JP2002188030A - Uv-curable surface wrinkle-forming ink - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a UV-curable surface wrinkle-forming ink capable of forming wrinkle patterns excellent in design by forming innumerable contraction wrinkles having an almost certain size at the same time through curing, when a coating film applied by screen printing, curtain coating and the like on a material such as a plastic, a glass, a metal or the like is cured. SOLUTION: This UV-curing and surface wrinkle-forming ink is obtained by using a >=2 functional epoxy compound as an ink vehicle and a photo- cationic catalyst having low catalytic activity when irradiated with UV rays, i.e., mainly acting on curing of the coated surface as the photo cationic catalyst. Thus, the curing and contraction of the surface are taken place and numerous number of wrinkles having almost certain size are formed on the surface.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a paint and ink for surface decoration, which gives a decorative effect to a material such as plastic, glass, metal or the like by curing a coating applied by screen printing, curtain coating or the like on the material. The present invention relates to an ultraviolet-curable surface wrinkle forming ink used for, for example, an ink.

With respect to conventional UV-curable paints and inks for surface decoration, the film obtained by curing is almost smooth. For decoration, silica or talc is blended to form a mat or beads. A quasi-etching feeling is added by blending an acrylic resin or a styrene resin in a shape.

Further, Japanese Patent Application Laid-Open No. H11-158428 discloses an ink which forms wrinkles by ultraviolet curing, but in this case, a decorative effect is obtained by forming large and small wrinkles. Further, Japanese Patent Application Laid-Open No. 9-53024 discloses a method for forming wrinkles by irradiation with ultraviolet rays. However, this method is based on the fact that the main component of the resin composition to be a coating film is acrylate, and the method for curing an ultraviolet-curable ink. An ultraviolet irradiator equipped with a high-pressure mercury lamp or a metal halide lamp, which is generally widely used, has a disadvantage that wrinkles are not formed.

The applied coating film is cured by ultraviolet rays, and at the same time as the curing, an infinite number of shrinking wrinkles of almost constant size are generated on the coating film to form a wrinkle pattern excellent in design. To provide a UV curable surface wrinkle forming ink to be produced.

[0004]

Means for Solving the Problems In the ink vehicle component,
An epoxy compound having two or more functionalities is used, and as a photocationic catalyst, a photocationic catalyst having a low catalytic activity upon irradiation with ultraviolet rays, that is, a photocationic catalyst mainly acting on curing of the coating film surface is used. As a result, the surface of the coating film undergoes curing shrinkage, and numerous wrinkles of almost constant size are formed on the surface.

[0005] Further, a bifunctional or higher epoxy compound is used as an ink vehicle component, and a photocationic catalyst having a low catalytic activity upon irradiation with ultraviolet rays, that is, a photocationic catalyst mainly acting on curing of the coating film surface, is used as a photocationic catalyst. This causes curing shrinkage of the coating film surface and forms wrinkles on the surface. In addition, when using a UV irradiator to be used, the catalytic activity is higher, that is, a photo cation that cures to the inside of the coating film. A catalyst is further used. This accelerates the curing of the coating. That is, the curing of the coating film is promoted while forming wrinkles.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The vehicle component of the ink of the present invention includes a cycloaliphatic epoxy compound, bisphenol A
Epoxy resins such as epoxy resin, bisphenol F epoxy resin, novolac epoxy resin, polyglycol epoxy resin, butyl glycidyl ether, phenyl glycidyl ether, 1.4 butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, Examples include trimethylolpropane triglycidyl ether, hexahydrophthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, epoxy-modified polymers, etc. It is not something to be done. As a vehicle component of the ink of the present invention, an epoxy compound having two or more functionalities is basically used, but an epoxy compound having three or more functionalities or a cycloaliphatic epoxy compound may be used in order to enhance wrinkle formation and reactivity. preferable. As an example, trimethylolpropane triglycidyl ether, trimethylolethane triglycidyl ether, aliphatic polyol polyglycidyl ether, phenol novolak epoxy resin, cresol novolak epoxy resin, sorbitol polyglycidyl ether, 3,4 epoxycyclohexylmethyl (3 , 4-epoxycyclohexane) carboxylate, 3,4 epoxy-6 methylcyclohexylmethyl 3,4 epoxy-6 methylcyclohexanecarboxylate, bis (3,4-epoxy-6methylcyclohexylmethyl) adipate, vinylcyclohexene diepoxide, Cyclopentadiene oxide, bis (2
3-epoxycyclopentyl) ether, limonenedoxide, and the like. Furthermore, monomers and oligomers of vinyl ether compounds such as triethylene glycol divinyl ether having an active double bond, 1.4 cyclohexane dimethanol divinyl ether, and hydroxybutyl vinyl ether; 2-hydroxyethyl (meth) acrylate; Acrylate monomers or oligomers such as (meth) acrylate and trimethylolpropane tri (meth) acrylate can be added.

