KR20070023667A - Radiation curable composition - Google Patents

Abstract

The present invention provides a radiation curable resin composition exhibiting excellent adhesive strength, excellent processability, heat resistance and water resistance to PET, TAC, Arton, and the like, and exhibiting high speed curing properties. The radiation curable resin composition of the present invention comprises (A) 30 to 70% by weight of a urethane (meth) acrylate having a number average molecular weight of 10,000 to 40,000; And (B) 0.1 to 70 wt% of an ethylenically unsaturated monomer comprising a cyclic ether.

Radiation curable resin composition, urethane (meth) acrylate, ethylenically unsaturated monomer

Description

Radiation-Curable Composition

The present invention relates to a radiation curable resin composition. More specifically, the present invention relates to films made of glass and plastic substrates, in particular styrene-methyl methacrylate (MS) copolymers, polyethylene terephthalate (PET), triacetyl cellulose (TAC), and various cyclic olefin polymers. Because of its excellent adhesiveness and excellent heat resistance, water resistance and moldability, it is useful as an adhesive in the fields of building materials, packaging materials, printing materials, display materials, electrical / electronic component materials, optical component materials, liquid crystal panels, etc. It relates to a radiation curable resin composition.

Curable liquid adhesives are widely used in a variety of fields such as packaging materials, display materials such as labels, electronic components, precision instruments, and building materials. In recent years, the radiation curable liquid adhesive which irradiates and hardens various radiations, such as an ultraviolet-ray or an electron beam, for the purpose of speeding up a manufacturing process and improving productivity, is widely used instead of the conventional thermosetting adhesive. With the expansion of such fields of application and the increase in the required performance for the application, there is a demand for high performance for radiation curable liquid adhesives. For example, high adhesive strength as well as high heat resistance are required for adhesives for laminating PET films.

(a) a small number average molecular weight (5,000-15,000) urethane (meth) acrylate, (b) acryloyl morpholine, dimethylacrylamide, diethylacrylamide and diisopropylacrylamide, and (c It has been reported that curable liquid adhesive compositions containing phenoxy polyethylene glycol (PEG = 1 to 5) acrylate show excellent adhesion to PVC and PET (see Japanese Patent Laid-Open No. 7-310067). .

Moreover, (A) urethane (meth) acrylate, (B) silane compound which has a mercapto group, (C) photoinitiator, (D) ethylenically unsaturated monomer which has an amino group, and (E) (meth) acrylate compound It has been reported that the photocurable resin composition containing the is useful as a coating layer for the copper-coated wire used as a tension member of the optical fiber unit (see Japanese Patent Laid-Open No. 2000-198824).

However, none of the above compositions had sufficient adhesive strength, so polyethylene terephthalate (PET), styrene-methyl methacrylate (MS), glass, triacetyl cellulose (TAC), and Arton (JSR Corporation (JSR) There is still a need for a radiation curable resin composition that exhibits excellent adhesive strength to norbornene-based resins).

Accordingly, an object of the present invention is to provide a radiation curable resin composition exhibiting excellent adhesive strength, excellent molding processability, heat resistance, and water resistance to PET, TAC, Arton, and the like, and exhibiting high-speed curing.

<Overview of invention>

According to the present invention, the following radiation curable resin compositions can be obtained.

1. (A) 30 to 70% by weight of urethane (meth) acrylate having a number average molecular weight of 10,000 to 40,000; And

(B) 0.1 to 70% by weight of ethylenically unsaturated monomer containing cyclic ether in structure

Radiation curable resin composition comprising a.

2. The radiation curable resin composition according to item 1, further comprising an ethylenically unsaturated monomer having a glass transition temperature of (C) homopolymer of 60 ° C or higher.

3. The radiation curable resin composition according to the above 1 or 2, further comprising (D) γ-mercaptopropyltrimethoxysilane.

4. The method according to any one of items 1 to 3 above,

(A) 30 to 70% by weight of urethane (meth) acrylate having a number average molecular weight of 10,000 to 40,000;

(B) 0.1 to 70 wt% of an ethylenically unsaturated monomer comprising a cyclic ether;

(C) 10 to 60% by weight of an ethylenically unsaturated monomer having a glass transition temperature of at least 60 ° C. of the homopolymer; And

(D) 0.1 to 5% by weight of γ-mercaptopropyltrimethoxysilane

Radiation curable resin composition comprising a.

5. Radiation curable resin composition according to item 4, wherein component (A) is present in an amount of 45 to 70% by weight.

6. Radiation curable resin composition according to item 4 or 5, wherein component (B) is present in an amount of 1 to 20% by weight.

