JP2003165930A - Photo-setting solventless painting composition and method for forming pattern by using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a photo-setting solventless painting composition and to provide a method for forming a pattern by using the same. <P>SOLUTION: The photo-setting solventless painting composition comprises a photo-setting composition containing a compound having polymerizable unsaturated groups and a photopolymerization initiator, preferably with a skin toxicity index (PII value: Primary Irritation Index) of 3 or lower. The composition is used in the method for forming a pattern. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a photocurable solventless painting composition and a pattern forming method using the same.

[0002]

2. Description of the Related Art Painting compositions, in particular, those for drawing pictures and characters on a substrate such as glass, tile, ceramics such as ceramics, metal, plastics, wood, etc., with a brush etc. The thing using a carbon-carbon double bond type unsaturated monomer is not marketed at all.

The reason for this is that, on January 5, 1986, issued by the International Trade Materials Survey Committee, supervised by the Basic New Materials Countermeasures Office, Ministry of International Trade and Industry, "New Material Handbook, 1986-1987", No. 16
As described on page 3, Table 2.1.78 “Various properties of vinyl compounds used in photocurable coatings”, styrene and hydroxyethyl acrylate, which are monomers for producing the resin, are handled. Since it is necessary to wear a mask and 2-ethylhexyl acrylate and diethylene glycol diacrylate are both toxic to the human body, they cannot be used in the monomer form and are polymerized. This is because it had to be used only as a non-toxic resin. Also, 1
December 10, 986 Published by Asakura Shoten Co., Ltd., Shunsuke Murahashi, two authors, "Revised New Edition Plastic Handbook" No. 3
According to Table 2.6.2 on page 80, LD of methyl acrylate
50 (test with rats) is stated to be 25 ppm, again with considerable toxicity.

Therefore, a painting composition inevitably requires a combination of a polymer and a solvent, but the solvent is not preferable for the human body.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a photocurable solventless painting composition and a pattern forming method using the same.

[0006]

The first aspect of the present invention relates to a photocurable solventless painting composition containing a polymerizable unsaturated group-containing compound and a photopolymerization initiator. The second aspect of the present invention is that the photocurable non-curable composition according to claim 1, wherein a surfactant having a polymerizable unsaturated group is blended as one kind of the polymerizable unsaturated group (carbon-carbon unsaturated group) -containing compound. It relates to a solvent-based painting composition. Third of the present invention
Relates to the photocurable solventless painting composition according to claim 1 or 2, wherein the polymerizable unsaturated group-containing compound contains acryloylmorpholine. The content of acryloylmorpholine is preferably 20 to 50% by weight. The fourth aspect of the present invention is a skin toxicity index (PII value:
(Primary Irritation Index)
It is 3 or less, It relates to the photocurable solventless-type painting composition in any one of Claims 1-3. Fifth of the present invention
Relates to the photocurable solventless painting composition according to any one of claims 1 to 4, wherein the formed cured film has a water swelling ratio of 0.5 to 30%. Sixth of the present invention
Relates to the photocurable solventless painting composition according to any one of claims 1 to 5, which contains at least one coloring component selected from the group consisting of dyes and pigments, pearlescent agents and lame agents. A seventh aspect of the present invention relates to a pattern forming method, which comprises coloring the substrate or forming a pattern using the photocurable solventless painting composition according to any one of claims 1 to 6. An eighth aspect of the present invention is to form the photocurable solventless solvent-free painting composition layer according to any one of claims 1 to 6 on a transparent or opaque substrate, and place a photograph or a pattern paper on it. A pattern forming method, comprising laminating a transparent substrate on the photocurable solventless painting composition according to any one of claims 1 to 6.
A ninth aspect of the present invention is to form a photocurable solventless painting composition layer according to any one of claims 1 to 6 on a pattern paper or a pattern board, and to form a film or plate-like article having a hologram-processed surface thereon. The present invention relates to a pattern forming method characterized by placing and pressing.