In the ultraviolet curable surface wrinkle forming ink of the present invention, the UV irradiation causes the photocationic catalyst having low catalytic activity to cure and shrink the surface of the coating film to form wrinkles on the surface. The photocationic catalyst having a low catalytic activity, which mainly acts to form wrinkles, has a catalytic activity such that the curing inside the coating film does not proceed and the curing of the coating film surface proceeds, but in particular, the counter anion is PF ₆ ^{In the above,} it is preferable to select a sulfonium salt having 0 to 3 aromatic rings in the chemical formula. In particular, by using the compound represented by the chemical formula 1, it is possible to obtain innumerable almost uniform wrinkles. it can. After the formation of wrinkles, if further curing of the coating film is necessary, a heat treatment or in advance, a curing agent generally used for curing the epoxy resin, for example, amines, amine adducts, polyamide, imidazole, acid Curing can be accelerated by adding an anhydride or the like in a range that does not prevent the formation of wrinkles.

In the UV curable surface wrinkle forming ink of the invention, wrinkles are formed while wrinkles are formed by using a photocatalytic catalyst having high catalytic activity, which mainly promotes hardening of the coating rather than wrinkles. Curing can be accelerated. Such photocationic catalysts having high catalytic activity are known and commonly used, for example, diphenyl [(phenylthio) phenyl] sulfonium = hexafluorophosphate, diphenyl [(phenylthio) phenyl] sulfonium = hexafluoroantimonate, (thiodiphenyl) bis [ Diphenylsulfonium] = bis [hexafluorophosphate], (thiodiphenyl) bis [diphenylsulfonium] = bis [hexafluoroantimonate], 4-
4'bis [di (β-hydroxyethoxy) phenylsulfonio] phenyl sulfide = bis [hexafluorophosphate], 4-4'bis [di (β-hydroxyethoxy) phenylsulfonio] phenyl sulfide = bis [hexafluoroantimony Nate like, one or two or more, can be used in combination with sensitizers such as thioxanthone, etc. if necessary, especially iron arene complex (eta ^{5-2,4-cyclopentadiene-1} Ill)
By using [(1,2,3,4,5,6-η)-(1-methylethyl) benzene] -iron (1 +)-hexafluorophosphate (1-), formation of wrinkles is largely prevented. The curing of the coating film can be promoted without wrinkles, and wrinkles excellent in design can be obtained.

A dye, a pigment, a leveling agent, a defoaming agent, a stabilizer for preventing gelation, a solvent, a reactive monomer, and the like can be added to the ultraviolet curable surface wrinkle forming ink of the present invention.

The ultraviolet curable surface wrinkle forming ink of the present invention can be used for paints and sprays by adjusting the viscosity by changing the vehicle components and the compounding ratio thereof.

[0010]

Next, the present invention will be described based on embodiments. The indication of parts shown in the following formulations indicates parts by weight.

(Example 1) Phenol novolak type epoxy resin (epoxy equivalent: 172 to 179) 55 parts 3,4 epoxycyclohexylmethyl (3,4-epoxycyclohexane) carboxylate 40 parts trimethylolpropane triglycidyl ether 5 parts 3 new chemical Co., Ltd. "San-Aid SI-110" (trade mark) 1.5 parts (eta ^{5-2,4-cyclopentadiene-1-yl)} [(1, 2, 3, 4, 5, 6-eta )-(1-Methylethyl) benzene] -iron (1 +)-hexafluorophosphate (1-) 0.5 part Modified polymer silicone resin solution 0.5 part Aluminum is evaporated on the film to give a mirror finish.
Using a 90-mesh silk screen plate, apply a solid printing to a thickness of about 20 microns on a 3 mm printing sheet, and use an aluminum reflector type, condensing type UV irradiating device to apply a lamp load of 80 w / cm. It was passed once at a transport speed of 2 m / min at a distance of 10 cm under one ozone-type high-pressure mercury lamp. Innumerable wrinkle patterns of almost constant size were formed on the surface of the cured product. FIG. 1 is an enlarged copy diagram thereof.

