WO2005087886A1 - Composition durcissable par rayonnement - Google Patents

Composition durcissable par rayonnement Download PDF

Info

Publication number
WO2005087886A1
WO2005087886A1 PCT/NL2005/000185 NL2005000185W WO2005087886A1 WO 2005087886 A1 WO2005087886 A1 WO 2005087886A1 NL 2005000185 W NL2005000185 W NL 2005000185W WO 2005087886 A1 WO2005087886 A1 WO 2005087886A1
Authority
WO
WIPO (PCT)
Prior art keywords
acrylate
meth
radiation
curable resin
resin composition
Prior art date
Application number
PCT/NL2005/000185
Other languages
English (en)
Inventor
Keiichi Yamamoto
Shinji Tonsho
Takeo Shigemoto
Zen Komiya
Original Assignee
Jsr Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jsr Corporation filed Critical Jsr Corporation
Publication of WO2005087886A1 publication Critical patent/WO2005087886A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds

Definitions

  • the present invention relates to a radiation-curable resin composition. More particularly, the present invention relates to a radiation-curable resin composition which exhibits excellent adhesiveness for glass and plastic substrates, in particular, films made of a styrene-methyl methacrylate (MS) copolymer, polyethylene terephthalate (PET), triacetyl cellulose (TAC), and various cyclic olefin polymers, exhibits excellent heat resistance, water resistance, and formability, and is therefore useful as an adhesive in the fields of building materials, packaging materials, printing materials, display materials, electric/electronic part materials, optical part materials, liquid crystal panels, and the like.
  • MS styrene-methyl methacrylate
  • PET polyethylene terephthalate
  • TAC triacetyl cellulose
  • various cyclic olefin polymers exhibits excellent heat resistance, water resistance, and formability, and is therefore useful as an adhesive in the fields of building materials, packaging materials, printing materials, display materials, electric/elect
  • a curable liquid adhesive has been widely utilized in various fields such as for packaging materials, display materials such as labels, electronic parts, precision equipment, and building materials.
  • a radiation-curable liquid adhesive which is cured by applying various types of radiation such as ultraviolet rays or electron beams, has been widely used instead of a conventional heat-curable adhesive in order to increase the speed of the production step and to improve productivity. Since the number of application fields and the performance required for the application are increased, an increase in the performance has been demanded for the radiation-curable liquid adhesive.
  • an adhesive for laminating PET films is required to have high heat resistance in addition to high bond strength.
  • a photocurable resin composition containing (A) a urethane (meth)acrylate, (B) a silane compound having a mercapto group, (C) a photoinitiator, (D) an ethylenically unsaturated monomer having an amino group, and (E) a (meth)acrylate compound is useful as a coating layer for a copper-coated wire used as a tension member of an optical fiber unit (Japanese Patent Application Laid- open No. 2000-198824).
  • an object of the present invention is to provide a radiation-curable resin composition exhibiting excellent bond strength for PET, TAC, Arton, and the like, excellent formability, heat resistance, and water resistance, and high-speed curability.
  • a radiation-curable resin composition comprising: (A) 30-70 wt% of a urethane (meth)acrylate with a number average molecular weight of 10,000-40,000; and (B) 0.1-70 wt% of an ethylenically unsaturated monomer including in its structure a cyclic ether.
  • the radiation-curable resin composition according to 1 further comprising (C) an ethylenically unsaturated monomer of which the homopolymer has a glass transition temperature of 60°C or more.
  • a radiation curable resin composition according to 1-3 comprising: (A) 30-70 wt% of a urethane (meth)acrylate with a number average molecular weight of 10,000-40,000; (B) 0,1-70 wt% of an ethylenically unsaturated monomer including a cyclic ether; (C) 10-60 wt% of an ethylenically unsaturated monomer of which the homo polymer has a glass transition temperature of 60°C or more; (D) 0,1-5 wt% of ⁇ -mercaptopropyltrimethoxysilane
  • component (C) is present in an amount of 20-60 wt%.
  • the invention also relates to the use of radiation curable resin compositions:
  • Object comprising a cured composition, which composition is a composition according to 1-8.