The above-mentioned skin toxicity index is also known as the PII value, and the The Consumer Product
t Safety Commission of the
U. S. A. By The Code of Feder
al Regulations, Title 16, S
section 1500.41.

Examples of the polymerizable unsaturated group-containing compound include
Mention may be made of monomers and oligomers having a polymerizable unsaturated group. Examples of the oligomer having a polymerizable unsaturated group include prepolymers having a polymerizable double bond such as epoxy acrylate, urethane acrylate, polyester acrylate and unsaturated polyester. Further, as the monomer having a polymerizable unsaturated group,
For example, water-soluble monomers include acrylamide, N-methylol acrylamide, acryloylmorpholine,
N-vinylformamide, N-vinylpyrrolidone, N,
There are N-dimethylaminoethyl acrylate, N, N-dimethylaminopropyl acrylate, diacetone acrylamide, polyethylene glycol diacrylate, bisphenol A ethylene oxide adduct diacrylate, etc., and general monomers include methyl (meth) acrylate and ethyl. (Meth) acrylate, butyl (meth) acrylate, glycidyl methacrylate, hydroxypropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isoamyl acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, butoxyethyl acrylate, ethoxy Diethylene glycol acrylate, methoxytriethylene glycol acrylate, methoxydipropylene glycol acrylate, Noxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, neopentyl glycol diacrylate, 1 , 6-hexanediol diacrylate, 1,9-nonanediol diacrylate, dimethylol tricyclodecane diacrylate, propylene oxide adduct diacrylate of bisphenol A, trimethylol propane triacrylate, ethylene oxide modified trimethylol propane triacrylate, Ditrimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate Dipentaerythritol hexaacrylate, dodecyl vinyl ether, hydroxybutyl vinyl ether, cyclohexanedimethanol divinyl ether, triethylene glycol divinyl ether, styrene, vinyl toluene, alpha-
Examples include methyl styrene and vinyl acetate.

As the polymerizable unsaturated group-containing compound satisfying the condition of PII value of 3 or less of the present invention, acryloylmorpholine (PII value = 0.5), polyethylene glycol (# 200) diacrylate (PII value = 2) .4),
Polyethylene glycol (# 300) diacrylate (PII value = 0.0), polyethylene glycol (# 4
00) diacrylate (PII value = 0.4), ethoxydiethylene glycol acrylate (PII value = 2.
1), acryloylmorpholine (PII value = 0.
5), phenoxyethyl acrylate (PII value = 1.
5), phenoxy polyethylene glycol acrylate (PII value = 0.7), bisphenol A-EO (ethylene oxide) modified diacrylate (PII value = 0.
4), pentaerythritol triacrylate (PII
Value = 2.8), dipentaerythritol hexaacrylate (PII value = 0.8), nonylphenoxyarylate (PII value = 2.0), lauryl acrylate (PI
I value = 3.0), isobornyl acrylate (PII value = 0.6), 3-methoxybutyl acrylate (P11
Value = 2.1), methoxytripropylene glycol acrylate (PII value = 2.7), 2-acryloyloxyethyl-2-hydroxypropyl phthalate (PII
Value = 0.7), 2-acryloyloxyethyl hydrogenophthalate (PII value = 2.5), 2-acryloyloxypropyl tetrahydrohydrogenphthalate (PII value = 2.8), 1,9-nonanediol diacrylate ( PII value = 2.0), tetraethylene glycol diacrylate (PII value = 2.3), tripropylene glycol diacrylate (PII value = 1.6),
Polypropylene glycol diacrylate (PII value =
0.8), trimethylolpropane triacrylate (PII value = 1.6), trimethylolpropane EO
(Ethylene oxide) -added triacrylate (PII
Value = 1.5), pentaerythritol tetraacrylate (PII value = 2.8), 1,6-hexanediol diacrylate (PII value = 1.02), diethylene glycol dimethacrylate (PII value = 0.5), polyethylene Glycol (# 200) Dimethacrylate (PI
I value = 0.5), 1,6-hexanediol dimethacrylate (PII value = 0.5), 2-hydroxy-1,3
-Dimethacryloxypropane (PII value = 0.6),
2,2-bis [4- (methacryloxydiethoxy) phenyl] propane (PII value = 1.0), 2,2-bis [4- (methacryloxypolyethoxy) phenyl] propane (PII value = 0.9), Tetrafurfuryl alcohol oligoacrylate (PII value = 2.3), ethylcarbitol oligoacrylate (PII value = 1.
6), 1,4-butanediol oligoacrylate (P
II value = 0.9), neopentyl glycol oligoacrylate (PII value = 0.3), 1,6-hexanediol oligoacrylate (PII value = 0.4), trimethylolpropane oligoacrylate (PII value = 0.
1), pentaerythritol oligoacrylate (PI
I value = 0.1), N-vinylformamide (PII value =
0.4), triethylene glycol divinyl ether (PII value = 0.15), and a reactive surfactant having a polymerizable unsaturated group. For example, allyloxy polyethylene glycol monomethacrylate [trade name of NOF Corporation: Blemmer PKE series], nonylphenoxy polyethylene glycol monomethacrylate [Nippon Yushi Co., Ltd. trade name: Blemmer PNE series], nonylphenoxy polypropylene glycol monomethacrylate [Nippon Yushi Co., Ltd. trade name: Blemmer PNP series], nonylphenoxy poly (Ethylene glycol-propylene glycol) monomethacrylate [Nippon Yushi Co., Ltd. trade name: Bremmer PNEP-600], Aqualon RN-10, RN-20, RN-30, RN-5
0, RN-2025, HS-05, HS-10, HS-
20 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and the like.