(Example 2) Phenol novolak type epoxy resin (Epoxy equivalent: 172 to 179) 55 parts 3,4 Epoxycyclohexylmethyl (3,4-epoxycyclohexane) carboxylate 40 parts Trimethylolpropane triglycidyl ether 5 parts 3 new chemical Co., Ltd. "San-Aid SI-180L" (trade mark) 1 part (eta ^{5-2,4-cyclopentadiene-1-yl)} [(1,2,3, 4,5,6-η) - (1-methylethyl) benzene] -iron (1 +)-hexafluorophosphate (1-) 0.5 part Modified polymer silicone resin solution 0.5 part The coating was cured under the curing conditions. Innumerable wrinkle patterns of almost constant size were formed on the surface of the cured product. FIG. 2 is an enlarged copy diagram thereof.

(Example 3) Phenol novolak type epoxy resin (Epoxy equivalent: 172 to 179) 85 parts Neopentyl glycol diglycidyl ether 15 parts "San Aid SI-110" (trademark) 1.5 manufactured by Sanshin Chemical Industry Co., Ltd. Part Modified polymer silicone resin solution 0.5 part This composition was applied and cured under the application and curing conditions set in Example 1, with only the conveying speed and the number of passes set to 3 m / min and 2 times. . Innumerable wrinkle patterns of almost constant size were formed on the surface of the cured product. FIG. 3 is an enlarged copy diagram thereof.

(Example 4) Phenol novolak type epoxy resin (epoxy equivalent: 172 to 179) 30 parts Bisphenol A type epoxy resin (epoxy equivalent: 180 to 190) 30 parts 3,4 epoxycyclohexylmethyl (3,4-epoxycyclohexane) ) carboxylate 20 parts of trimethylolpropane triglycidyl ether 20 parts by Sanshin Chemical Industry Co., Ltd., "San-Aid SI-110" (trade mark) 1.5 parts (eta ^{5-2,4-cyclopentadiene-1-yl)} [ (1,2,3,4,5,6-η)-(1-methylethyl) benzene] -iron (1 +)-hexafluorophosphate (1-) 0.5 part Modified polymer silicone resin solution 0 .5 parts Under the application and curing conditions set in Example 1, only the lamp was loaded with a lamp load of 80 parts. The coating and curing were performed in place of an ozone-less single metal halide lamp of w / cm. Innumerable wrinkle patterns of almost constant size were formed on the surface of the cured product. FIG. 4 is an enlarged copy diagram thereof.

(Example 5) Phenol novolak type epoxy resin (Epoxy equivalent: 172 to 179) 40 parts Bisphenol A type epoxy resin (Epoxy equivalent: 180 to 190) 30 parts Trimethylolpropane triglycidyl ether 30 parts Nippon Soda Co., Ltd. "CI-2639" (trademark) 3 parts This formulation was applied and cured under the application and curing conditions set in Example 1. Innumerable wrinkle patterns of almost constant size were formed on the surface of the cured product. FIG. 4 is an enlarged copy diagram thereof.

Comparative Example 1 Phenol novolak type epoxy resin (epoxy equivalent: 172 to 179) 55 parts 3,4 epoxycyclohexylmethyl (3,4-epoxycyclohexane) carboxylate 40 parts trimethylolpropane triglycidyl ether 5 parts diphenyl 1.5 parts of a mixture of [(phenylthio) phenyl] sulfonium = hexafluorophosphate and (thiodiphenyl) bis [diphenylsulfonium] = bis [hexafluorophosphate] (η ⁵ -2,4-cyclopentadien-1-yl ) [(1,2,3,4,5,6-η)-(1-methylethyl) benzene] -iron (1 +)-hexafluorophosphate (1-) 0.5 part Modified polymer silicone resin Solution 0.5 part This formulation was set up in Example 1. Cloth, was coated cured at curing conditions, but the surface of the cured product has become a thing of no wrinkle pattern smooth.

Comparative Example 2 Phenol novolak type epoxy resin (Epoxy equivalent: 172 to 179) 55 parts 3,4 Epoxycyclohexylmethyl (3,4-epoxycyclohexane) carboxylate 40 parts Trimethylolpropane triglycidyl ether 5 parts 4 -4'bis [di (β-hydroxyethoxy) phenylsulfonio] phenylsulfide-bis- [hexafluorophosphate] 1.5 parts Modified polymer silicone resin solution 0.5 parts This formulation was set up in Example 1. The coating was cured under the conditions of application and curing, but the surface of the cured product was smooth without wrinkles.

Comparative Example 3 Phenol novolak type epoxy resin (Epoxy equivalent: 172 to 179) 85 parts Neopentyl glycol diglycidyl ether 15 parts Diphenyl [(phenylthio) phenyl] sulfonium hexafluorophosphate and (thiodiphenyl) bis [diphenyl 1.5 parts of a mixture of [sulfonium] = bis [hexafluorophosphate] 0.5 parts of a modified polymer silicone resin solution This composition was applied and cured under the application and curing conditions set in Example 1 or Example 3. However, the surface of the cured product became smooth with no wrinkle pattern.