  • Object according to 10 comprising a substrate and a coating layer thereon, which coating layer consists of a composition according to 1-8, either cured or uncured.
  • the substrate is a film or sheet of a styrene-methyl methacrylate (MS) coploymer, polyethylene terephralate (PET), triacetyl cellulose (TAC), cyclic olefin polymers, and Arton, a norbornene type of heat resistant transparant resin.
  • MS styrene-methyl methacrylate
  • PET polyethylene terephralate
  • TAC triacetyl cellulose
  • Arton a norbornene type of heat resistant transparant resin.
  • the radiation-curable resin composition of the present invention exhibits excellent adhesiveness, excels in heat resistance, water resistance, and formability, and is useful as an adhesive composition.
  • the component (B) causes a film to swell, whereby the bond strength between the film and the adhesive is increased.
  • the radiation-curable resin composition of the present invention exhibits excellent adhesiveness for PET, MS, glass, and plastic substrates, in particular, TAC and an Arton film.
  • the component A used in the present invention is a urethane (meth)acrylate compound with a number average molecular weight of 10,000-40,000.
  • the component A is preferably produced by reacting a polyol compound, a polyisocyanate compound, and a hydroxyl group-containing (meth)acrylate .
  • the component A is preferably produced by reacting the isocyanate group of the polyisocyanate compound with each of the hydroxyl group of the polyol compound and the hydroxyl group of the hydroxyl group-containing (meth)acrylate compound.
  • the following four methods can be given as the reaction method, for example.
  • Method 1 A method of reacting the polyol compound, the polyisocyanate compound, and the hydroxyl group-containing (meth)acrylate compound all together.
  • Method 2 A method of reacting the polyol compound with the polyisocyanate compound, and reacting the resulting product with the hydroxyl group- containing (meth)acrylate compound.
  • Method 3 A method of reacting the polyisocyanate compound with the hydroxyl group-containing (meth)acrylate compound, and reacting the resulting product with the polyol compound.
  • Method 4 A method of reacting the polyisocyanate compound with the hydroxyl group-containing (meth)acrylate compound, reacting the resulting product with the polyol compound, and reacting the resulting product with the hydroxyl group- containing (meth)acrylate compound.
  • the polyol used as the raw materials for the component A of the present invention include an aromatic polyether polyol, an aliphatic polyether polyol, an alicyclic polyether polyol, a polyester polyol, a polycarbonate polyol, a polycaprolactone polyol, and the like.
  • aromatic polyether polyol examples include ethylene oxide addition diol of bisphenol A, propylene oxide addition diol of bisphenol A, butylene oxide addition diol of bisphenol A, ethylene oxide addition diol of bisphenol F, propylene oxide addition diol of bisphenol F, butylene oxide addition diol of bisphenol F, alkylene oxide addition diol of hydroquinone, alkylene oxide addition diol of naphthoquinone, and the like.
  • the aromatic polyether polyols are commercially available as Uniol DA700, DA1000 (manufactured by Nippon Oil and Fats Co., Ltd.), and the like.
  • (co)polymers obtained by ring-opening (co)polymerization of at least one compound selected from ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, 2-methyltetrahydrofuran, 3- methyltetrahydrofuran, substituted tetrahydrofuran, oxetane, substituted oxetane, tetrahydropyran, and oxepane can be given.
  • aliphatic polyether polyol examples include polyethylene glycol, 1 ,2-polypropylene glycol, 1 ,3- polypropylene glycol, polytetramethylene glycol, 1 ,2-polybutylene glycol, polyisobutylene glycol, a copolymer polyol of propylene oxide and tetrahydrofuran, a copolymer polyol of ethylene oxide and tetrahydrofuran, a copolymer polyol of ethylene oxide and propylene oxide, a copolymer polyol of tetrahydrofuran and 3- methyltetrahydrofuran, a copolymer polyol of ethylene oxide and 1 ,2-butylene oxide, and the like.
