JPS58198571A - Coating composition - Google Patents

Abstract

PURPOSE:To provide a coating compsn. giving films excellent in physical properties by crosslinking and hardening by heat or radiation energy, by incorporating a particular reaction product as a film forming component. CONSTITUTION:A reaction product is obtained by reacting a monohydroxyl or monoamine compd. having an alpha,beta-ethylenically unsatd. carboxyl group [e.g., 2- hydroxyethyl (meth)acrylate], a polyhydroxy or polyamine compd. having an alpha,beta-ethylenically unsatd. carboxyl group, a polyhydroxy or polyamino-terminated digomer having a MW of 1,000-4,000, and polyisocyanate in an eq. ratio of 3:2-8:4-10:8-20. Then 1-40wt% said reaction product is dissolved or dispersed in water and/or org. solvent (e.g., toluene).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel coating composition, and more specifically, aims to provide a novel coating composition that is cross-cured by heat or radiation energy and provides a coating with excellent physical properties. shall be.

Conventionally, a coating material that is cross-linked and cured by radiation has been used! Many j#lFl compositions are known, but the main film-forming properties of these conventional coating compositions are relatively low molecular weight fluorophores and oligomers.
-, the formed film has insufficient adhesion, 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 can be solved by using a multifunctional polymer with a specific composition as the main film-forming agent. After discovering this, the present invention was completed.

That is, according to the present invention, a, a monohydroxy t + monoamino compound (A) having a monoethylenically unsaturated carbonyl group, a polyhydroxy or polyamino compound (B) having a monoethylenically unsaturated carbonyl group, molecular weight This is a coating composition containing a reaction product obtained from a polyhydroxy or polyamino oligomer (C) having a terminal polyhydroxy or polyamino oligomer (C) of about i, ooo to 4ooo and a polyisocyanate compound as the main film-forming components.

To explain the present invention in more detail, the compounds used in the present invention (acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, etc.) and diol compounds, polyol compound,
It is obtained by reacting a polyfunctional compound such as a monoamino polyalcohol compound so that one hydroxyl group and one amino group remain, and preferable examples include 2-hydroxyethyl (meth)acrylate,
These include 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, and the like. These compounds (Al) form terminal functional groups of the polyfunctional polymer that is the film-forming component used in the present invention.

In the compound (11Fi, (1) trifunctional or more functional polyol, aminopolyol, a as described above is added so that two functional groups remain.
.

A method for reacting β-ethylenically unsaturated carboxylic acid with a metal conductor, (2) 11th P monoamine compound,
.

Adding one glycidyl group or γ-halogeno β-hydroxy-1-propyl group to a compound having two hydroxyl groups, a secondary amino group, a carboxyl group, a phenolic hydroxyl group, etc.
It can be obtained by reacting a,β-ethylenically unsaturated carbonyl compounds.

In the method (1) above, it is preferable to use polyols such as glycerin, trimethylolpropane, pentaerythol, jetanolamine, and diglobanolamine. In the method (2) above, ethylene glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, their dimers, trimers, polymers, neopentyl glycol, ethylene oxide of bisphenol A, or propylene oxide addition products, polyethylene Diols such as adipate glycol, polybutylene adipate glycol, and polybutadiene glycol; Amino alcohols such as N-methylethanolamine, N-propylethanolamine, N-methylpropaturamine, and N-ethylpropaturamine; hexyl amine, laurylamine,
Primary amines such as aniline; those using bisphenols such as bisphenol A are preferred; unsaturated carbonyl compounds to be reacted with these 1 include glycidyl (meth)acrylate, r-chloro-β-hydroxy ---Propyl (meth)acrylate is a preferred book.

Another method is to react an unsaturated carboxylic acid such as (meth)acrylic acid with a diglycidyl compound or a di(r-halo β-hydroxy-n-propyl) compound obtained by reacting epihalohydrin with the above-mentioned diol. It may be used as a compound (B) obtained by

The oligomer (C) has a hydroxyl group and an amino group at the end of the polymer chain, and for example, as the poly-chain, 1,2- or 1,4-polybutadiene, polyisoprene, polychloroprene, butadiene-styrene copolymer. , styrene-isoprene copolymers, butadiene-acrylonitrile copolymers, or partial or complete additives thereof; polyethylene, polypropylene, polybutylene, ethylene-globylene copolymers, etc.; polystyrene, etc.; poly-limethyl acrylate, etc.;
polyethylene oxide, polypropylene oxide,
Ethylene oxide-propylene oxide copolymer, polytetramethylene ether, etc.: polyethylene adipate, polybutylene adipate, polyethylene butylene adipate, polycaprolactone, polybutylene terephthalate, addition product of bisphenol A and propylene oxide and adipine compound , polyesters with terephthalic acid, isophthalic acid, etc.; polyamides with dimer acids and alkylene diamines such as ethylene diamine and hexamethylene diamine; polyamides with dicarboxylic acids such as azelaic acid and sebacic acid and hexamethylene diamine; diols and diisocyanates. 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 t.oo.

