JPS6094468A - Active energy ray curing coating material composition - Google Patents

Abstract

PURPOSE:The titled composition, containing an active energy ray curing composition and powder of a polymer containing fluorine atoms in a specific proportion, capable of giving improved protective and decorative coating films on metal, plastics, etc., an having improved flexibility of the films. CONSTITUTION:An active energy ray curing coating material composition obtained by incorporating (A) an active energy ray curing resin, e.g. triacrylate, having 5-10wt% tri- or polyfunctional reactive groups, with (B) preferably 1- 20wt%, based on the total composition, powder or beads of a polymer containing fluorine atoms, e.g. polytetrafluoroethylene having 0.5-20mu particle diameter.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an active energy ray-curable coating composition,
The purpose of the present invention is to provide an active energy ray-curable coating composition that provides excellent protective and decorative coatings to metals, glass, various plastics, wood, and other base materials.

Conventionally, active energy ray-curable coating compositions that are easily cured by irradiation with active energy rays such as ultraviolet rays and electron beams have been known. It is becoming widely used as a decorative paint. However, although these coatings have comparable surface hardness, they have the disadvantage that they are easily damaged by various types of friction and scratching. In order to solve these drawbacks, it is conceivable to use a large amount of polyfunctional resin as the active energy ray-curable resin, but in this case, the flexibility of the coating will decrease and the coated article will be difficult to bend. Another drawback is that the coating may crack.

As a result of intensive research to solve the above-mentioned drawbacks, the present inventor has found that when adding a specific material to an active energy ray-curable resin coating, it is possible to improve the abrasion resistance without impairing the flexibility of the formed film. The present invention was completed based on the finding that a coating material capable of forming a film with excellent scratch resistance can be obtained.

That is, the present invention comprises an active energy ray curable resin and a fluorine atom-containing polymer powder or beads, and about 5 to 100% by weight or more of the active energy ray curable resin has a trifunctional or higher functional reactive group, The present invention is an active energy radiation curable coating composition characterized in that the fluorine-containing polymer occupies about 0.1 to 40% by weight of the entire composition.

The invention will be explained in detail below.

The active energy ray curable resin composition used in the present invention is a known material and consists of an active energy ray curable resin, a sensitizer if necessary, and other optional components. Typical examples of active energy ray-curable resins include relatively low molecular weight polyester resins, polyether resins, acrylic resins, epoxy resins, urethane resins, which have radically polymerizable unsaturated double bonds in their molecular structures, It includes alkyd resins, oligomers or prepolymers such as acrylates and methacrylates of polyfunctional compounds such as polyhydric alcohols, and addition polymerizable compounds such as styrene, methylstyrene, divinylbenzene, and acrylic acid (or methacrylic acid) esters. It contains the following components singly or as a mixture. Further, as other examples of active energy ray-curable resins, cationic polymerization type resins such as vinyl ethers and epoxy resins can be used in the same manner as the radical polymerization type resins described above. These cationic polymerization types use a photosensitive catalyst, such as an aryl diazonium salt of a halide, to generate a Lewis acid with active energy rays, and produce vinyl-2-ethylhexyl ether, vinyl decyl ether, vinyl allyl ether, etc. vinyl ethers or mixtures thereof, 1,2-epoxycyclohexane, 1,2-epoxy-4-(epoxyethyl)cyclohexane, dicyclopentadiene dioxide, sorbitol polyglycidyl ether, 2゜21-bisC
Epoxy resins such as p-(2,3-epoxy)phenyl]propane or mixtures thereof are cationically polymerized. In the present invention, about 5 to 100 of these active stingrays are used as the Lugi's gland hardening resin:
It is desirable to use polyacrylates, polymethacrylates, or polyepoxides with a trifunctional or higher functional content such as triacrylate, trimethacrylate, sorbitol triglycidyl ether, etc., and when such polyacrylates are 5% by weight or less, sufficient surface Unable to form a hard film.

In addition, the sensitizers required when using ultraviolet rays as active energy rays are compounds that generate radicals by the energy of ultraviolet rays, such as carbonyl compounds such as benzoin, benzophenone or their esters, and peroxide. Examples include organic peroxides such as benzoyl, azo compounds such as azobisisobutyronitrile, and sulfur compounds such as diphenyl disulfide. In the case of cationic polymerization type, 2,5-jethoxy-4-(P-)lylthio)
The aryl diazonium salts of complex halides such as benzenediazonium hexafluorophosphate are used.

Other optional ingredients include small amounts of superposition solvents, coloring agents such as dyes and pigments, waxes and other various additives.

