JPH0987357A - Resin composition and cured product thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition excellent in curability and capable of giving a cured product excellent in gloss and adhesion by mixing a urethane- based alicyclic epoxy resin with a cationically polymerizable substance and/or a (meth)acrylate compound and a photopolymerization initiator. SOLUTION: This resin composition comprises a urethane-based alicyclic epoxy resin (A) prepared by a reaction of an organic polyisocyanate with a hydroxylated alicyclic epoxy resin (e.g. a compound of formula I or II) and a polyol compound as an optional component, a cationically polymerizable substance other than component A and/or a (meth)acrylate compound (B), and a photopolymerization initiator. Because this composition has excellent curability and can give a cured product having high gloss and excellent adhesion, it is desirable for overprinting varnishes, coating materials, printing inks, adhesives, etc., for various substrates.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention typifies ultraviolet rays, which are excellent in curability and whose cured product is an urethane-based alicyclic epoxy resin (A) having an excellent gloss and adhesion and a specific structure as an essential component. And a cured product thereof. The composition of the present invention and its cured product are
It has excellent curability and high gloss, and is suitable for overprint varnishes for paper, woodworking, metal cans, etc., but can be used for various other purposes.

[0002]

2. Description of the Related Art Conventionally, various fields, such as printing inks, paints,
Ultraviolet curable resin compositions have been studied and put to practical use for adhesives, overprint varnishes and the like. Conventionally, glossy paper has been used for books and magazines, but most of them have a plastic film laminated on the paper as a method of producing gloss, and a problem occurs in the paper recycling process. However, 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 is a urethane-based alicyclic epoxy which is a reaction product of an organic polyisocyanate (a), a hydroxyl group-containing alicyclic epoxy resin (b) and a polyol compound (c) as an optional component. Resin (A) and (A)
It relates to a resin composition containing a cationically polymerizable substance other than the components and / or a (meth) acrylate compound (B) and a photopolymerization initiator (C), and a cured product thereof.

In the present invention, a urethane alicyclic epoxy resin (A) is used. Specific examples of the urethane alicyclic epoxy resin (A) include, for example, a polyol compound (C) (for example, ethylene glycol, 1,4-butanediol, 3-methyl-1,5-pentanediol, neopentyl glycol). Polyester diol of 1,4-butanediol and adipic acid, 3-methyl-1,5-
Adipate of pentanediol, 3-methyl-1,5-
Polyester diol of pentanediol and isophthalic acid, polycaprolactone diol of ethylene glycol and ε-caprolactone, polytetramethylene glycol, polyethoxydiol of bisphenol A) and organic polyisocyanate (a) (for example, tolylene diisocyanate, isophorone diisocyanate, A urethane oligomer is obtained by reacting xylylene diisocyanate, methylenebis (4-isocyanatephenyl), hexamethylenediisocyanate, methylenebis (4-isocyanatocyclohexane), trimethylhexamethylenediisocyanate, etc. Next, a hydroxyl group-containing alicyclic epoxy resin (b) (for example,

[0006]

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[0007]

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[0008]

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[0009]

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Etc.) to obtain a urethane-based alicyclic epoxy resin (A-1) or the above organic polyisocyanate (a) and a hydroxyl group-containing alicyclic epoxy resin (b). The urethane alicyclic epoxy resin (A-2) etc. which can be mentioned are mentioned. In the case of urethane type alicyclic epoxy resin (A-1), the reaction between the polyol compound (c) and the organic polyisocyanate (a) is carried out by reacting 1 equivalent of the hydroxyl group of the component (c) with 1. The reaction is preferably carried out at a ratio of 1 to 2.0 equivalents, a reaction temperature of 70 to 100 ° C. and a reaction time of 5 to 15 hours are preferable. Next, it is preferable to react about 1 equivalent of hydroxyl groups of component (b) with 1 equivalent of isocyanate groups of the urethane oligomer obtained by the reaction of component (c) and component (a). The reaction temperature is preferably 70 to 100 ° C. and the reaction time is preferably 5 to 15 hours. In the case of the urethane-based alicyclic epoxy resin (A-2), it is preferable to react about 1 equivalent of hydroxyl groups of the component (b) with 1 equivalent of isocyanate groups of the organic polyisocyanate (a).
The reaction temperature is preferably 70 to 100 ° C. and the reaction time is preferably 5 to 15 hours.