7. Radiation curable resin composition according to item 6 above, wherein component (B) is present in an amount of 4 to 20% by weight.

8. The radiation curable resin composition according to any one of items 3 to 7, wherein component (C) is present in an amount of 20 to 60% by weight.

Moreover, this invention relates to the use of a radiation curable resin composition.

9. The radiation curable resin composition according to any one of items 1 to 8, which is used as an adhesive.

According to the invention, the following articles can also be obtained.

10. An article comprising a cured composition, wherein the composition is a composition according to any of the preceding clauses.

11. An article according to item 10, comprising a substrate and a coating layer thereon, wherein the coating layer consists of the composition according to any one of items 1 to 8, with or without the coating layer cured.

12. Arton according to the above 10, wherein the substrate is a styrene-methyl methacrylate (MS) copolymer, polyethylene terephthalate (PET), triacetyl cellulose (TAC), a cyclic olefin polymer, and a norbornene heat-resistant transparent resin. An article that is a film or sheet.

Effect of the Invention

The radiation curable resin composition of this invention shows the outstanding adhesiveness, is excellent also in heat resistance, water resistance, and molding processability, and is useful as an adhesive composition. In particular, component (B) increases the adhesive strength between the film and the adhesive by swelling the film. The radiation curable resin composition of the present invention exhibits excellent adhesion to PET, MS, glass and plastic substrates, especially TAC and Arton films.

Component (A) used in the present invention is a urethane (meth) acrylate compound having a number average molecular weight of 10,000 to 40,000. Component (A) is preferably prepared by reacting a polyol compound, a polyisocyanate compound and a hydroxyl group-containing (meth) acrylate.

Specifically, component (A) is preferably prepared by reacting an isocyanate group of a polyisocyanate compound with a hydroxyl group of a polyol compound and a hydroxyl group of a hydroxyl group-containing (meth) acrylate compound, respectively. The following four methods can be presented as examples of such reaction methods.

Method 1: A method in which a polyol compound, a polyisocyanate compound, and a hydroxyl group-containing (meth) acrylate compound are all reacted together.

Method 2: A method of reacting a polyol compound with a polyisocyanate compound and reacting the product with a hydroxyl group-containing (meth) acrylate compound.

Method 3: A method of reacting a polyisocyanate compound with a hydroxyl group-containing (meth) acrylate compound and reacting the product with the polyol compound.

Method 4: A method of reacting a polyisocyanate compound with a hydroxyl group-containing (meth) acrylate compound, reacting the product with a polyol compound, and then reacting the product with a hydroxyl group-containing (meth) acrylate compound .

Examples of polyols used as raw materials for component (A) of the present invention include aromatic polyether polyols, aliphatic polyether polyols, alicyclic polyether polyols, polyester polyols, polycarbonate polyols, polycaprolactone polyols, and the like.

Examples of aromatic polyether polyols include ethylene oxide addition diols of bisphenol A, propylene oxide addition diols of bisphenol A, butylene oxide addition diols of bisphenol A, ethylene oxide addition diols of bisphenol F, and propylene oxide of bisphenol F Addition diols, butylene oxide addition diols of bisphenol F, alkylene oxide addition diols of hydroquinone, alkylene oxide addition diols of naphthoquinone, and the like. The aromatic polyether polyols are commercially available as Uniol DA700, DA1000 (Nippon Oil and Fats Co., Ltd.) and the like.

Examples of aliphatic polyether polyols include ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, substituted tetrahydrofuran, oxetane, substituted oxetane, (Co) polymers obtained by ring-opening (co) polymerizing at least one compound selected from tetrahydropyran and oxepan. Specific examples of the aliphatic polyether polyols include polyethylene glycol, 1,2-polypropylene glycol, 1,3-polypropylene glycol, polytetramethylene glycol, 1,2-polybutylene glycol, polyisobutylene glycol, and propylene jade. Seed and tetrahydrofuran copolymer polyol, ethylene oxide and tetrahydrofuran copolymer polyol, ethylene oxide and propylene oxide copolymer polyol, tetrahydrofuran and 3-methyltetrahydrofuran polyol, ethylene Copolymer polyols of oxide and 1,2-butylene oxide, and the like.

Examples of alicyclic polyether polyols include ethylene oxide added diols of hydrogenated bisphenol A, propylene oxide added diols of hydrogenated bisphenol A, butylene oxide added diols of hydrogenated bisphenol A, and ethylene oxide of hydrogenated bisphenol F The addition diol, the propylene oxide addition diol of hydrogenated bisphenol F, the butylene oxide addition diol of hydrogenated bisphenol F, the dimethylol compound of dicyclopentadiene, a tricyclodecane dimethanol, etc. are mentioned.

