JP2002187243A - Uv curing-type covering material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a UV curing-type covering material having good workability and capable of providing a film having sufficient surface properties and smoothness. SOLUTION: A UV curable resin composition consists of (A) 10-90 pts.wt. of a UV curable monomer, (B) 10-90 pts.wt. of a vinyl polymer having an anionic dissociation group such as a carboxyl group or a sulfo group, and relative to 100 pts.wt. of the sum of the component (A) and the component (B), (C) 1-10 pts.wt. of a photo-polymerization initiator and (D) 0-20 pts.wt. of a wax. The UV curing-type covering material is made by laminating the UV curable resin composition with a UV transmitting film.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ultraviolet-curable coating material.

[0002]

2. Description of the Related Art Existing building materials such as floors and walls, structures and moldings are coated with a coating material to prevent dirt, protect a base material, and maintain aesthetic appearance. Is common.

[0003] As such a coating material, a solvent type in which a synthetic resin is dissolved with a solvent is generally used. However, due to the danger to the working environment and fire, the synthetic resin, a reactive compound and the like are dissolved in water. A dispersed emulsion type (Japanese Patent No. 2597238, Japanese Patent Application Laid-Open No. 9-59568),
JP-A-9-71720), an ultraviolet-curable type using an ultraviolet-curable paint (JP-A-6-279566,
JP-A-9-77820) and the like have been variously developed.

[0004]

However, in such conventional coating materials, the emulsion type requires a large amount of energy to evaporate water after application, and in the case of drying at room temperature, it takes one week or more to completely cure. In addition, the ultraviolet curable type has a problem that it is difficult to exhibit sufficient surface properties as a coating agent due to inhibition of curing by oxygen.

[0005] In order to eliminate curing inhibition by oxygen, a photocationic polymerization system or a cation-radical hybrid polymerization system has been proposed (Japanese Patent Application Laid-Open No. 9-137079).
JP-A-9-151237) and a problem that the curing speed is slower than that of a radical polymerization system.

[0006] Further, in any type, it is general to apply by a roll, brushing or the like, and it is also a serious problem that in order to obtain smoothness which can be used as a coating material in field coating, skill is required. It has become one of.

Further, for the purpose of simplifying repair and design change, it is desired to remove the coating material, and a coating material having good removability has been developed (Japanese Patent No. 2549288).
No.).

The present invention has been made in view of the above circumstances, and provides a coating having good workability, a sufficient surface physical property and smoothness, and excellent removability. The purpose is to provide.

[0009]

The ultraviolet-curable coating material of the present invention is obtained by laminating an ultraviolet-curable resin composition comprising the following (A) to (D) with an ultraviolet-transmitting film.

(A) 10 to 90 parts by weight of an ultraviolet-curable monomer (B) 10 to 90 parts by weight of a vinyl polymer having an anionic dissociating group, based on 100 parts by weight of the total of the components (A) and (B) (C) Photopolymerization initiator 1 to 10 parts by weight (D) Wax 0 to 20 parts by weight.

[0011]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The matters relating to the implementation of the present invention will be described below in detail.

As the UV-curable monomer (A) in the present invention, known and commonly used ones can be used. Typical examples thereof include 2-ethylhexyl acrylate and 2-ethylhexyl acrylate.
Styrene, methyl methacrylate, tetrahydrofurfuryl (meth) acrylate, phenoxyethyl (meth)
Acrylate, isobornyl (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,4 butanediol di (meth) acrylate , 1,6 hexanediol di (meth) acrylate, EO-modified bisphenol di (meth)
Acrylate, PO-modified bisphenol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth)
Acrylate, PO-modified trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris ((meth) acryloxyethyl) isocyanurate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate And the like. These may be used alone or in combination of two or more.

The vinyl polymer having an anionic dissociating group (B) is a vinyl polymer having an anionic dissociating group such as a carboxyl group or a sulfo group in the molecule.
As the monomer, not only a typical vinyl compound but also a polymer / copolymer using various ethylene substituents such as a vinylidene compound and a vinylene compound can be used.