-4,000, and those having a molecular weight outside this range cannot achieve the object of the present invention.

In addition, the most preferred terminal group is Mononoke hydroxyl group,
Preferably 2 pieces.

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 diinocyanate, lysine diisocyanate, trimethylhexamethyl diisocyanate, and the like.

The above-mentioned compounds (A) to (CI) and polyisocyanates are all examples, and known compounds (A) to (C) and polyisocyanates other than these U can also be used in the present invention. Either compound can be used alone or in mixtures.

The film-forming agent used in the present invention is manufactured by reacting the above-mentioned components, and the manufacturing method itself is similar to the conventional manufacturing method of polyurethane or raw polyurea. However, since the raw materials have α,β-ethylenic groups, about 50 to 2. o o o ppm of hydroquinone, butylhydroquinone, benzoquinone, P
- Inhibition of polymerization of methoxyphenol, etc.! 1 of the raw materials and products in the presence of 1! ! It is preferable to prevent bridges.

Although all the raw materials may be reacted simultaneously, in order to form the desired structure and to narrow the molecular weight distribution of the product as much as possible, the reaction order of the raw material 1 is defined and the reaction is performed in stages. It is preferable to adopt the polymer method. 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.

The solvent used for a.phi. is a known solvent that can be used as is.

The coating composition obtained in the manner 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 coating composition of the present invention has an average molecular weight of about 2. ,000 to 20,000, and the α,β-ethylenic group has a molecular weight of 1,000 to 20,000, and
Approximately 0.2 to 6 books per 000. The film-forming properties of such a force composition are as follows: (A):
(B): (C): Polyisocyanate = 2:2~
It is obtained by setting the ratio to be 8:4 to 10:8 to 20.

*lk of the polymer used in the present invention for 4 minutes of film formation
is a polyurethane or polyurea chain consisting of oligomer (q) and polyisocyanate, both ends are residues of compound (4), compound (B) is incorporated into the main chain, and compound ( This is a structure in which the α,β-ethylenically unsaturated carbonyl group of B) is bonded to the main chain as an indentation.

The coating composition of the present invention has the above-mentioned film-forming agent and a medium for dispersing the component in the solution M as essential components. When the substance 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 S-containing solvents, such as hydrocarbons such as toluene, xylene, solvent naphtha, cyclohexane, methylcyclohexane, isoparaffins, ligroin, mineral spirits, etc.: ethyl acetate, butyl acetate, butyl butyrate, etc. Ester systems; Ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexane, and diacetone alcohol; Ethers such as dioxane and tetrahydrofuran; alcohols such as ethanol, propanol, and butanol; butyl cellosolve, ethyl cellosolve, butyl cellosolve , ethers and esters such as methyl cellosolve acetate and ethyl cellosolve acetate; amide types such as dimethylformamide and dimethylacetamide are preferred;
These solvents may be used alone or as a mixture, and inert ones may be used as a reaction solvent during the production of the coating composition and may also be used as a medium for the coating composition. The amount of film-forming quarter added to such a medium varies depending on the method of use of the coating composition, required additives, etc., but is generally 5 to 80, preferably 10 to 40, of the total amount of the composition. weight%
range.

The coating composition of the present invention cross-links and cures the coating edges and film-forming properties on the surface of the article to form an excellent film. Add additives.

In the case of heat-crosslinking and curable compositions, benzoyl peroxide, lauroyl peroxide, cumennohydroboroxide, methyl ethyl lactone peroxide,
Persulfate, azobisisobutyronitrile, azobiscyanovaleric acid, and other polymerization initiators are added to the film forming component i.
oo about 0.1 to 10 per part by weight, preferably 05 to 5
Use parts by weight. Further, it is also preferable to use N,N-dimethylaniline, cobalt nanthenate, sodium abort sulfate, etc. in combination to form a redox system.

In the case of photocurable type, benzoin, benzoin alkyl ether, benzophenone, benzyl, anthraquinone,
The photopolymerization initiator, such as benzoin dimethyl ketal, 2-ethylthioxanthone, etc., is used in a proportion of about 0.1 to 10, preferably about 1 to 5, parts by weight per 100 parts by weight of film-forming mass.