The amount of the urethane type alicyclic epoxy resin (A) used in the composition of the present invention is preferably 5 to 90% by weight,
It is 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 epoxide monomers. Here, as an example of the aromatic epoxy resin, a polyglycidyl ether of a polyhydric phenol having at least one aromatic nucleus or an alkylene oxide adduct thereof, such as bisphenol A, bisphenol F, and bisphenol S Compounds or glycidyl ethers produced by reacting alkylene oxide (eg, ethylene oxide, propylene oxide, butylene oxide, etc.) adducts of bisphenol compounds with epichlorohydrin, novolac type epoxy resins (eg, phenol novolac type epoxy) Resin, cresol / novolak type epoxy resin, bromine phenol / novolak type epoxy resin, etc.), trisphenol methane triglycidyl ether and the like. Specific examples of the alicyclic epoxy resin include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, bis- (3,4-epoxycyclohexylmethyl) adipate, and bis (2,2. 3-epoxycyclopentyl) ether, EHPE-3150 (manufactured by Daicel Chemical Industries, Ltd., alicyclic epoxy resin, softening point 71 ° C.) and the like.

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

Examples of the cationically polymerizable vinyl compound include hydroxyethyl vinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, cyclohexane-1,4-dimethylol divinyl ether, 1,4-butanediol divinyl ether and polyester. Examples thereof include divinyl ether and polyurethane divinyl ether. Further, these cationically polymerizable substances may be used alone or as a mixture of two or more kinds. 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
It is 70% by weight.

Specific examples of the photopolymerization initiator (C) include those which generate cathiin only by irradiation with ultraviolet rays and cationic polymerization initiators which generate cations by heat in addition to ultraviolet rays (for example, triphenyl). Sulfonium hexafluorophosphate, triphenylsulfonium hexasuluroantimonate, diphenyliodonium hexafluoroantimonate, diphenyliotonium hexafluorophosphate, Asahi Denka Kogyo KK, Adeka Optomer SP-170 (hexafluoroantimonate type), SP-150 (hexafluorophosphate type), manufactured by Nippon Soda Co., Ltd., pyridinium salt type, etc., or a photoradical polymerization initiator (for example, 2) that generates radicals by irradiation with ultraviolet rays.
-Hydroxy-2-methyl-1-phenyl propane-
1-one, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyldiphenyl-phosphine oxide, acetophenone dimethyl ketal, benzophenone and the like). 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 ray absorbents, antioxidants, polymerization inhibitors, colorants, inorganic fillers and the like can also be added.

The composition of the present invention can be obtained by blending the blending components preferably in the above proportions, heating, dissolving and mixing. The cured product of the composition of the present invention can be obtained by curing as described below according to a conventional method. That is, the composition of the present invention is applied to various substrates, for example, paper, wood, plastic, metal, etc. by a coating method such as roll coater, screen printing, gravure printing, offset printing, curtain coater, etc. in a thickness of 1 to 50 μm. A cured product can be obtained by applying the composition, irradiating it with ultraviolet rays, and optionally applying heat.

When the composition of the present invention is used as an overprint varnish (luster varnish) of a white coated metal can of a beverage metal can, for example, it is cured as follows,
Obtain a cured product. That is, a cured coating is 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 and the like, but is also suitable as an adhesive, a paint and an ink. The resin composition of the present invention has excellent curability,
The cured product has excellent gloss and adhesion.

[0021]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. Parts in the examples are parts by weight. (Synthesis example of urethane-based alicyclic epoxy resin (A)) Synthesis example 1 Polyester diol of 3-methyl-1,5-pentanediol and adipic acid (molecular weight 500, hydroxyl value 224)
Charge 500 parts and 348 parts of tolylene diisocyanate,
Reacted at 85 ° C. for 12 hours, then the compound of the following structural formula

[0022]

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269 parts were charged and reacted at 85 ° C. for 15 hours to obtain a urethane type alicyclic epoxy resin.

