JPH0940708A - Resin composition and cured product thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition having a low viscosity and excellent curability and giving a cured product excellent in gloss and adhesion by mixing a specified vinyl ether compound with another cationically polymerizable substance or a (meth)acrylate compounds and a photopolymerization initiator. SOLUTION: This resin composition comprises a vinyl ether compound (A) of the formula (n is 1-10), a cationically polymerizable substance and/or a (meth) acrylate compound (B) other than component A and a photopolymerization initiator. The mixing ratio of this composition is particularly desirably such that 10-70wt.% component A, 10-70wt.% component B and 1-10wt.% component C are used. This composition can be converted into a cured product by applying it to a substrate (e.g. paper, wood, a plastic or a metal) by means of a roll coater, gravure printing or the like, irradiating the wet film with ultraviolet rays and optionally heating the film.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention typifies ultraviolet rays containing a vinyl ether compound (A) having a specific structure as an essential component, which has a low viscosity and excellent curability, and has a cured product having excellent gloss and adhesion. And a cured product thereof. The composition of the present invention and a cured product thereof have low viscosity, excellent curability, and high gloss, and
It is suitable for overprint varnishes such as woodworking and metal cans, but can be used for various purposes other than this.

[0002]

2. Description of the Related Art Conventionally, UV curable resin compositions have been studied and put into practical use in various fields, for example, printing inks, paints, adhesives, overprint varnishes, etc., for reasons such as energy saving, no pollution, and quick curing. Is coming. Conventionally, glossy paper has been used for books and magazines, but most of the methods for producing gloss are those in which a plastic film is laminated on paper, which causes problems in the paper recycling process, and therefore UV curing type Although print varnishes have been studied, the present situation is that the curability and coating performance have not been sufficiently satisfied.

[0003]

DISCLOSURE OF THE INVENTION The object of the present invention is a resin which is excellent in curability and coating performance, and a cured product is a resin particularly suitable for luster of paper, woodwork or metal can, which is excellent in high gloss and adhesion. The present invention provides a composition and a cured product thereof.

[0004]

The present invention provides a vinyl ether compound (A) represented by the formula (I).

[0005]

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(Wherein n is an integer of 1 to 10), a cationically polymerizable substance other than the component (A) and / or a (meth) acrylate compound (B) and a photopolymerization initiator (C). The present invention relates to a resin composition and a cured product thereof.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a vinyl ether compound (A) represented by the above formula (I) is used. Specific examples of the vinyl ether compound (A) include ethylene glycol monovinyl ether, diethylene glycol monovinyl ether, triethylene glycol monovinyl ether, tetraethylene glycol monovinyl ether, and pentaethylene glycol monovinyl ether. The amount of the vinyl ether compound (A) used in the composition of the present invention is preferably 5 to 90% by weight, particularly preferably 10 to 70% by weight.

Next, a cationically polymerizable substance other than the component (A) and / or a (meth) acrylate compound (B) is used. Specific examples of the cationically polymerizable substance include, for example,
Examples thereof include cationically polymerizable vinyl compounds such as epoxy resin, styrene and vinyl ether, and cyclic ethers such as spiro orthoester, bicyclo orthoester and spiro orthocarbonate. Examples of the epoxy resin include conventionally known aromatic epoxy resins, alicyclic epoxy resins, aliphatic epoxy resins, and further epoxide monomers. An example of the aromatic epoxy resin is a polyglycidyl ether of a polyhydric phenol having at least one aromatic nucleus or an alkylene side adduct thereof, and is, for example, bisphenol A, bisphenol F or bisphenol S. Glycidyl ethers produced by reacting a compound or an alkylene oxide (for example, ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of a bisphenol compound with epichlorohydrin,
Examples thereof include novolac type epoxy resins (for example, phenol / novolac type epoxy resin, cresol / novolac type epoxy resin, brominephenol / novolac type epoxy resin, etc.) and trisphenolmethane triglycyl ether. Specific examples of the alicyclic epoxy resin include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and bis- (3,4-epoxycyclohexylmethyl).
Adipate, bis (2,3-epoxycyclopentyl)
Ether, EHPE-3150 (manufactured by GYCEL CHEMICAL INDUSTRIES, LTD., Alicyclic epoxy resin, softening point 71 ° C.) and the like can be mentioned.

Further, examples of the aliphatic epoxy resin include polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof. Typical examples thereof are diglycidyl ethers of 1,4-butanediol, 1, 6-Hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, potaethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, ethylene glycol, propylene glycol, glycerin Examples include polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides (ethylene oxide, propylene oxide) to a polyhydric alcohol. It is. Further, examples of the epoxide monomers include monoglycidyl ether of aliphatic higher alcohol, phenol, cresol, butylphenol, and monoglycidyl ether of polyether alcohol obtained by adding alkylene oxide to these.