  • alicyclic polyether polyol ethylene oxide addition diol of hydrogenated bisphenol A, propylene oxide addition diol of hydrogenated bisphenol A, butylene oxide addition diol of hydrogenated bisphenol A, ethylene oxide addition diol of hydrogenated bisphenol F, propylene oxide addition diol of hydrogenated bisphenol F, butylene oxide addition diol of hydrogenated bisphenol F, dimethylol compound of dicyclopentadiene, tricyclodecanedimethanol, and the like can be given.
  • Examples of commercially available products of the aliphatic polyether polyols and the alicyclic polyether polyols include Unisafe DC 1100, Unisafe DC 1800, Unisafe DCB 1800 (manufactured by Nippon Oil and Fats Co., Ltd.); 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 (manufactured by Asahi Glass Co., Ltd.); PBG 3000, PBG 2000, PBG 000, Z 3001 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.); Acclaim 2200, 3201 , 4200, 6300, 8200 (manufactured by Sumika Bayer Urethane Co., Ltd.); NPML-2002,
  • polyester polyol examples include a polyester polyol obtained by reacting a polyhydric alcohol such as ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1 ,6- hexanediol, neopentyl glycol, 1 ,4-cyclohexanedimethanol, 3-methyl-1 ,5-pentanediol, 1 ,9-nonanediol, or 2-methyl-1 ,8-octanediol with a polybasic acid such as phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, adipic acid, or sebacic acid, and the like.
  • a polyhydric alcohol such as ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol
  • the polyester polyols are commercially available as Kurapol P-2010, PMIPA, PKA-A, PKA-A2, PNA-2000 (manufactured by Kuraray Co., Ltd.), and the like.
  • the polycarbonate polyol 1 ,6-hexanepolycarbonate and the like can be given.
  • Examples of commercially available products of the polycarbonate polyols include DN-980, 981 , 982, 983 (manufactured by Nippon Polyurethane Industry Co., Ltd.), Placcel CD-205, CD-983, CD-220 (manufactured by Daicel Chemical Industries, Ltd.), PC-8000 (made by PPG of the U.S.), and the like.
  • polycaprolactone polyol examples include a polycaprolactone diol obtained by reacting ⁇ -caprolactone with a dihydric diol such as ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1 ,2-polybutylene glycol, 1,6-hexanediol, neopentyl glycol, 1 ,4-cyclohexanedimethanol, or 1,4-butanediol, and the like.
  • a dihydric diol such as ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1 ,2-polybutylene glycol, 1,6-hexanediol, neopentyl glycol, 1 ,4-cyclohexanedimethanol, or 1,4-
  • Examples of commercially available products of the polycaprolactone polyols include Placcel 205, 205AL, 212, 212AL, 220, 220AL (manufactured by Daicel Chemical Industries, Ltd.), and the like.
  • Examples of other diols which 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- ⁇ -methyl- ⁇ - valerolactone, hydroxy-terminated polybutadiene, hydroxy-terminated hydrogenated polybutadiene, castor oil-modified polyol, diol-terminated compound of polydimethylsiloxane, polydimethylsiloxane carbitol-modified polyol, and the like.
  • polypropylene glycol ethylene oxide-propylene oxide copolymer diol, ethylene oxide-1 ,2-butylene oxide copolymer diol, and propylene oxide-tetrahydrofuran copolymer diol are preferable, with ethylene oxide-1 ,2-butylene oxide copolymer diol being particularly preferable.
  • the number average molecular weight of the polyol compound to be used is preferably 500-12,000, still more preferably 1 ,500-9,000, and most preferably 3,500-9,000.
  • the number average molecular weight of the polyol compound is less than 500, since the Young' s modulus of the resulting cured product at room temperature and low temperature is increased, sufficient adhesiveness may not be obtained, whereby zipping may occur. If the number average molecular weight exceeds 12,000, since the viscosity of the composition is increased, applicability may be decreased when coating a substrate with the composition.
  • Examples of the hydroxyl group-containing (meth)acrylate compound as one of the raw materials for the component A include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3- phenyloxypropyl (meth)acrylate, 1,4-butanediol mono(meth)acrylate, 2-hydroxyalkyl (meth)acryloyl phosphate, 4-hydroxycyclohexyl (meth)acrylate, 1 ,6-hexanediol mono(meth)acrylate, neopentyl glycol mono(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolethane di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and (meth)acrylates shown by the following formulas (1) and (2). CH
  • R 1 represents a hydrogen atom or a methyl group
  • m is an integer of 1-15.