Examples of commercially available products of the aliphatic polyether polyols and alicyclic polyether polyols include Unisafe DC 1100, Unisafe DC 1800, Unisafe DCB 1800 (Nipbon Oil & Fats Company Limited); PPTG 4000, PPTG 2000, PPTG 1000, PTG 2000, PTG 3000, PTG 650, PTGL 2000, PTGL 1000 (manufactured by Hodogaya Chemical Co., Ltd.); Exenol 4020, Exenol 3020, Exenol 2020, Exenol 1020 (Asahi Glass Co., Ltd. product); PBG 3000, PBG 2000, PBG 1000, Z 3001 (made by Daiichi Kogyo Seiyaku Co., Ltd.); Acclaim 2200, 3201, 4200, 6300, 8200 (manufactured by Sumika Bayer Urethane Co., Ltd.); NPML-2002, 3002, 4002, and 8002 (Asahi Glass Company Limited).

Examples of the polyester polyol include ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, 3 Polyhydric alcohols such as -methyl-1,5-pentanediol, 1,9-nonanediol or 2-methyl-1,8-octanediol to phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, adipic acid or sebacic acid And polyester polyols obtained by reacting with a polybasic acid such as the like. Polyester polyols are commercially available as Kurapol P-2010, PMIPA, PKA-A, PKA-A2, PNA-2000 (manufactured by Kuraray Co., Ltd.) and the like.

Examples of the polycarbonate polyols include 1,6-hexanepolycarbonate and the like. Examples of commercially available polycarbonate polyols include DN-980, 981, 982, 983 (manufactured by Nippon Polyurethane Industry Co., Ltd), Plascel CD-205, CD-983, CD -220 (manufactured by Daicel Chemical Industries, Ltd.), PC-8000 (manufactured by US PPG), and the like.

Examples of polycaprolactone polyols include ε-caprolactone divalent diols (e.g. ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,2-polybutylene glycol, 1 And 6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol or 1,4-butanediol and the like. Examples of commercially available products of polycaprolactone polyols include PLACEL 205, 205AL, 212, 212AL, 220, and 220AL (product of Daicel Chemical Industries, Ltd.).

Examples of other diols that may be used in the present invention include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, Poly-β-methyl-δ-valerolactone, hydroxy-terminated polybutadiene, hydroxy-terminated hydrogenated polybutadiene, castor oil-modified polyols, diol-terminated compounds of polydimethylsiloxane, polydimethylsiloxane carbitol-modified Polyols and the like.

Among the polyol compounds, polypropylene glycol, ethylene oxide / propylene oxide copolymer diol, ethylene oxide / 1,2-butylene oxide copolymer diol and propylene oxide / tetrahydrofuran copolymer diol are preferable, Ethylene oxide / 1,2-butylene oxide copolymer diol is particularly preferred.

The number average molecular weight of the polyol compound to be used is preferably 500 to 12,000, more preferably 1,500 to 9,000, and most preferably 3,500 to 9,000. When the number average molecular weight of the polyol compound is less than 500, since the Young's modulus at room temperature and low temperature of the resulting cured product rises, sufficient adhesion cannot be obtained, whereby zipping may occur. . When the number average molecular weight exceeds 12,000, the viscosity of the composition rises and the coatability at the time of coating the substrate with the composition may decrease.

Examples of the hydroxyl group-containing (meth) acrylate compound which is one of the raw materials of component (A) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (Meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, 2-hydroxyalkyl (meth) acryloyl phosphate, 4-hydroxy Oxycyclohexyl (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolethane di (meth) acrylic Latex, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and (meth) acrylates represented by the following formulas (1) and (2).

In the above formula, R ¹ represents a hydrogen atom or a methyl group, and m is an integer of 1 to 15.

As a further example, a compound obtained by addition reaction of a glycidyl group-containing compound such as alkyl glycidyl ether, allyl glycidyl ether or glycidyl (meth) acrylate with (meth) acrylic acid is mentioned. Among these hydroxyl group-containing (meth) acrylate compounds, 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate are particularly preferred.