Preferably, a vinyl polymer having a carboxyl group or a sulfo group is used. Specifically, as a monomer, (meth) acrylic acid, crotonic acid, cinnamic acid, maleic acid (or a Monoalkyl ester), fumaric acid (or its monoalkyl ester)
And vinyl polymers polymerized using a polymerizable unsaturated group-containing sulfonic acid such as vinylsulfonic acid and 2-sulfoethylacrylamide. These monomers may be used alone or in combination of two or more. Further, it is desirable to use a monomer having no anionic dissociating group together with these monomers as a copolymerization component. As such a copolymer component, a known component can be used, and typical examples include styrene, ethyl acrylate, butyl acrylate, methyl methacrylate, and 2-ethylhexyl acrylate.

The vinyl polymer can be synthesized by a known method, and typical examples include solution polymerization, emulsion polymerization, suspension polymerization and the like.

Known photopolymerization initiators (C) can be used, and typical examples include 1-hydroxycyclohexylphenyl ketone and 2-hydroxy-2-methyl-1-phenylpropan-1-one. Benzyldimethyl ketal, benzoin isopropyl ether, benzophenone and the like. These can be used alone,
A plurality of types may be used in combination.

Known waxes can also be used as the wax (D), such as natural and synthetic hydrocarbon waxes, modified products thereof, oxides, mineral oils and vegetable oil waxes and modified products thereof. Is mentioned. Here, the wax (D) desirably has a melting point of 40 ° C. or higher.
When the melting point is lower than 40 ° C., the tackiness of the cured coating film is recognized at a high temperature, and it is difficult to exhibit a sufficient function as a coating material.

The mixing ratio of these components is as follows:
Component (B) is 90 to 10 parts by weight based on 0 to 90 parts by weight. When the amount of the component (B) is less than 10 parts by weight, the effect of the component (B), which enhances removability and adhesion, is hardly exhibited,
If the amount exceeds 90 parts by weight, the ultraviolet curability of the composition may be insufficient. Preferably, component (A) is 3
Component (B) is 70 to 30 parts by weight in 0 to 70 parts by weight.

The mixing ratio of the component (C) is 1 to 10 parts by weight, preferably 2 to 5 parts by weight, per 100 parts by weight of the total of the components (A) and (B).

The mixing ratio of the component (D) is 0 to 20 parts by weight based on 100 parts by weight of the total of the components (A) and (B). The component (D) is not essential, but by adding it, the gloss of the surface and the detergent resistance are further improved. The mixing ratio of the component (D) is preferably 0 to 10 parts by weight.

Anionic dissociative group-containing vinyl polymer (B)
The ultraviolet curable resin composition of the present invention containing
Preferably it is ~ 200 mgKOH / g. 30mgK
If it is less than OH / g, the removability is poor, and if it is more than 200 mgKOH / g, the water resistance is poor.

The UV-curable resin composition includes:
If necessary, additives such as a slip agent, a surfactant and a plasticizer may be added in addition to the components (A) to (D).

The ultraviolet-curable coating material of the present invention is obtained by laminating the above-mentioned ultraviolet-curable resin composition and an ultraviolet-transmitting film. That is, the present coating material is obtained by laminating the above-mentioned ultraviolet-curable resin composition on an ultraviolet-transparent film, thereby forming a laminate comprising at least two layers of a layer made of the ultraviolet-curable resin composition and a layer of the ultraviolet-transparent film Is configured as

Any film can be used as long as it transmits ultraviolet light, and examples of the film used for lamination include transparent films of polyethylene, polyethylene terephthalate, polyimide and the like.

As a method of laminating, one side of the film is coated with the above composition so as to have a predetermined thickness, or the above composition is coated so as to have a predetermined thickness between two films. Or a method of sandwiching them. When sandwiched between two films, both may be ultraviolet-transmitting films, but if one is an ultraviolet-transmitting film, the other may be a film that does not transmit ultraviolet light, such as release paper.

The ultraviolet-curable coating material of the present invention obtained as described above is applied to the surface of a base material of various structures and moldings, such as building materials such as floors and walls, furniture, and the like, with an ultraviolet-transmissive film attached. The resin composition is cured by irradiating the resin composition with ultraviolet rays in this state, and the resin composition is integrated with the base material. In detail, when laminated with two films, one of the films is peeled off and attached to the substrate, and when laminated with one film, the film is adhered to the substrate as it is and a film (ultraviolet transparent film) UV light is applied from above to cure. As described above, since the film can be cured with the film attached, the film (protective film) formed on the base material surface can be provided with smoothness, and the curing of the ultraviolet-curable resin is prevented from being inhibited by oxygen. be able to.