  • a compound obtained by the addition reaction of a glycidyl group-containing compound, such as alkyl glycidyl ether, allyl glycidyl ether, or glycidyl (meth)acrylate, with (meth)acrylic acid can be given.
  • a glycidyl group-containing compound such as alkyl glycidyl ether, allyl glycidyl ether, or glycidyl (meth)acrylate
  • 2-hydroxyethyl (meth)acrylate and 2- hydroxypropyl (meth)acrylate are particularly preferable.
  • polyisocyanate compound examples 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, bis(2-isocyanatoethyl) fumarate, 6- isopropyl
  • polyisocyanate compounds hydrogenated xylylene diisocyanate, isophorone diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and the like are preferable. These polyisocyanate compounds may be used either individually or in combination of two or more.
  • the number average molecular weight of the urethane (meth)acrylate compound which is the component A of the present invention obtained as described above is at least 10,000 and at most 40,000. If the number average molecular weight of the urethane (meth)acrylate compound is less than 10,000, desired bond strength may not be obtained. If the number average molecular weight of the urethane (meth)acrylate compound exceeds 40,000, the viscosity of the composition becomes too high.
  • the urethane (meth)acrylate compound which is the component A of the present invention is incorporated in the composition of the present invention in an amount of preferably 30-70 wt%, and particularly preferably 45-70 wt% from the viewpoint of applicability of the composition and the adhesive properties, processability, flexibility, and long-term reliability of the adhesive obtained by curing the composition.
  • the ethylenically unsaturated monomer including in its structure a cyclic ether which is the component B of the present invention include glycidyl (meth)acrylate, oxetanyl methyl (meth)acrylate, tetrahydrofurfuryl
  • (meth)acrylate tetrahydropyranyl (meth)acrylate, cyclic trimethylolpropane formal acrylate, ethylene oxide-modified (meth)acrylate, propylene oxide-modified (meth)acrylate, and caprolactone-modified (meth)acrylate of each compound, and the like.
  • monomers including a tetrahydrofuran (THF) skeleton indicated by the following formulas (3) and (4) are preferable, with tetrahydrofurfuryl acrylate being particularly preferable.
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents an alkylene group having 2-8, and preferably 2-5 carbon atoms
  • n is an integer of 0-8, and preferably 0-2.
  • R 3 represents a hydrogen atom or a methyl group
  • R 4 represents an alkylene group having 2-8, and preferably 2-5 carbon atoms
  • p is an integer of 0-8, and preferably 0-4.
  • the compound shown by the formula (3) or (4) is commercially available as Viscoat #150 (manufactured by Osaka Organic Chemical Industry, Ltd.), Light Ester THF, Light Acrylate THF-A (manufactured by Kyoeisha Chemical Co., Ltd.), SR285, SR203, CD611 (manufactured by Sartomer Co., Inc.), and the like.
  • the composition B is used in an amount of 0.1-70 wt%, preferably 1- 20 wt%, and particularly preferably 4-20 wt% for 100 wt% of the composition. If the amount is less than 0.1 wt%, the bond strength may be decreased. If the amount exceeds 70 wt%, a substrate may be damaged. If the amount exceeds 20 wt%, the viscosity of the liquid composition sometimes becomes too low, whereby handling may become difficult. It is an advantage of the composition according to the invention that the bond strength to TAC and Arton is increased by incorporation of the component B.
  • a component C that is preferably used in the present invention, is an ethylenically unsaturated monomer of which the homopolymer has a glass transition temperature of 60°C or more. The glass transition temperature is measured by differential scanning calorimetry. It should be noted that component C is an ethylenically unsaturated monomer other than component B.