Examples of polyisocyanate compounds include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 1,5-naphthalene Diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3 ' -Dimethylphenylene diisocyanate, 4,4'-biphenylene diisocyanate, 1,6-hexane diisocyanate, isophorone diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 1,4-hexamethylene diisocyanate Isocyanate, bis (2-isocyanatoethyl) fumarate, 6-isopropyl-1,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, lysine diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated Xylylene die Cyano and the like carbonate, tetramethyl xylylene diisocyanate, and norbornane diisocyanate. Among these polyisocyanate compounds, hydrogenated xylylene diisocyanate, isophorone diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate and the like are preferable. These polyisocyanate compounds may be used independently or may use 2 or more types together.

The number average molecular weights of the urethane (meth) acrylate compound which is the component (A) of this invention obtained as mentioned above are 10,000 or more and 40,000 or less. If the number average molecular weight of a urethane (meth) acrylate compound is less than 10,000, a desired adhesive strength cannot be obtained. When the number average molecular weight of the urethane (meth) acrylate compound exceeds 40,000, the viscosity of the composition becomes excessively high.

The urethane (meth) acrylate compound which is the component (A) of the present invention is preferably 30 to 70% by weight in view of the coating property of the composition and the adhesiveness, processability, flexibility, and long-term reliability of the adhesive obtained by curing the composition. It is included in the composition of the present invention in an amount of%, particularly preferably in an amount of 45 to 70% by weight.

Examples of the component (B) of the present invention, i.e., an ethylenically unsaturated monomer including a cyclic ether in its structure, include glycidyl (meth) acrylate, oxetanylmethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylic Latex, tetrahydropyranyl (meth) acrylate, cyclic trimethylolpropane formal acrylate, ethylene oxide-modified (meth) acrylate, propylene oxide-modified (meth) acrylate and caprolactone-modified of each compound (Meth) acrylates, and the like. Among these, monomers containing a tetrahydrofuran (THF) skeleton represented by the following formulas (3) and (4) are preferable, and tetrahydrofurfuryl acrylate is particularly preferred.

In the above formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkylene group having 2 to 8 carbon atoms, preferably 2 to 5 carbon atoms, n is an integer of 0 to 8, preferably 0 to 2, and R ³ represents a hydrogen atom or a methyl group, R ⁴ represents an alkylene group having 2 to 8 carbon atoms, preferably 2 to 5 carbon atoms, and p is an integer of 0 to 8, preferably 0 to 4;

Compound represented by the formula (3) or (4) is Viscoat # 150 (manufactured by Osaka Organic Chemical Industry, Ltd.), Light Ester THF, light acrylate ( Light Acrylate) THF-A (manufactured by Kyoeisha Chemical Co., Ltd.), SR285, SR203, CD611 (Sartomer Co., Inc.), and the like. have.

Component (B) is used in an amount of 0.1 to 70% by weight, preferably 1 to 20% by weight, particularly preferably 4 to 20% by weight, relative to 100% by weight of the composition. If the amount is less than 0.1% by weight, the adhesive strength may be lowered. If the amount exceeds 70% by weight, the substrate may be damaged. If the amount exceeds 20% by weight, the viscosity of the liquid composition may sometimes be excessively low, making handling difficult. The advantage of the composition according to the invention is that the adhesion strength to TAC and Arton is increased by including component (B).

Component (C) preferably used in the present invention is an ethylenically unsaturated monomer in which the glass transition temperature of the homopolymer is 60 ° C or higher. Glass transition temperature is measured by differential scanning calorimetry. It should be noted that component (C) is an ethylenically unsaturated monomer different from component (B). Specific examples of component (C) include acryloyl morpholine, dimethylacrylamide, diethylacrylamide, diisopropylacrylamide, isobornyl (meth) acrylate, dicyclopentenyl acrylate, dicyclopentanyl ( Meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, cyclohexyl methacrylate, dicyclopentadienyl (meth) acrylate, tri Cyclodecanyl (meth) acrylate, diacetone acrylamide, isobutoxymethyl (meth) acrylamide, N-vinylpyrrolidone, N-vinylcaprolactam, 3-hydroxycyclohexyl acrylate, 2-acryloyl Cyclohexyl succinate and the like. Among them, acryloyl morpholine, dimethyl acrylamide, N-vinylpyrrolidone and N-vinyl caprolactam are preferable. A component (C) may be used independently or may use 2 or more types together.

Among the compounds given as examples of component (C), isobornyl acrylate, dicyclopentenyl acrylate, dicyclopentanyl acrylate and dicyclopentanyloxyethyl acrylate have the advantage of improving the water resistance of the cured product of the present invention. . In addition, N-vinylpyrrolidone and N-vinylcaprolactam have the advantage of improving the curability of the composition of the present invention. Therefore, further excellent physical properties can be obtained by using two or more kinds of the above compounds arbitrarily combined as component (C). Particularly preferred combinations are at least one compound selected from acryloyl morpholine, dimethylacrylamide, N-vinylpyrrolidone and N-vinylcaprolactam with isobornyl acrylate, dicyclopentenyl acrylate and dicyclopentanyl Combination with at least one compound selected from acrylate and dicyclopentanyloxyethyl acrylate.