The material of the substrate is not particularly limited, and typical examples thereof include synthetic resins such as vinyl chloride resin, polyester resin, polyurethane resin, epoxy resin, acrylic resin, and polyolefin resin.
Examples include natural materials such as wood and stone, and metals.

[0028]

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples. In the following, “parts” and “%” are all based on weight unless otherwise specified.

The UV curable resin compositions of Formulations 1 to 5 were prepared according to the formulations shown in Table 1 below.

[0030]

[Table 1]

For Examples 1 to 3 and Comparative Examples 1 and 2, the compositions of the respective formulations shown in Table 2 below were used.
A coating material for a laminated product was formed by sandwiching two transparent polyethylene films so as to have a thickness of 20 μm. Then, one film of the laminated coating material is attached to the PVC flooring material while peeling it off, and the integrated illuminance is 350 mJ / cm ² using a high-pressure mercury lamp of 80 W / cm as it is.
After curing, the film on the surface was peeled off and subjected to the following test.

Further, as Comparative Example 3, using a solvent-based coating material obtained by dissolving Formulation 2 in ethyl acetate, this was applied on a PVC flooring material at a thickness of 50 μm, and dried at 80 ° C. for 30 minutes. Then, after curing with a high-pressure mercury lamp, the same test was performed. Further, as Comparative Example 4, using a commercially available emulsion-based coating material, Polyase Yushilon Coat C Ground (manufactured by Yushiro Chemical Co., Ltd.), this was applied three times on a PVC flooring material, and allowed to stand for at least 24 hours. And then subjected to the same test.

The test items and conditions for the obtained film are as follows.

Surface condition: The surface condition of the cured film was evaluated visually and by finger touch.

Gloss: Gloss (%) was measured with a specular gloss meter according to JIS K 3920-14.

Water resistance: The whitening state of the surface was visually evaluated according to JIS K 3920-17. ○ indicates that no change was observed.

Removability: 3 cured films in 5% KOH aqueous solution
After immersion for 0 minutes, the film was sufficiently rinsed with running water, and the state of the film was visually evaluated. ○ indicates good removability, and X indicates poor removability.

Adhesion: The same coating material as the coating was laminated on each of the obtained coatings in the same manner.
Regarding the film after lamination, JIS K 5400-8.5
The measurement was carried out according to the (cross-cut tape method), and the evaluation was made based on the number of remaining pieces out of 100 pieces (1 mm intervals).

Detergent resistance: The gloss before and after washing was measured according to JIS K 3920-18, and the gloss retention was evaluated.

Heel mark resistance: JIS K 3920-
According to No. 15, the degree of adhesion of the heel mark was visually evaluated.ほ と ん ど indicates that there was little adhesion, and X indicates that adhesion was significant.

[0041]

[Table 2] The results are as shown in Table 2.

The coating materials of Examples 1 to 3 cure in a shorter time than Comparative Example 4 of the emulsion type requires curing for 24 hours or more. High glossiness. In addition, since the film was cured with the film attached, the film surface was excellent in smoothness as compared with Comparative Example 3, and exhibited good surface properties without being inhibited from curing by oxygen. In addition, since the composition contained a vinyl polymer having an anionic dissociating group, the removability and the adhesion were good compared to Comparative Examples 1 and 2.

[0043]

As described above, the UV-curable coating material of the present invention has good workability when coating the substrate, and the obtained film has gloss, water resistance and washing resistance. Good surface properties such as properties. In addition, it is excellent in adhesiveness at the time of recoating and also excellent in removability, so that repair of a coating material and design change are easy.

Claims (3)

[Claims] 1. An ultraviolet-curable coating material, wherein an ultraviolet-curable resin composition comprising the following (A) to (D) is laminated with an ultraviolet-transmissive film. (A) 10 to 90 parts by weight of an ultraviolet curable monomer (B) 10 to 90 parts by weight of a vinyl polymer having an anionic dissociating group (C) based on 100 parts by weight of the total of the components (A) and (B) Photopolymerization initiator 1 to 10 parts by weight (D) Wax 0 to 20 parts by weight 2. The ultraviolet-curable resin composition has an acid value of 30.
2. The composition according to claim 1, wherein the amount is from 200 mgKOH / g.
The ultraviolet-curable coating material according to the above. 3. The ultraviolet-curable coating material according to claim 1, wherein the vinyl polymer as the component (B) is a vinyl polymer having a carboxyl group or a sulfo group.