Among them, acryloylmorpholine having a PII of 2 or less (PII value = 0.5), polyethylene glycol (# 300) diacrylate (PII value = 0.0),
Phenoxyethyl acrylate (PII value = 1.5),
Bisphenol A-EO (ethylene oxide) modified diacrylate (PII value = 0.4), dipentaerythritol hexaacrylate (PII value = 0.8), isobornyl acrylate (PII value = 0.6), trimethylolpropane Triacrylate (PII value = 1.
6), trimethylolpropane EO (ethylene oxide) addition triacrylate (PII value = 1.5), isobornyl acrylate (PII value = 0.6), diethylene glycol dimethacrylate (PII value = 0.5),
Polyethylene glycol (# 200) dimethacrylate (PII value = 0.5), 1,6-hexanediol dimethacrylate (PII value = 0.5), 2-hydroxy-
1,3-Dimethacryloxypropane (PII value = 0.
6), ethyl carbitol oligoacrylate (PII
Value = 1.6), 1,4-butanediol oligoacrylate (PII value = 0.9), neopentyl glycol oligoacrylate (PII value = 0.3), 1,6-hexanediol oligoacrylate (PII value =) 0.
4), trimethylolpropane oligoacrylate (P
II value = 0.1), pentaerythritol oligoacrylate (PII value = 0.1), N-vinylformamide (PII value = 0.4), and triethylene glycol divinyl ether (PII value = 0.15) are preferable.

The photopolymerization initiator used in the present invention is 2
-Methyl-1- [4- (methylthio) phenyl] -2-
In addition to morpholinopropane-1, 4-phenoxydichloroacetophenone, 4-t-butyldichloroacetophenone, 4-t-butyltrichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one , 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-
Hydroxyethoxy) -phenyl (2-hydroxy-2
-Propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, benzyl dimethyl ketal, benzophenone, benzoyl benzoic acid,
Methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3'-dimethyl-4-methoxybenzophenone, thioxanthone, 2-chlorothioxanthone, 2
-Methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diisopropylthioxanthone, α-acyloxime ester, acylphosphinoxide, Methylphenylglyoxylate, benzyl 9,10-phenanthrenequinone, camphorquinone,
Examples thereof include dibenzosuberone.