Commercially available components (C) include ACMO, DMAA (Kohjin Ltd.), New Frontier IBA (Daiichi Kogyo Seiyaku Company Limited), IBXA (Osaka Organic Chemical Industries Limited), FA511A, FA512A, FA513A (manufactured by Hitachi Chemical Co., Ltd.), light ester M, E, CH, TB, IB-X and IB-XA (manufactured by Kyoeisha Chemical Company Limited), Aronix M150, M156, TO1315, TO1316 (manufactured by Toagosei Co., Ltd.), FA544A, 512M, 512MT, and 513M (Hitachi Chemical Company Limited).

Component (C) is preferably included in the composition in an amount of 10 to 60% by weight, more preferably 20 to 60% by weight. If the amount of component (C) is less than 10% by weight, the desired adhesive strength cannot be obtained. If the amount exceeds 60% by weight, the desired adhesive strength may not be obtained but the water resistance may be lowered.

The adhesive strength to a board | substrate can be improved by including (gamma)-mercaptopropyl trimethoxysilane as a component (D) in the radiation curable resin composition of this invention. Component (D) is preferably used in the composition of the present invention in an amount of 0.1 to 5% by weight.

In the present invention, in addition to the essential components (A) and (B) and the optional components (C) and (D), other monofunctional and polyfunctional polymerizable monomers other than the components (B), (C) and (D) may also be used. Can be used arbitrarily. In one preferred embodiment, the mono- and polyfunctional polymerizable monomers, except for the monomers present in the composition comprising components (A), (B), (C) and (D), comprise components (A), (B), It is used in addition to (C) and (D).

Examples of monofunctional monomers include n-alkyl (meth) acrylates such as benzyl (meth) acrylate, nonyl (meth) acrylate, dodecyl (meth) acrylate and lauryl (meth) acrylate, isobutyl (meth Isoalkyl (meth) acrylates such as) acrylate, 2-ethylhexyl (meth) acrylate, 2-ethylhexylcarbitol (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy Propyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (Meth) acrylate, 2-acryloyloxyethyl succinate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylic Yite, t-butyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, iso-octyl (meth) acrylate, iso -Decyl (meth) acrylate, undecyl (meth) acrylate, octadecyl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, cyclohexyl acrylate, ethoxy Ethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, bornyl (meth) acrylate, t-octyl (meth) acrylamide, dimethylaminoethyl (meth ) Acrylate, diethylaminoethyl (meth) acrylate, and 7-amino-3,7-dimethyloctyl (meth) acrylate. Moreover, the (meth) acrylate compound represented by following General formula (5) is also mentioned.

In the above formula, R ¹ represents a hydrogen atom or a methyl group, R ⁵ represents an alkylene group having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms, and R ⁶ represents a hydrogen atom or 1 to 12 carbon atoms, preferably 1 to 9 carbon atoms. Represents an alkyl group, and l is 0 to 12, preferably an integer of 1 to 8.

Commercially available products of the compound represented by the formula (5) include AIB, 2-MTA, Biscot # 158, # 3700 (manufactured by Osaka Organic Chemicals Limited), LA, PO-A, P-200A, HOA-MS Isha Chemical Company Limited), Aronix M111, M113, M114, M117 and M120 (Doagosei Company Limited), Kayayarad TC110S, R629, R644 (Nippon Kayaku Co., Ltd. ), Saromer 506 (manufactured by Somar Corp.), and the like.

The acrylate compound represented by the following formula (6) is preferably excluded from the monofunctional monomer.

Wherein q is an integer from 1 to 5.