(Comparative Example 4) Phenol novolac type epoxy resin (epoxy equivalent: 172 to 179) 30 parts Bisphenol A type epoxy resin (epoxy equivalent: 180 to 190) 30 parts 3,4 epoxycyclohexylmethyl (3,4-epoxycyclohexane) ) carboxylate 20 parts 20 parts of trimethylolpropane triglycidyl ether 4-4 'bis [di (beta-hydroxyethoxy) phenylsulfonyl O] phenyl sulfide = bis [hexafluorophosphate] 1.5 parts (eta ^5-2,4 -Cyclopentadien-1-yl) [(1,2,3,4,5,6-η)-(1-methylethyl) benzene] -iron (1 +)-hexafluorophosphate (1-) 5 parts Modified polymer silicone resin solution 0.5 parts The coating was cured under the application and curing conditions set in the above, but the surface of the cured product was smooth without wrinkles.

(Comparative Example 5) Phenol novolak type epoxy resin (epoxy equivalent: 172 to 179) 40 parts Bisphenol A type epoxy resin (epoxy equivalent: 180 to 190) 30 parts Trimethylolpropane triglycidyl ether 30 parts 4-4'bis [ Di (β-hydroxyethoxy) phenylsulfonio] Phenylsulfide-bis- [hexafluoroantimonate] 1.5 parts Modified polymer silicone resin solution 0.5 parts This composition was coated and cured as set in Example 1. The coating was cured under the conditions, but the surface of the cured product was smooth without wrinkles.

According to the present invention, plastics, glasses, metals, and other materials that can be applied and cured with ink, such as decoration of sheets for labels and stickers, decoration of outer boxes for cosmetics, decoration of materials for wallpaper, production of stained glass, etc. And a decorative effect by adding a wrinkle pattern excellent in design.

[Brief description of the drawings]

FIG. 1 is an enlarged copy diagram of a wrinkle pattern obtained in Example 1.

FIG. 2 is an enlarged copy diagram of a wrinkle pattern obtained in Example 2.

FIG. 3 is an enlarged copy diagram of a wrinkle pattern obtained in Example 3.

FIG. 4 is an enlarged copy of the wrinkle pattern obtained in Example 4.

FIG. 5 is an enlarged copy of the wrinkle pattern obtained in Example 5.

Claims (5)

[Claims] The present invention relates to a photocationic catalyst which uses an epoxy compound having two or more functionalities as an ink vehicle component and has a low catalytic activity when irradiated with ultraviolet light, that is, (A) mainly acts on the curing of the coating film surface. UV curable surface wrinkle-forming ink, which cures and shrinks the surface of the coating film to form wrinkles on the surface. 2. An ink vehicle component comprising a bifunctional or higher epoxy compound and having a low catalytic activity upon irradiation with ultraviolet light as a photocationic catalyst, that is, (A) a photocationic catalyst which mainly acts on curing of the coating film surface. Is used, whereby the coating film surface undergoes curing shrinkage, forming wrinkles on the surface,
Further, when using the UV irradiator to be used, (A)
A photocationic catalyst having a higher catalytic activity than the photocationic catalyst mainly acting on the curing of the surface of the coating film, that is, a photocationic catalyst capable of curing the inside of the coating film more than (B) and (A) is further used, An ultraviolet curable surface wrinkle forming ink that promotes curing, that is, promotes curing of a coating film while forming wrinkles. (A) The photocationic catalyst which mainly acts on the curing of the coating film surface is a sulfonium salt having a counter ion represented by PF ₆ ^- and having 0 to 3 aromatic rings in its chemical formula. Item 3. An ultraviolet-curable surface wrinkle-forming ink according to item 1 or 2. 4. A sulfonium salt having a counter ion represented by PF ₆ ^- and having 0 to 3 aromatic rings in the chemical formula, is represented by the formula: The ultraviolet curable surface wrinkle forming ink according to claim 1, which is a compound represented by the formula: 5. The photocationic catalyst which cures (B) to the inside of the coating film more than (A) is (η ⁵ -2,4-cyclopentadien-1-yl) [(1,2,3,4) , 5,6-
η)-(1-methylethyl) benzene] -iron (1
+)-Hexafluorophosphate (1-),
The ultraviolet curable surface wrinkle forming ink according to any one of claims 1, 2, 3, and 4.