In the present invention, a photopolymerization initiation auxiliary agent can be used in combination. As the photopolymerization initiation aid, triethanolamine, methyldiethanolamine, triisopropanolamine, 4,4-dimethylaminobenzophenone, 4,4-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, 4-dimethylaminoethylbenzoic acid, Examples thereof include isoamyl 4-dimethylaminoethylbenzoate, 2-ethylhexyl 4-dimethylaminoethylbenzoate, and a polymerizable tertiary amine.

In the present invention, the presence of the polymerizable unsaturated group-containing compound and a photopolymerization initiator is essential, and in addition to this, a photopolymerization initiation auxiliary agent, a coloring agent, a pearling agent, a laminating agent,
Matting agents, fragrances, ultraviolet absorbers, wetting agents, defoaming agents, coupling agents, thixotropic agents and the like can be added as required.

The colorant that can be used in the present invention is not particularly limited, but various natural and synthetic dyes and pigments used for painting can be used.

Specific dyes and pigments include Red No. 2 and 3
No. 102, No. 104 (1), No. 105 (1),
No. 106, Yellow No. 4, No. 5, Green No. 3, Blue No. 1, 2
No. Red No. 201-208, 213-215, 2
No. 18-221, No. 223, No. 225-228, 2
No. 30 (1), No. 230 (2), No. 231, 232
No., Daidai No. 201, No. 203 to No. 207, Yellow 2
No. 01, No. 201 (1), No. 201 (2), 203
No. 205 to No. 205, green No. 201, 202, 204, 2
05, blue 201 to 205, brown 201, purple 201, red 401, 404, 405, 501
No. ~ 506, Daidai color No. 401 ~ 403, yellow 4
01-407, green 401, 402, blue 40
No. 3, 404, purple 401, black 401 and other legal dyes (August 31, 1941, Ministry of Health and Welfare No. 30), organic dyes and pigments, silicic anhydride, magnesium silicate, talc, kaolin, Bentonite, mica, mica titanium,
Inorganic dyes such as bismuth oxychloride, zirconium oxide, magnesium oxide, zinc oxide, titanium oxide, calcium carbonate, magnesium carbonate, yellow iron oxide, red iron oxide, black iron oxide, Gunjou, chromium oxide, chromium hydroxide, carbon black and calamine. Examples include natural pigments such as pigments, carotenoids, flavonoids, fuchbins, quinones, porphyrins, diketones, and petacyanidines.

The blending ratio (based on the total amount) of the pearlescent agent and / or lame agent in the present invention is 0.01 to 20% by weight, preferably 0.1 to 5% by weight.

As the pearlescent agents used in the present invention, both natural pearl essences and synthetic pearlescent pigments can be used (19
November 4, 1986, CMC Co., Ltd., "Latest Pigment Application Technology", pp. 61-65). Natural pearl essence has plate-like or needle-like crystals collected and purified from fish scales or skins, which is also commonly called fish scale foil. Synthetic pearl pigments are roughly classified into metal oxide-coated mica type, bismuth acid chloride type and basic lead carbonate. The metal oxide mica-based and bismuth acid-acid-based systems include those in which muscovite flakes are coated with a thin layer of titanium oxide, iron oxide-coated mica iron, and bismuth acid chloride.

The laminating agent is a polyethylene terephthalate film, a polyolefin film or the like laminated with an adhesive resin and finely cut (metal flakes such as aluminum, gold and tin do not transmit light and thus can be photocured in the present invention). It can't be used because it runs out).

A laminated laminating agent composed of a synthetic resin film having fine grooves, for example, a polyethylene terephthalate film, and a vapor-deposited metal and a binder resin, for example, an epoxy resin, has fine grooves such as a hologram pattern on the surface of the synthetic resin film, for example, polyethylene terephthalate film. For this reason, one of the visible rays interferes and shines in a rainbow color due to the prism effect, or three-dimensionally develops into red, blue, green, and orange depending on the viewing angle. Examples of a method for forming fine grooves in a synthetic resin film such as a polyethylene terephthalate film include a method of embossing using a press die in which a hologram pattern is etched with a laser. Examples of the vapor-deposited metal include aluminum and gold. Aluminum is preferable from the viewpoint of exhibiting an iris color appearance even when wet with a solvent.

The laminated laminating agent is prepared by first forming a fine groove in a synthetic resin film, for example, a polyethylene terephthalate film, vapor-depositing a metal on the groove, and then coating it with a binder resin, for example, an epoxy resin, and then sizing it with an appropriate size.
It is obtained by cutting into a shape. When the epoxy resin is coated, a binder resin, for example, an epoxy resin mixed with or dissolved in an inorganic coloring pigment such as red iron oxide or yellow iron oxide or an organic coloring matter such as a tar-based coloring matter is also used to coat a coloring matter. It is possible.

The size of the laminated laminating agent used in the present invention is selected depending on the usability, the feeling of use and the cosmetic effect, but is generally 0.001 to 5 mm, preferably 0.01 to 3 m.
m. Further, the shape thereof is also selected depending on usability, feeling of use, and cosmetic effect, and examples thereof include a star shape, a round shape, a square shape, a strip shape, a heart shape, a hexagonal shape, and an oval shape.

The laminated laminating agent composed of a polyethylene terephthalate film having fine grooves and a metal and an epoxy resin used in the present invention is commercially available as diamond hologram HG-S20EP and diamond hologram HG-S40E.
P (manufactured by Diamond Industrial Co., Ltd.), Epocrystal 0.1M, Epocrystal 0.3M (manufactured by Nakatsuka Metal) and the like. Further, one kind or two or more kinds of these laminated laminating agents can be used if necessary. Further, if necessary, general oil agents, silicone oils, fluorine compounds, and those whose surface is treated with a surfactant can be used.

In the present invention, the polymerizable unsaturated group is added to the coating composition so that the coating composition attached to the application tool such as a brush used for applying the coating composition can be removed by washing with water. It is preferable to incorporate a surfactant having As a result, the water swelling rate of the cured coating changes. The amount of the surfactant having a polymerizable unsaturated group so that the painting composition attached to the brush can be removed by washing with water depends on the surfactant ability of the surfactant and the characteristics of other monomers. However, it is usually preferably 1% by weight or more, and particularly preferably 3% by weight or more, based on all monomers. When the amount of the surfactant having a polymerizable unsaturated group is small, the degree of cross-linking is high, and the resulting cross-linked product has low hydrophilicity, the formed film does not even swell even if it is in contact with warm water for a long time, and the film is It remains firmly attached to the material.

In the present invention, in order to prevent the substrate from being damaged when the painting composition is removed, for example, by changing the design drawn with the painting composition, the coating film is covered with water. It is preferable to impart swelling property, and the degree of water swelling property in this case is represented by a water swelling ratio, and the water swelling ratio is 0.5 to 30%, preferably 2 to 30.
%, Particularly preferably 3 to 5%.

The water swelling ratio refers to a film having a thickness of 200 to 300 μm which is cured by irradiation with light such as ultraviolet rays.
The film weight (A) was measured after immersing in water at 0 ° C ± 2 ° C for 1 hour and removing the attached water with a filter paper.
Film weight after drying at 5 ° C ± 22 ° C for 2 hours (B)
Was measured and calculated according to the following formula.

## EQU1 ## Water swelling rate (%) = {1-A / B} × 100

In any case, it is preferable to use the above-mentioned surfactant having a polymerizable unsaturated group as one kind of the polymerizable unsaturated compound. The amount of the surfactant having a polymerizable unsaturated group used is not particularly limited because it varies depending on its purpose, the properties of the surfactant and other monomers, and is not particularly limited. It is 1 to 20% by weight based on the total weight of the contained compounds. By increasing the proportion of the polymerizable unsaturated compound having a strongly hydrophilic structure, the water swelling property can be enhanced even if the amount of the surfactant having a polymerizable unsaturated group is small. .

In the present invention, the painting layer of the present invention can be protected by another top coat agent, if necessary.