Examples of polyfunctional monomer components include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol ethylene oxide-modified tri (meth) acrylate, pentaerythritol tetra (meth) acrylic Polyethylene glycol di (meth) acrylates, such as pentaerythritol ethylene oxide-modified tetra (meth) acrylate, ethylene glycol di (meth) acrylate and tetraethylene glycol di (meth) acrylate, 1,4 -Butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate, tris (2-hydroxy Ethyl) isocyanurate tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tricyclodecane dimethanol Epoxy (meth) acrylate etc. which are obtained by adding (meth) acrylate to the diglycidyl ether of di (meth) acrylate, ethylene oxide addition bisphenol A di (meth) acrylate, and bisphenol A are mentioned. . Examples of commercially available polyfunctional monomers include Yupimer UV, SA 1002, SA 2007 (manufactured by Mitsubishi Chemical Corp.), Biscot @ 700 (Osaka Organic Chemical Industries Limited), Kayard R- 604, DPCA-20, DPCA-30, DPCA-60, DPCA-120, HX-620, D-310, D-330 (made by Nippon Kayaku Co., Ltd.), Aronix M-210, M-215, M- 315, M-325 (Toagosei Co., Ltd. product) etc. are mentioned.

The monofunctional and polyfunctional polymerizable monomers other than the components (A), (B), (C) and (D) are preferably 0 to 70% by weight, more preferably 0 to 40 from the viewpoint of adhesive strength and the like. It is included in the composition in an amount by weight.

In addition to the above components, the radiation curable resin composition of the present invention contains various additives such as colorants, light stabilizers, silane coupling agents, antioxidants, thermal polymerization inhibitors, leveling agents, surfactants, preservatives, plasticizers, Lubricants, solvents, fillers, anti-aging agents, wettability modifiers and coating surface modifiers may optionally be added.

The radiation curable resin composition of the present invention can be cured by irradiating radiation. As used herein, "radiation" refers to activated energy rays such as visible light, ultraviolet light, electron beams and X-rays. When hardening a radiation curable resin composition with an ultraviolet-ray, it is preferable to use a UV sensitive photoinitiator. Examples of UV sensitive photoinitiators include 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole , 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, Michler's ketone, benzoin propyl ether, benzoin ethyl ether , Benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, thioxanthone , Diethyl thioxanthone, 2-isopropyl thioxanthone, 2-chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide etc. are mentioned. Commercially available products of the compounds include Irgacure 184, 651, 500, 907, CG 1369, CG 24-61 (manufactured by Ciba Geigy), Lucirine TPO (BASF), Taro Darocure 1116, 1173 (manufactured by Merck), Ubecryl P36 (manufactured by UCB), and the like.

In the case of curing the composition with visible light, it is preferable to use a visible light sensitive photopolymerization initiator such as camphorquinone.

By adding other additives having a sensitization effect, the photopolymerization sensitivity can be improved. Examples of the photosensitizers include triethylamine, diethylamine, N-methyldiethanolamine, ethanolamine, 4-dimethylaminobenzoic acid, 4-methyl dimethylamino benzoate, 4-ethyl dimethylaminobenzoate and 4-iso Amyl dimethylaminobenzoate and the like, and examples of commercially available products include Ubecryl P102, 103, 104, 105 (manufactured by UCB). The photopolymerization initiator is preferably included in the composition in an amount of 0.1 to 10% by weight.

The radiation curable resin composition of this invention can be manufactured by mixing the said components using the conventional method. The viscosity of the composition of the present invention thus prepared is usually 100 to 20,000 cps / 25 ℃, preferably 200 to 10,000 cps / 25 ℃.

The invention is illustrated in more detail by the following examples. However, the present invention is not limited to these examples.

<Synthesis example 1 of urethane (meth) acrylate>

In a reaction vessel equipped with a stirrer, 1552 g of polypropylene glycol having a number average molecular weight of 4000, 114.8 g of isophorone diisocyanate, 0.41 g of 2,6-di-t-butyl-p-cresol, and 0.14 g of phenothiazine were added. Put in. The mixture was then cooled to 15 ° C. with stirring. After addition of 1.4 g of dibutyltin dilaurate, the mixture was slowly heated to 35 ° C. in 1 hour with stirring. The mixture was then heated to 50 ° C. to react. After the residual isocyanate group concentration was reduced to 1.63% by weight or less (ratio relative to initial amount, the same below), 30.0 g of 2-hydroxybutyl acrylate was added. The mixture was then allowed to react at about 60 ° C. with stirring. When the residual isocyanate group concentration became 0.1 wt% or less, the reaction was terminated to obtain a urethane (meth) acrylate having a number average molecular weight of 13,120 (hereinafter referred to as "UA-1").