As the cationically polymerizable vinyl compound, for example, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, cyclohexane-1,4-dimethylol divinyl ether, 1,4-
Examples thereof include butanediol divinyl ether, polyester divinyl ether, polyurethane divinyl ether and the like. Further, these cationically polymerizable substances may be used alone or as a mixture of two or more kinds. Used in the present invention (meta)
Examples of the acrylate compound include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxybutyl (meth) acrylate; ethylene glycol, methoxytetraethylene glycol, polyethylene glycol and propylene glycol. Mono or di (meth) acrylates; (meth) acrylamides such as N, N-dimethyl (meth) acrylamide and N-methylol (meth) acrylamide; aminoalkyl (s such as N, N-dimethylaminoethyl (meth) acrylate. (Meth) acrylates; hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, tris-hydroxyethyl isocyanurate Polyhydric alcohols such as glutamine and the like, or polyhydric (meth) acrylates of adducts of these ethylene oxides or propylene oxides; phenoxy (meth) acrylates, bisphenol A di (meth) acrylates and ethylene of these phenols (Meth) acrylates such as oxides or propylene oxide adducts; Reactivity of (meth) acrylates of glycidyl ethers such as glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl isocyanurate and melamine (meth) acrylate Monomer, epoxy resin (for example, phenol novolac epoxy resin, cresol novolac epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin Trisphenolmethane epoxy resins, polybutadiene-modified epoxy resins, alicyclic epoxy resins, brominated phenol novolak epoxy resin, brominated bisphenol A type epoxy resin, amino group-containing epoxy resin) and (meth)
Epoxy (meth) acrylate which is a reaction product of acrylic acid, polybasic acid anhydrides such as the above epoxy (meth) acrylate (for example, maleic anhydride, succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc. ) Modified carboxylic acid-modified epoxy (meth) acrylate, a polyol component (for example, ethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, 3-methyl-1,5). -Pentanediol, polyethylene glycol, polypropylene glycol, 1,
4-dimethylolbenzene, trimethylolpropane,
Pentaerythritol) and acid components (eg, maleic acid, succinic acid, adipic acid, phthalic acid, isophthalic acid,
(Meth) acrylic acid ester of polyester polyol which is a reaction product of a dibasic acid such as terephthalic acid or tetrahydrophthalic acid, or a dibasic acid anhydride, or a polyol (eg, ethylene glycol, neopentyl glycol, polytetramethylene) Glycol, polyester polyol, polycaprolactone polyol, etc.) and organic polyisocyanate (for example, tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, etc.) and hydroxyl group-containing (meth) acrylate (for example, 2-hydroxyethyl (meth) acrylate, 2- Hydroxypropyl (meth) acrylate,
1,4-butanediol mono (meth) acrylate etc.)
Examples thereof include reactive oligomers such as urethane (meth) acrylate which is a reaction product of The proportion of the component (B) used in the composition of the present invention is preferably 5 to 90% by weight, particularly preferably 10 to 70% by weight.

Specific examples of the photopolymerization initiator (C) include those which generate cations only by irradiation with ultraviolet rays, and those which generate cations not only by ultraviolet rays but also by heat (for example, cations). Triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium hexafluoroantimonate, diphenyliotonium hexafluorophosphate, Asahi Denka Kogyo KK, Adeka Optomer SP-170 (hexaflufluoroantimonate type) ), SP-150 (hexafluorophosphate type), Nippon Soda Co., Ltd., pyridinium salt type, etc.) or a photo-radical polymerization initiator that generates radicals by irradiation with ultraviolet rays (eg, 2-hydroxy). 2-Methyl-1-phenyl-propan-1-one, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyldiphenyl-phosphine oxide, acetophenone dimethyl ketal , Benzophenone, etc.). These can be used alone or in combination of two or more.

The proportion of the photopolymerization initiator (C) used in the composition of the present invention is preferably 0.5 to 20% by weight, particularly preferably 1 to 10% by weight.

The composition of the present invention further comprises a non-reactive resin (eg, acrylic polymer, polyester, polyurethane, polystyrene, polyvinyl chloride, etc.), organic solvent, alcohols such as ethylene glycol and diethylene glycol, leveling agent, defoaming agent. Agents, slip agents, ultraviolet absorbers, antioxidants, polymerization inhibitors, colorants or inorganic fillers can also be added.