Active energy ray-curable resin compositions comprising the above-mentioned components are already known, and are used by changing the components and their quantitative ratios depending on the intended use. For example, when the application is a paint (coating agent) as in the present invention and ultraviolet rays are used, the sensitizer is used at a ratio of about 1 to 10 parts by weight per 100 parts by weight of the active energy ray-curable resin. is preferable. The viscosity of the paint is preferably adjusted to about 50 to 1000 cp using a liquid oligomer, monomer, or organic solvent. Such conventional active energy ray-curable coating compositions cure in a few seconds to several minutes by applying to the surface of a substrate and irradiating it with electron beams or ultraviolet rays of appropriate energy, creating a glossy and tough coating composition. A film can be formed.

The fluorine atom-containing polymer used in the present invention and which mainly characterizes the present invention is a homopolymer such as tetrafluoroethylene, hexafluoropropylene, chlorotrifluoroethylene, vinylidene fluoride, or a copolymer with other monomers. It is a powder pulverized to a particle size of about 0.1 to 100 μm or beads of a larger particle size, preferably a powder of about 0.0 μm of poly(y)lafluoroethylene.
It is a powder with a particle size of 5 to 20 microns. Such a fluorine atom-containing polymer is present in an amount of about 0.1 to 40% by weight in the entire composition;
It is preferably used in a proportion of about 1 to 10 parts by weight.

If the amount is below this range, good abrasion resistance and scratch resistance cannot be obtained, and if the amount is above the above range, the strength of the coating will be insufficient.

The essential components of the coating composition of the present invention are the same as those mentioned above, and the coating composition of the present invention can be obtained by simply mixing these components.

The coating composition of the present invention obtained as described above contains polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyamide, polyester, polycarbonate, A
When used as a coating for surface protection and surface decoration of base materials such as BS, As and other plastic molded products, glass, ceramics, metals, etc. (not limited to these base materials), it is much more effective than conventional similar paints. Provides a protective coating exhibiting excellent adhesion strength, surface abrasion resistance and scratch resistance.

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

In the text, the parts are based on weight.

Example 1 10 parts of polytetrafluoroethylene (Luburon L-2, manufactured by Daikin Industries, Ltd., average particle size of about 0.3 μm), bifunctional epoxy acrylate (molecular weight of about 400 to 800) 2(1,) riftylolpropane triacrylate 20 parts, 2-hydroxy-2methyl-1-phenylpropan-1-one 1
parts, isopropyl 7/l/cole 20 parts, toluene 20 parts
20 parts of Lucerosolve were uniformly mixed to obtain a coating composition of the present invention having a viscosity of ≠4 Ford cup 15 seconds (at 25°C).This coating was applied to a spray gun (nozzle diameter Goo 1.3 proverbs, air pressure 3 surprises) and 5 on the ABS board
It was applied to a thickness of ~15 μm, dried at 60°C to 80°C for 5 minutes, and then irradiated with ultraviolet rays for 5 to 20 seconds using a high-pressure mercury lamp at 80 W/cm to cure the coating film.
The exterior has a beautiful translucent matte finish, and 1
It is 100/100 in the column pitch cross-cut test, and the limit load of the rotary steel wool test ("000
A circular pad of steel wool is pressed under a constant load and rotated 100 times at 60 rpm, and the minimum load at which scratches begin to clearly appear on the sample is 2.
It had good resistance to scratching at Kf and good chemical resistance. For comparison, the method of Example 1 was repeated except that polytetrafluoroethylene was not used, and the steel wool test limit load of the resulting coating film was 300 V. In alkali resistance (48-hour spot test with IN NaOH aqueous solution), paint film whitening and deterioration occurred.

In addition, as a substitute for trimethylolpropane triacrylate, the method of the above example was repeated using 20 parts of triethylene glycol diacrylate. /100 close contact.

Example 2 Copolymer of tetrafluoroethylene and ethylene (770
yCOP Z-8820, manufactured by Asahi Glass, average particle size 20μ
m) 15 parts, bifunctional urethane acrylate (molecular weight 1.
500 to 2,000), 30 parts of dipentaerythritol hexaacrylate, 10 parts of tripropylene glycol diacrylate, 2 parts of jetoxyacetophenone, 1 part of benzophenone, and 15 parts of toluene were uniformly mixed at 350CP (25°C). A coating composition of the present invention was obtained with a viscosity of . This coating material was coated on polycarbonate for glazing to a thickness of 30 μm using a natural roll coater.
When the coating was cured by irradiating it with ultraviolet rays for 4 to 10 seconds using an RA high-pressure mercury lamp, the appearance was similar to that of frosted glass, and it showed scratch strength, chemical resistance, abrasion resistance, stain resistance, and weather resistance. A coating film with excellent properties is obtained with a load of 500v C8-
Taper wear male due to 17) 1. The wear loss during OOO rotation was 1.5 q, and the cross cut test after 1,000 hrs of sunshine weather off-tering was 100/100 T, and the weight was 0. For comparison, Aphron polymer was not used. Weight loss u50W9 of the taper abrasion test of the coating film formed by repeating the above example as is except for the following. After 1,000 hrs of Sunshine Unisaometer, the first cross canto was 0/100.