<Synthesis example 2 of urethane (meth) acrylate>

In a reaction vessel equipped with a stirrer, 1628 g of polypropylene glycol having a number average molecular weight of 8000, 56.5 g of isophorone diisocyanate, 0.41 g of 2,6-di-t-butyl-p-cresol, and 0.14 g of phenothiazine were added. Put in. The mixture was cooled to 15 ° C. with stirring. After addition of 1.4 g of dibutyltin dilaurate, the mixture was slowly heated to 35 ° C. in 1 hour with stirring. The mixture was then heated to 50 ° C. to react. 11.8 g of 2-hydroxyethyl acrylate was added when the residual isocyanate group concentration decreased to 0.76% by weight or less (ratio relative to initial amount, same as below). The mixture was allowed to react at about 60 ° C. with stirring. When the residual isocyanate group concentration became 0.1 wt% or less, the reaction was terminated to obtain a urethane (meth) acrylate having a number average molecular weight of 33,300 (hereinafter referred to as "UA-2").

<Synthesis example 3 of urethane (meth) acrylate>

In a reaction vessel equipped with a stirrer, 449.9 g of polypropylene glycol having a number average molecular weight of 4000, 26.1 g of 2,4-tolylene diisocyanate, 0.11 g of 2,6-di-t-butyl-p-cresol, and phenoti 0.04 g of azine was added. The mixture was cooled to 15 ° C. with stirring. After addition of 0.39 g of dibutyltin dilaurate, the mixture was slowly heated to 35 ° C. in 1 hour with stirring. The mixture was then heated to 50 ° C. to react. After the residual isocyanate group concentration was reduced to 1.65% by weight or less (ratio relative to initial amount, the same below), 8.70 g of 2-hydroxyethyl acrylate was added. The mixture was allowed to react at about 60 ° C. with stirring. When the residual isocyanate group concentration became 0.1 wt% or less, the reaction was terminated to obtain a urethane (meth) acrylate having a number average molecular weight of 12,900 (hereinafter referred to as "UA-3").

<Synthesis example 4 of urethane (meth) acrylate>

In a reaction vessel equipped with a stirrer, 1451 g of polypropylene glycol having a number average molecular weight of 4000, 61.1 g of isophorone diisocyanate, 0.41 g of 2,6-di-t-butyl-p-cresol, and 0.14 g of phenothiazine were added. Put in. The mixture was cooled to 15 ° C. with stirring. After addition of 1.4 g of dibutyltin dilaurate, the mixture was slowly heated to 35 ° C. in 1 hour with stirring. The mixture was then heated to 50 ° C. to react. 84.2 g of 2-hydroxyethyl acrylate was added when the residual isocyanate group concentration was reduced to 2.83% by weight or less (ratio relative to initial amount, same as below). The mixture was allowed to react at about 60 ° C. with stirring. When the residual isocyanate group concentration became 0.1 wt% or less, the reaction was terminated to obtain a urethane (meth) acrylate having a number average molecular weight of 4680 (hereinafter referred to as "UA-4").

<Examples 1 to 7 and Comparative Examples 1 to 3>

The urethane acrylate oligomer, components (B), (C) and (D), a reaction diluent, a polymerization initiator, and the like were placed in a reaction vessel provided with a stirrer at a ratio shown in Table 1. The mixture was stirred at about 50-60 ° C. to obtain samples of Examples 1-7 and samples of Comparative Examples 1-3. The components used are as follows.

Ingredient (B)

Vis150: tetrahydrofurfuryl acrylate

Vis150D: tetrahydrofurfuryl acrylate

Ingredient (C)

ACMO: N-acryloyl morpholine (Tg: 145 ℃)

       N-vinyl caprolactam (Tg: 178 ° C)

IBXA: Isobornyl acrylate (Osaka Organic Chemical Industries Limited) (Tg: 94 ℃)

Ingredient (D)

SH6062: γ-mercaptopropyltrimethoxysilane (Toray-Dow Corning Silicone Co., Ltd. product)

polymerization Initiator

Lucirin TPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide (manufactured by BASF)

Irg. 184: 1-hydroxycyclohexyl phenyl ketone (product of Ciba Specialty Chemicals Co., Ltd.)

Reaction diluent

M113: Nonylphenyl EO-Modified Acrylate (Toagosei Company Limited)

Other ingredients

GP: Phosphorus-containing antioxidant "Sumilizer GP" (manufactured by Sumitomo Chemical Industries Co., Ltd.)

GA-80: Phenolic antioxidant "Smaller GA-80" (Sumitomo Chemical Industries, Ltd.)

The test piece was produced using the liquid composition obtained by making it above, and evaluation was performed. The results are shown in Table 1.

1. Preparation of Test Piece

The liquid composition was applied to a 100 μm thick PET film, a 100 μm thick TAC film or a 3 mm thick Arton plate using an applicator bar with a gap size of 254 μm. Subsequently, a 100 μm-thick transparent PET film was attached to the applied liquid resin so that no bubbles entered between the PET film and the liquid composition. The liquid composition was cured by irradiating 1.0 J / cm ² ultraviolet rays from the transparent PET film side.