The base material for drawing patterns (including pictures and letters) by the photocurable solventless painting composition of the present invention includes various ceramics such as glass, tiles, pottery and ceramics, plastics and metals. , Wood, plywood, fiberboard, paper (including synthetic paper), and the like. In particular, since the painting composition of the present invention has a property that a painting film cured by immersion in water can be peeled off, in order to take advantage of this property, a non-penetrable ceramic, plastics, or the like, which does not allow the painting composition to penetrate inside, Application to metals is preferred.

Means for applying the photocurable solventless painting composition of the present invention to a substrate include brushes, brushes, brushes, sprays, bar coaters, screen printing and hologram duplication (see, for example, JP-A-58). -35578). In particular, the present invention is extremely suitable as a painting composition for individual tastes.

The painting composition of the present invention can be cured in a short time after being applied to a substrate by irradiation with light (visible light, ultraviolet rays, electron beams, etc.).

[0031]

The present invention will be described below with reference to examples.
The present invention is not limited thereby.

Example 1 Bisphenol A-EO modified diacrylate [trade name:
Aronix M-211B Toa Gosei Co., Ltd. PII value 0.6] 60 parts by weight, Acryloylmorpholine [trade name: ACMO Co., Ltd. Kojin PII value 0.5] 35 parts by weight, containing a polymerizable unsaturated group Surfactant [Brand name: Aqualon RN-20, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.] 5 parts by weight, modified dimethylpolyxylosan [Brand name: BYK-307
Manufactured by Big Chemie Japan Co., Ltd.] 0.1 part by weight, photoinitiator 2-methyl-1- [4- (methylthio) phenyl]
-2- Morpholinopropanone-1 [Product name: Irgacure 907 manufactured by Ciba Specialty Chemicals Co., Ltd.] 5 parts by weight, Red No. 225 (English name Sudan III)
After mixing 0.5 parts by weight, the mixture was heated and stirred at 60 ° C. for 30 minutes, whereby a uniformly curable photocurable solventless painting composition could be produced. This was drawn on a clean stainless steel plate with a brush and was irradiated with a hot cathode UV lamp [output 6W Harrison Toshiba Lighting Co., Ltd.] for 3 minutes. As a result, a red transparent film with good pencil hardness F adhesion was obtained. Was obtained.
The brush used could be washed with water to wash the photocurable solventless painting composition. Further, when this cured drawing was immersed in water at 25 ° C. for 1 hour, it could be easily peeled off.

Example 2 A photocurable solventless painting composition was produced in the same manner as in Example 1 except that Red No. 225 of Example 1 was omitted. This is applied to a clean glass plate using a brush, a photograph smaller than the face glass plate is placed in the middle, and the photocurable solventless painting composition is applied to another clean glass plate. After the coated surfaces were overlaid and adhered to each other, they were irradiated with a hot-cathode UV lamp [output 6W, manufactured by Harrison Toshiba Lighting Co., Ltd.] for 3 minutes, and the back surface was also irradiated for 3 minutes in the same manner. I was able to glue the glasses together. The brush used could be washed with water to wash the photopolymerizable composition.

Example 3 The photocurable solventless painting composition of Example 2 was applied to a printing paper with a bar coater # 5, and the processed surface of a hologram-processed polyester film was superposed on the applied surface.
After squeezing out the air between the film and the printing surface, the film was peeled off by irradiating with a hot cathode UV lamp [output 6 W, manufactured by Harrison Toshiba Lighting Co., Ltd.] for 5 minutes,
A holographically processed printing paper was obtained. The bar coater used was capable of washing the photopolymerizable composition by washing with water.

Example 4 The photocurable solventless painting composition 10 of Example 2
0 parts by weight of lame agent [Product name: Crystal Color X
-5No3 Diamond Industrial Co., Ltd.] 5 parts by weight were mixed to produce a photocurable solventless solvent-type painting composition containing lame. This was applied to a clean glass bottle with a brush and irradiated with a hot cathode UV lamp [output 6 W, manufactured by Harrison Toshiba Lighting Co., Ltd.] for 3 minutes to cure and cure into a beautiful bottle with lame. The brush used could be washed with water to wash the photocurable solventless painting composition.
Further, when the cured coating surface was immersed in water at 25 ° C. for 1 hour, it could be easily peeled off.