The composition of the present invention can be obtained by blending the blending ingredients preferably in the above proportions, heating, dissolving and mixing. A cured product can be obtained by curing the composition of the present invention in the following manner. That is, the composition of the present invention various substrates, for example, paper, wood, plastic, metal, etc. roll coater, screen printing,
A cured product can be obtained by applying a film having a thickness of 1 to 50 μm by a coating method such as gravure printing, offset printing, or a curtain coater, irradiating with ultraviolet rays, and further applying heat as necessary.

When the composition of the present invention is used as a white-coated metal-based overprint varnish (luster varnish) of a beverage metal can, for example, it is cured as follows,
Obtain a cured product. That is, a cured coating can be obtained by applying a white coated metal can to a thickness of 2 to 5 μm by a roll coating method and then irradiating it with ultraviolet rays to cure it.

The composition of the present invention is useful as an overprint varnish (luster varnish) for paper, wood, plastics, metals, etc., but is also suitable as an adhesive, a paint and an ink. The resin composition of the present invention has a low viscosity and excellent curability, and the cured product has excellent gloss and adhesion.

[0017]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. Parts in the examples are parts by weight. Examples 1 to 3 and Comparative Examples 1 to 3 Compositions were blended according to the blending composition (numerical values are parts by weight) shown in Table 1 below, and mixed, heated and dissolved to prepare. By a roll coating method, a white coated metal can was applied to a thickness of 5 μm, and a test piece having a cured film obtained by curing by irradiating with ultraviolet rays was subjected to the curability, gloss, and adhesion tests described below. .

[0018]

Table 1 Example Comparative Example 1 2 3 1 2 3 (A) Component 2-hydroxyethyl vinyl ether 50 35 50 Diethylene glycol monovinyl ether 15 (B) Component 3,4-epoxycyclohexyl methyl-3,4-epoxycyclohexyl Sun carboxylate 50 50 Epicoat 828 * 1 50 50 KAYARAD R-114 * 2 50 50 1,6-hexanediol diacrylate 50 Triethylene glycol divinyl ether 50 50 (C) component Adeka optomer SP-170 * 3 3 3 3 3 33 Irgacure 184 * 4 1.5 3 Viscosity (25 ℃, CPS) 9 60 16 16 230 32 Curability (mJ / m ² ) 30 35 35 1000 400 100 or more Adhesion ○ ○ ○ × × ── Gloss ○ ○ ○ ○ ○ ──

The test method and evaluation method are as follows. Viscosity (25 ° CPS): The composition was measured at 25 ° C with a B-type viscometer. The lower the viscosity, the better the coatability.

Curability (mJ / cm ² ): Irradiation dose (mJ / cm ² ) to make the composition tack-free by applying a composition to a white-coated metal can with a thickness of 5 μm by a roll coating method and irradiating with ultraviolet rays. Was measured.

Adhesion: According to JIS K5400, 100 pieces of 1 mm squares were made on a test piece and a peeling test was conducted using cellophane tape. The peeling state of the first eye was observed and evaluated according to the following criteria. ○ ・ ・ ・ ・ 100/100 without peeling △ ・ ・ ・ ・ 50/100 to 90/100 × ・ ・ ・ ・ 0/100 to 50/100

Gloss: The test piece was observed and evaluated according to the following criteria.・ ・ ・: Good gloss. △ ・ ・ ・ ・ Something is not glossy. × ・ ・ ・ ・ No gloss

Note * 1 Epicoat 828: Yuka Shell Epoxy Co., Ltd.
Bisphenol A type epoxy resin * 2 KAYARAD R-144: Nippon Kayaku Co., Ltd.
Manufactured by Asahi Denka Kogyo Co., Ltd., 4,4′-bis [bis ([2-hydroxyethoxyphenyl) sulfonio] phenyl sulfide bishexafluoroantimolybdenum, acrylate of bisphenol A type epoxy resin * 3 Nate, cationic heavy initiator, propylene carbonate 50% diluted product, * 4 Irgacure 184: manufactured by Ciba Geigy,
1-hydroxycyclohexyl phenyl ketone, photopolymerization initiator

As is clear from the evaluation results in Table 1, the composition of the present invention has low viscosity and excellent curability, and the cured product has high gloss and excellent adhesion.

[0025]

The novel resin composition of the present invention has a low viscosity and excellent curability, and the resulting cured product has excellent gloss and adhesion, and is used as an overprint varnish (varnish) for various base materials and paints. It is suitable for printing inks, adhesives, etc.

Claims (2)

[Claims] 1. A vinyl ether compound (A) represented by the following formula (I): (In the formula, n is an integer of 1 to 10), a cationically polymerizable substance other than the component (A) and / or a (meth) acrylate compound (B), and a photopolymerization initiator (C). A resin composition comprising: 2. A cured product of the composition according to claim 1.