The cured test piece was allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 24 hours to prepare a test piece for evaluation of adhesive strength.

The test piece using Arton was allowed to stand for 5 days in a dry oven at 100 ° C., and then left for 24 hours at a temperature of 23 ° C. and a relative humidity of 50% to prepare a test piece for evaluation of adhesive strength after the heat resistance test.

2. Measurement of adhesive strength

The adhesive strength of the test piece was measured according to JIS K 6854 using a tensile tester with a tensile rate of 50 mm / min at a temperature of 23 ° C. and a relative humidity of 50%. The adhesive strength between PET films and the adhesive strength between PET film and TAC film were measured by T-peel method, and the adhesive strength between PET film and Arton plate was 180-degree peeling method. It measured using.

In the evaluation of the adhesive strength after the heat resistance test, the PET film and the Arton plate were subjected to a 180-degree peeling method according to JIS K 6854 using a tensile tester having a tensile speed of 50 mm / min at a temperature of 23 ° C. and 50% relative humidity. The adhesive strength of was measured.

As evident from Table 1, the compositions of the present invention showed good adhesion strength to each substrate, while the compositions of Comparative Examples 1 to 3 were found to be resistant to TAC and Arton due to the absence of component (A) or (B) Insufficient adhesive strength was shown. As shown in Table 1, the effect when using the component (A) and (B) of this invention compares Example 1 and Comparative Example 1, compares Example 3 and Comparative Example 2, and is Example This is clearly demonstrated by comparing 1-3 with Comparative Example 3. Even when the component (C) was used in a predetermined amount or more, the adhesive strength was properly maintained after the heat resistance test.

The radiation curable resin composition of this invention is excellent in adhesiveness, heat resistance, water resistance, and molding processability, and is useful as an adhesive composition. In particular, since the radiation curable resin composition of the present invention exhibits excellent adhesion to glass and plastic substrates (especially TAC and Arton films), the radiation curable resin composition may be applied to PET or TAC on optical glass or optical plastic substrates. Or for laminating Arton films. The radiation curable resin composition of the present invention is also useful in the fields of display materials, electrical / electronic component materials, optical component materials, liquid crystal panels, building materials, packaging materials, printing materials and the like.

Claims (12)

(A) 30 to 70% by weight of urethane (meth) acrylate having a number average molecular weight of 10,000 to 40,000; And (B) 0.1 to 70% by weight of ethylenically unsaturated monomers containing cyclic ethers in the structure (wherein the above weight percentages are calculated for the total composition) Radiation curable resin composition comprising a. The radiation curable resin composition according to claim 1, further comprising an ethylenically unsaturated monomer having a glass transition temperature of (C) homopolymer of 60 ° C or higher. The radiation curable resin composition according to claim 1 or 2, further comprising (D) γ-mercaptopropyltrimethoxysilane. The method according to any one of claims 1 to 3, (A) 30 to 70% by weight of urethane (meth) acrylate having a number average molecular weight of 10,000 to 40,000; (B) 0.1 to 70 wt% of an ethylenically unsaturated monomer comprising a cyclic ether; (C) 10 to 60% by weight of an ethylenically unsaturated monomer having a glass transition temperature of at least 60 ° C. of the homopolymer; And (D) 0.1 to 5% by weight of γ-mercaptopropyltrimethoxysilane Radiation curable resin composition comprising a. The radiation curable resin composition according to claim 4, wherein component (A) is present in an amount of 45 to 70% by weight. The radiation curable resin composition according to claim 4 or 5, wherein the component (B) is present in an amount of 1 to 20% by weight. The radiation curable resin composition according to claim 6, wherein the component (B) is present in an amount of 4 to 20% by weight. The radiation curable resin composition according to any one of claims 3 to 7, wherein component (C) is present in an amount of 20 to 60% by weight. The radiation curable resin composition of any one of Claims 1-8 used as an adhesive agent. An article comprising a cured composition, wherein the composition is a composition according to claim 1. The article of claim 10, comprising a substrate and a coating layer thereon, wherein the article is made of the composition according to claim 1, wherein the coating layer is cured or uncured. The film of Arton according to claim 10, wherein the substrate is a styrene-methyl methacrylate (MS) copolymer, polyethylene terephthalate (PET), triacetyl cellulose (TAC), a cyclic olefin polymer, and a norbornene-based heat-resistant transparent resin. Or an article that is a sheet.