  • component C examples include acryloylmorpholine, dimethylacrylamide, diethylacrylamide, diisopropylacrylamide, isobomyl (meth)acrylate,dicyclopentenyl acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, cyclohexyl methacrylate, dicyclopentadienyl (meth)acrylate, tricyclodecanyl (meth)acrylate, diacetoneacrylamide, isobutoxymethyl(meth)acrylamide, N-vinylpyrrolidone, N-vinylcaprolactam, 3- hydroxycyclohexyl acrylate, 2-acryloylcyclohexyl succinate, and the like.
  • acryloylmorpholine, dimethylacrylamide, N-vinyl pyrrolidone, and N-vinylcaprolactam are preferable.
  • the component C may be used either individually or in combination of two or more.
  • isobornyl acrylate, dicyclopentenyl acrylate, dicyclopentanyl acrylate, and dicyclopentanyloxyethy lacrylate have an advantage of improving water resistance of the cured product of the present invention.
  • N-vinylpyrrolidone and N- vinylcaprolactam have an advantage of improving curability of the composition of the present invention.
  • a particularly preferable combination is a combination of one or more compounds selected from acryloylmorpholine, dimethylacrylamide, N-vinylpyrrolidone, and N- vinylcaprolactam and one or more compounds selected from isobornyl acrylate, dicyclopentenyl acrylate, dicyclopentanyl acrylate, and dicyclopentanyloxyethy lacrylate.
  • ACMO electrically available products of the component C
  • DMAA manufactured by Kohjin Ltd.
  • New Frontier IBA manufactured by Daiichi
  • the component C is incorporated in the composition in an amount of preferably 10-60 wt%, and still more preferably 20-60 wt%. If the amount of the component C is less than 10 wt%, desired bond strength may not be obtained. If the amount exceeds 60 wt%, not only desired bond strength may not be obtained, but also the water resistance may be decreased. Bond strength to a substrate can be improved by incorporating ⁇ - mercaptopropyltrimethoxysilane into the radiation-curable resin composition of the present invention as the component D.
  • the component D is used in the composition of the present invention in an amount of preferably 0.1 -5 wt%.
  • monofunctional and polyfunctional polymerizable monomers other than the components B, C, and D may optionally be used in addition to the essential components A and B and optional components C and D.
  • monofunctional and polyfunctional polymerizable monomers other than those present in a composition comprising A, B, C and D are used in addition to A, B, C, and D.
  • an n-alkyl (meth)acrylate such as benzyl (meth)acrylate, nonyl (meth)acrylate, dodecyl (meth)acrylate, and lauryl (meth)acrylate
  • an isoalkyl (meth)acrylates such as isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-ethylhexylcarbitol (meth)acrylate, 2- hydroxyethyl (meth)acrylate, 2-hydroxypropyl (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, isoprop
  • (meth)acrylate, bornyl (meth)acrylate, t-octyl(meth)acrylamide, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and 7-amino-3,7-dimethylocty! (meth)acrylate can be given.
  • a (meth)acrylate compound shown by the following formula (5) can be given.
  • R 1 represents a hydrogen atom or a methyl group
  • R 5 represents an alkylene group having 2-6, and preferably 2-4 carbon atoms
  • R 6 represents a hydrogen atom or an alkyl group having 1-12, and preferably 1-9 carbon atoms
  • I is an integer of 0- 12, and preferably of 1-8.
  • AIB, 2-MTA, Viscoat #158, #3700 (manufactured by Osaka Organic Chemical Industry, Ltd.), L-A, PO-A, P-200A, HOA-MS (manufactured by Kyoeisha Chemical Co., Ltd.), Aronix M111 , M113, M114, M117, and M120 (manufactured by Toagosei Co., Ltd. Ltd.), Kayarad TC110S, R629, R644 (manufactured by Nippon Kayaku Co., Ltd.), Sartomer 506 (manufactured by Somar Corp.), and the like can be given.
  • an acrylate compound shown by the following general formula (6), wherein q is an integer of 1-5 be excluded from the monofunctional monomer.
  • polyethylene glycol di(meth)acrylates such as trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol ethylene oxide-modified tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 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, and trimethylolpropane trioxyethyl (meth)acrylate, tris(
  • Yupimer UV, SA 1002, SA 2007 manufactured by Mitsubishi Chemical Corp.
  • