, and if the molecular weight is outside this range, it will be difficult to achieve the intended purpose of the present invention.

Furthermore, the most preferable terminal group is a hydroxyl group,
Approximately two pieces is preferred.

Examples of the polyisocyanate used in the present invention include tolylene diisocyanate, 4,4''-diphenylmethane diisocyanate, naphthalene diisocyanate,
These include toridine diisocyanate, phenylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, dicyclohexylmethane diisocyanate, lysine diisocyanate, trimethylhexamethyl diisocyanate, and the like.

The above-mentioned compounds (4) to (C) and polyisocyanates are all examples, and other known compounds (4) to (C) and polyisocyanates can also be used in the present invention.

Further, any of the compounds can be used alone or in a mixture. The film-forming components used in the present invention are manufactured by reacting the above-mentioned components, and the manufacturing method itself is similar to the conventional manufacturing method of polyurethane or polyurea. However, since the raw material has α/β monoethylenic groups, approximately 50 to 2000 ppm of a polymerization inhibitor such as hydroquinone, butylhydroquinone, benzoquinone, or P-methoxyphenol is present in the reaction system during the reaction to inhibit the raw material and product. Preferably, crosslinking is prevented. Although all raw materials may be reacted at the same time, the prepolymer method involves specifying the reaction order of the raw materials and reacting them in stages in order to form the desired structure and to narrow the molecular weight distribution of the product as much as possible. It is desirable to adopt Such a prepolymer method itself is known, and any known method can be employed. Such a reaction may be carried out in an inert solvent or without a solvent. As the solvent itself, any known solvent can be used as is. The film-forming components obtained as described above can be obtained with various molecular weights by changing the ratio of raw materials used and the reaction method, but a particularly preferred film composition of the present invention has an average molecular weight of about 2000. ~20000, and α
・β-ethylenic group is about 0.2 to 1000 molecular weight
There are 6 pieces.

The film-forming components having such a composition are compounds (4) to (C
) and the usage ratio (equivalent ratio) of polyisocyanate (
A):(B):(C):Polyisocyanate 2:2~
It is obtained by setting the ratio to be 8:4 to 10:8 to 20. The structure of the polymer that is the film-forming component used in the present invention is as follows:
Its main chain is a polyurthane or polyurea chain consisting of oligomer (C) and polyisocyanate, both ends are residues of compound (4), compound (B) is incorporated into the main chain, and compound (B) It has a structure in which α and β monoethylenically unsaturated carbonyl groups are bonded to the main chain as pendants.

The coating composition of the present invention contains the above-mentioned film-forming components and a medium for dissolving or dispersing the components as essential components.

When the medium is water, it is generally a dispersion in water or an emulsion in water, and when the medium is an organic solvent, it is generally a solution or a water-in-oil emulsion. Preferred organic solvents are relatively volatile organic solvents, such as hydrocarbons such as toluene, xylene, solvent naphtha, cyclohexane, methylcyclohexane, imparaffins, ligroin, mineral spirits; ethyl acetate, butyl acetate, butyl butyrate. Ester systems such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diacetone alcohol, etc.; ethers such as dioxane, tetrahydrofuran; methanol, ethanol,
Alcohols such as propanol and butanol; ethers and esters such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, and ethyl cellosolve acetate; dimethyl formamide,
Amide solvents such as dimethylacetamide are preferred, and these solvents may be used alone or as a mixture;
An inert solvent may be used as a reaction solvent during the production of film-forming components, and may be used as a medium for the film composition as it is. The amount of film-forming components added to such a medium varies depending on the method of use of the film composition, required additives, etc., but is generally 5 to 80% of the total amount of the composition, preferably 10 to 4% of the total amount of the composition. % range. After the coating composition of the present invention is applied to the surface of an article, the coating composition is crosslinked and cured to form an excellent coating. Add various additives.

In the case of heat crosslinking curable compositions, polymerization initiation of benzoyl peroxide, lauroyl peroxide, kyumene hydroperoxide, methyl ethyl ketone peroxide, persulfate, azobisisobutyronitrile, azobiscyanovaleric acid, etc. Apply the agent for 1 minute to form a film.
About 0.1-10, preferably 0.5-10 per 00 parts by weight
It is used in a proportion of 5 parts by weight.

It is also preferable to use N●N-dimethylaniline, cobalt naphthenate, sodium sulfite, etc. in combination to form a redox system. In the case of photocurable type, benzoyl, benzoin alkyl ether, benzophenone, benzyl,
Anthraquinone, benzoin dimethyl ketal, 2-ethylthioxanthone and other photopolymerization initiators are added in an amount of about 0.1 to 101, preferably about 1
~5 parts by weight.

When crosslinking and curing with high energy beams such as electron beams,
The use of polymerization initiators as described above is not essential. The coating composition of the present invention as described above may contain various other additives.

Examples include polyfunctional monomers and relatively low molecular weight (usually less than 1000) oligomers that promote crosslinking of film-forming components.

For example, ethylene glycol di(meth)acrylate,
Diethylene glycol di(meth)acrylate, triethine glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexaacrylate, epoxy acrylate , urethane acrylate, polyester acrylate, polyether acrylate, and the like can be used in an amount of 0 to 100 parts by weight per 10 parts by weight of the above-mentioned film-forming components. Such monomers and/or oligomers can also serve as the organic medium. As other additives, dyes and pigments, colorants, fillers, ferromagnetic fine particle materials, conductive materials, mineral fibers, and other arbitrary additives may be added as necessary.

The coating composition of the present invention as described above can be applied to metal products, plastic molded products, wood, plywood, paper, plastic films,
Protective coatings and decorative coatings for leather, woven fabrics, and various other items.
Binders for printing inks, printing agents, etc., image resists for plate making, shadow masks, name plates, printed wiring,
It can be used as a resist for corrosion processing of integrated circuits, etc., and various other products.

The application of the composition of the present invention to various articles and the crosslinking and curing method itself may be conventionally known methods.

The crosslinked cured coating obtained from the coating composition of the present invention has better performance in various properties such as adhesion, flexibility, impact resistance, elasticity, toughness, and electrical properties compared to conventional ultraviolet or radiation-curable coatings. It is excellent.

Such superior performance is attributable to the specific configuration of the coating components of the present invention described above.

Next, the present invention will be specifically explained with reference to Reference Examples and Examples.

In addition, it is based on the middle part of the sentence, %, or weight. Reference Example 1 Pentaerythritol triacrylate, 1●2-bis(γ-acryloyloxy-β-hydroxy-n-propyloxy)ethane, 1,2-polybutadiene glycol (average molecular weight about 3000) and tolylene diisocyanate in an equivalent ratio of 2: It is dissolved in about 3 times the weight of methyl ethyl ketone in a ratio of 6:8:16, and further contains 0.0% of non-volatile matter.
0.05% hydroquinone and 0.1% dibutyltin dilaurylate were added and reacted at 50 to 80°C for a period of time to obtain a polyurethane resin having an average molecular weight of about 15,000.

Reference Examples 2 to 18 Various polyurethane resins were obtained in the same manner as in Reference Example 1, except that the materials in Table 1 below were used in place of the materials in Reference Example 1.

Example 1 Polyurethane resin tap part, styrene monomer head part, trimethylolpropane triacrylate 2? of Reference Example 1? , 5 parts benzoin dimethyl ketal, 2 parts N-methyldiethanolamine and small amounts of additives (wax,
An antifoaming agent, a leveling agent) were added to obtain a coating composition of the present invention.

Examples 2 to 8 Coating compositions of the present invention having the compositions shown in Table 2 below were obtained in the same manner as in Example 1.

Examples 1 to 8 The results of using the above coating composition of the present invention are shown in Table α3 below.

In addition, the film composition of the present invention obtained in the same manner as Examples 1 to 8 using the polyurethanes of Reference Examples 9 to 18 was used in Use Example 1.
A film with excellent performance was obtained using the same method as in Example 8.

Claims (1)

[Scope of Claims] 1. A monohydroxy or monoamino compound having an α/β-ethylenically unsaturated carbonyl group, a polyhydroxy or polyamino compound having an α/β-ethylenically unsaturated carbonyl group, and having a molecular weight of approximately 1,000 to 4,000. A coating composition comprising a reactive composition obtained from a terminal polyhydroxy or polyamino oligomer and a polyisocyanate compound as the main coating component. 2. The coating composition according to claim 1, wherein the α/β-ethylenically unsaturated carbonyl group is an acryloyl group or a methacryloyl group.