In addition, the weight loss in the taper abrasion test of the coating film formed by repeating the above example using Aphron polymer and using 30 parts of tetrahydrofuryl acrylate in place of dipentaerythritol hexaacrylate was 10~, and Sunshine Weather. After 1,000 hrs of off-season, the adhesion of loss cut in the first round was 30/100.

Example 3 Polyethylene beads coated with polyfluoroethylene (Celidas) 9610F, manufactured by Hoechst, average particle size 1
5 μm) 20 parts, wax-free unsaturated polyester resin face (containing 3 or more functional groups, fat content 60%, styrene monomer 30%) 75 parts, styrene monomer 5 parts,
2 parts benzoin isobutyl ether and 20 parts toluene
A coating composition of the present invention having a viscosity of 5000 P (30° C.) was obtained by uniformly mixing the two parts. This paint was applied to the surface of a board made of lauan plywood laminated with wood grain printing paper (23~soy/m') using a curtain flow coater at 50~100f/r.
r? After applying at a ratio of
/cWL mercury lamp for 20 to 30 seconds to cure and dry the coating film. The resulting coating film has a beautiful matte appearance, scratch strength and abrasion resistance (soof
Taper wear test with load C8-17 i, wear loss at ooo rotation 2v9), cold and heat cyclic test) (-30°C
A good coating film was obtained (10 cycles at 70°C, 6 hour intervals).

For comparison, the coating film formed by repeating the above example without using Ceridus 9610F had a taper abrasion loss of 645 or more and cracked in the cold/hot cyclic test.

Example 4 20 parts of polytetrafluoroethylene (TLP-10p-1, manufactured by Mitsui Fluorochemical, 8-16μ), 40 parts of bifunctional urethane acrylate (molecule ill, 500-2°000), 20 parts of trimethylolpropane trimethacrylate and 20 parts of N-vinyl 2-pyrrolidone are uniformly mixed;
An electron beam curable coating composition of the present invention having a viscosity of 500 CP (25° C.) was obtained.

Apply this paint to polyvinyl chloride flooring with a roll coater for 40 minutes.
When the coating was applied to a thickness of μm and cured by irradiation with a 50 Mrad electron beam for 3 seconds, a beautiful translucent matte coating was obtained. It has excellent scratch strength, chemical resistance, abrasion resistance, stain resistance, and blocking resistance, and the weight loss at 1.000 revolutions was 25 ■ in the 5002 load taper wear test.

For comparison, the coating film formed by repeating the above example without using TLP-10F-1 had a tapered abrasion test of 45 cm and poor blocking resistance. .

Further, when TLP-10F-1 was used and 20 parts of tripropylene glycol dimethacrylate was used in place of trimethylolpropane trimethacrylate, the taper abrasion test weight loss was 12 ■.

Example 5 10 parts of polytetrafluoroethylene (Fluon L-171° manufactured by Asahi Fluoropolymer, 3-4 μm), 40 parts of sorbitol polyglycidyl ether (average 4 functional), 2,2'
-bis(P-(2,3-epoxy)phenyl]furopane 40 parts, 2,5-jethoxy-4-(p-tolylthio)
2 parts of benzenediazonium hexafluorophosphate and 10 parts of ethyl acetate were mixed uniformly to make 100
A coating composition of the present invention having a CP/30°C was obtained. This paint was applied to an aluminum plate with a roll coater to a thickness of 20 μm, and after drying with hot air at 60°C for 2 minutes, it was heated to 80 W/cIIL.
When the coating was cured by irradiating it with a high-pressure mercury lamp for 5 to 10 seconds, a beautiful translucent matte coating was obtained, with excellent scratch resistance and
A coating film with excellent chemical resistance, abrasion resistance, salt water spray test (96 hours no change), and 2-bit cross-cut sellotape peeler test of 100/100 was obtained.

For comparison, the coating film formed by repeating the above example except that Fluon L-171 was not used rusted after 48 hours of salt water spraying, and the cross-cut adhesion was 40%.
/100.

Also, in place of sorbitol polyglycidyl ether, 1.
When 40 parts of 4-bis(epoxypropoxy)butane was used, the adhesion after 96 hours of salt water spraying was 5/100.
Met.

Claims (1)

[Claims] (1) Composed of an active energy ray curable resin and a fluorine atom-containing polymer powder or beads, about 5 to 100% by weight of the active energy ray curable resin has a trifunctional or higher functional reactive group, and the fluorine atom A photocurable coating composition characterized in that the contained polymer accounts for about 01 to 40% by weight of the entire composition.