Example 5 In the same manner as in Example 1 except that the red No. 225 of Example 1 was replaced by 0.5 parts by weight of purple No. 201 (English name: Alizurin purple SS), a photocurable solventless type was used. A painting composition was produced. Draw a pattern on a cosmetic container made of acrylonitrile-styrene copolymer resin using a brush and irradiate with a hot cathode UV lamp [output 6W Harrison Toshiba Lighting Co., Ltd.] for 3 minutes to cure the pattern. It became a packaged cosmetic container. The brush used could be washed with water to wash the photocurable solventless painting composition. When the gauze moistened with water was left on the pattern for 2 hours and then the gauze was removed, the pattern was swollen and could be easily peeled off.

[0037]

EFFECTS OF THE INVENTION (1) Since the painting composition of the present invention contains no solvent at all, it is extremely friendly to humans and the global environment. (2) When the PII value is suppressed to a low level, the composition is gentle on the human body and can be painted with the hands. (3) Conventional paints usually cannot be easily peeled off once used, and in the case of oil painting, it is necessary to top-coat, but if the painting composition of the present invention is used, it can be immersed in water. Can be easily peeled off and the substrate can be reused.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08F 290/00 ZAB C08F 290/00 ZAB C09D 4/02 C09D 4/02 F term (reference) 4D075 CA47 CA50 CB13 CB15 DA03 DA06 DB01 DB14 DB21 DB31 EA05 EA21 EB22 EC11 EC37 4F100 AK01B AK01C AK25 AK53 AL05B AL06 AP00A BA02 BA03 BA07 BA10A BA10C CA13B CA30B CC00B DG10ABA24 BA24BA01 BA24BA01 BA20BA14BA20BA14BA20BA14BA14BA14BA14BA14BA14BA14BA14BA14BA14BA14BA14BA14BA14BA14BA14BA14BA14BA14BA14BA14BA14BA14BA14BA14BA14BA14BA14BA14BA14BA14BA14BA14BA21BA21BA14BA14BA14BA21BA14BA14BA21BA14BA14BA14BA21BA21BA14BA14BA21BA14BA21BA14BA21BA21BA14BA14BA14BA14BA21BA14BA14BA14BA14BA14BA14BA21BA14BA24BA4BA21BA21BA14BA14BA14A4 BA27 4J038 FA161 KA04 KA08

Claims (9)

[Claims] 1. A photocurable solvent-free painting composition comprising a compound having a polymerizable unsaturated group and a photopolymerization initiator. 2. The photocurable solventless painting composition according to claim 1, wherein a surfactant having a polymerizable unsaturated group is blended as one kind of the compound having a polymerizable unsaturated group. 3. The polymerizable unsaturated group-containing compound according to claim 1, which contains acryloylmorpholine.
The photocurable solventless painting composition described. 4. A skin toxicity index (PII value: Primar)
y Irritation Index) is 3 or less, The photocurable non-solvent type painting composition in any one of Claims 1-3. 5. The photocurable solventless painting composition according to claim 1, wherein the formed cured film has a water swelling ratio of 0.5 to 30%. 6. The photocurable solvent-free painting composition according to claim 1, which contains at least one coloring component selected from the group consisting of dyes and pigments, pearlescent agents and laminating agents. 7. A pattern forming method, comprising coloring a substrate or forming a pattern by using the photocurable solventless painting composition according to claim 1. 8. A transparent or opaque substrate on which the substrate according to claims 1-6.
The photocurable solventless painting composition layer according to any one of claims 1 to 6 is formed, and a photo or a pattern paper is placed on the photocurable solventless painting composition layer, and the photocurable solventless pane according to any one of claims 1 to 6. A method for forming a pattern, which comprises laminating a transparent substrate with a coating composition. 9. A photocurable solventless painting composition layer according to any one of claims 1 to 6 is formed on a pattern paper or a pattern plate, and a film or plate-like product having a hologram processed surface is formed thereon. A pattern forming method comprising placing and pressing.