Synthesis Example 2 31 parts of ethylene glycol, 500 parts of polytetramethylene glycol (molecular weight 1000, hydroxyl value 112) and 422 parts of trimethylhexamethylene diisocyanate were charged, reacted at 85 ° C. for 12 hours, and then of the following structural formula. Charge 508 parts of compound and react at 85 ° C for 15 hours

[0025]

[Chemical 6]

A urethane alicyclic epoxy resin was obtained.

Synthesis Example 3 222.2 parts of isophorodiisocyanate, a compound of the following structural formula

[0028]

[Chemical 7]

748 parts were charged and reacted at 85 ° C. for 15 hours to obtain a urethane type alicyclic epoxy resin.

Examples 1 to 3 and Comparative Examples 1 to 3 The compositions were blended according to the blending composition shown in Table 1 (numerical values are parts by weight), mixed, heated and dissolved to prepare. A test piece having a cured film obtained by applying this to a white-coated metal can with a thickness of 5 μm by a roll coating method and curing by irradiating with ultraviolet rays was described below.
An adhesion test was performed.

[0031]

[Table 1] Table 1 Examples Comparative Examples 1 2 3 1 2 3 (A) Component Urethane-based epoxy resin obtained in Synthesis Example 1 50 Urethane-based epoxy resin obtained in Synthesis Example 2 30 Urethane-based epoxy resin obtained in Synthesis Example 3 Epoxy resin 30 Component (B) Triethylene glycol divinyl ether 20 20 1,4-butanediol monovinyl ether 50 50 KAYARAD R-114 * 1 30 30 60 1,6-hexanediol diacrylate 40 10 10 10 40 3,4- Epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate 30 30 50 (C) component ADEKA OPTOMER SP-174 * 2 4 3 3 3 4 Irgacure 184 * 3 2 2 2 5 5 Curable (mJ / cm ² ) 17 27 20 34 138 27 Gloss ○ ○ ○ ○ ○ ○ Adhesion ○ ○ ○ × × ×

The test method and evaluation method are as follows. Curability (mJ / cm ² ): The composition was applied to a white-coated metal can to a thickness of 5 μm by the roll coating method, and the amount of irradiation (mJ / cm ² ) at which the composition became tack-free by irradiating 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 performed using cellophane tape. The peeling state of the first eye was observed and evaluated according to the following criteria.・ ・ ・: 100/100 with no peeling. Δ ... 50/100 to 90/100. X ... 0/100 to 50/100. Gloss: The test piece was observed and evaluated according to the following criteria. ○ ... ・ Gloss was good. △ ・ ・ ・ ・ Something is not glossy. × ・ ・ ・ ・ No gloss

Note * 1 KAYARAD R-114: Nippon Kayaku Co., Ltd., bisphenol A type epoxy resin acrylate * 2 ADEKA OPTOMER SP-170: Asahi Denka Kogyo Co., Ltd. 4,4 'bis [bis ( [2-Hydroxyethoxyphenyl) sulfoniophenyl sulfide bishexafluoroandimonate, photocationic polymerization initiator propylene carbonate 59% diluent * 3 Irgacure 184: 1-hydroxycyclohexyl phenyl ketone, manufactured by Ciba-Geigy Polymerization initiator

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

[0036]

INDUSTRIAL APPLICABILITY The novel resin composition of the present invention is excellent in curability, and the cured product obtained is excellent in gloss and adhesion, and is a Toba print varnish (gloss varnish) for various substrates, paint, printing ink,
It is suitable for adhesives and the like.

Claims (2)

[Claims] 1. A urethane type alicyclic epoxy resin (A) and (A) which is a reaction product of an organic polyisocyanate (a), a hydroxyl group-containing alicyclic epoxy resin (b) and optionally a polyol compound (c). A resin composition comprising a cationically polymerizable substance other than the components and / or a (meth) acrylate compound (B) and a photopolymerization initiator (C). 2. A cured product of the composition according to claim 1.