When crosslinking and curing with high energy beams such as electron beams,
The use of a polymerization initiator as described above is essential.

The coating composition of the present invention as described above may contain various other additives. One example is Kishite Mori, a polyfunctional monomer that promotes cross-linking of film-forming components, and a relatively low molecular weight (:
There are oligomers with the following properties: For example, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra( Oligomers such as meth)acrylate, dipentaerythritol hexaacrylate, epoxy acrylate, urethane acrylate, polyester acrylate, and polyether acrylate are used to form the above-mentioned film.
It can be used in a proportion of 0 to 100 parts by weight per lj parts. Such monomers and/or oligomers can also serve as the above-mentioned organic sieve.

As other additives, dyes and pigments, coloring agents, fillers, ferromagnetic particle materials, conductive materials, acupuncture zelkova 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, glass molded products, wood, plywood, paper, plastic films,
Protective coating for leather, woven fabrics, and various other articles, decorative waves,
Binders for printing inks, printing agents, etc., resists for plate making, shadow masks, name plates, printed wiring,
It can be used as a resist for processing waste food such as integrated circuits, 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 using the coating composition of the present invention has various properties such as adhesion, flexibility, impact resistance, elasticity, toughness, electrical properties, and temperament, compared to conventional ultraviolet or radiation-curable coatings. Excellent in performance.

Such excellent performance is attributable to the specific structure of the film-forming substance of the present invention described above.
The present invention will be specifically explained with reference to Examples. In addition, the middle part of the sentence is F again! , 91, based on weight.

Reference Example 1 Pentaerythritol triacrylate, 1,2-bis(r-acryloyloxy-β-hydroxy-n-propyloxy)ethane, 1,2-polybutadiene glycol (average molecular weight approximately 3,000) and triacrylate Dissolve diisocyanate in an equivalent ratio of 2:6:8:16 in about 31 times the amount of methyl ethyl ketone, and further remove the nonvolatile content.
0.05-hydroquinone and 0.1-diptyltin silaurylate were added and reacted at 50 to 80°C for 20 hours to obtain a polyurethane resin having an average molecular weight of about 15,000.

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

稠 啼 I#M HE -
啼 aD w - 啼 ■
＋il 轡
-NN 4
111 8N 啼＠F
2O3soaOto
Example 1 80 parts of the polyurethane resin of Reference Example 1, 20 parts of Sugesin monomer, 2 parts of trimethylolpropane triacrylate
0 parts, 5 parts of benzoin dimethyl ketal, 2 parts of N-methyljetanolamine 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 In the same manner as in Example 1, layered compositions of the present invention having the compositions shown in Table 2 below were obtained.

Usage examples 1 to 8 The results of using the above coating composition of the present invention are shown below.

It is shown in Table 3.

Table 3 2011I/llllm 40+++/ml cooperative parts 50■/m1m
High wear resistance Example 4 Gravure coater
Electron beam electrical insulation outer size 4 polyester
srl & 50MR strong-Ichisei large film 40 strips/fIII
High adhesion side 5 Offset printing High pressure water correction High gloss S paper
1 @ Ow/emx 1 piece 30 +a/m
l Parrot 011 Slom/mi
In addition, the coating 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 t'Ifr performance was obtained immediately after use in the same manner as in Example 8.

Patent applicant: Dainichi Seishi Kogyo Co., Ltd. 1 Procedural amendment (spontaneous) June 2, 1980 Commissioner of the Japan Patent Office 1, Indication of case Percentage patent application 2 dated May 14, 1980, Covering the name of the invention Composition 3, relationship to the case of the person making the amendment Patent applicant address 7-6 Nihonbashi Bakurocho-chome, Chuo-ku, Tokyo Name (282) Dainichiseika Kagyo Co., Ltd. Representative Hata Takahashi 4, agent address Central Tokyo] Me Nihonbashi Bakurocho-chome 7-6 (
〒103) 5. Subject of amendment Application and specification 6. Contents of amendment Type and copy the attached application for abstract and specification (no changes to the contents).

497-

Claims (1)

[Claims] (t) ” + Monohydroxy or monoamino compound having a 7'-ethylenically unsaturated carbonyl group, direct,
-Polyhydroxymatasha polyamino compound having a monoethylenically unsaturated carbonyl group, with a molecular weight of about 1,000 or more
4,000-terminated polyhydroxy or polyamino oligomer and a reaction product obtained from a polyinocyanate compound as the main film-forming agent. (2) The coating composition according to item t'9 of claim (1), wherein the a.-monoethylenically unsaturated carbonyl group is an acryloyl group.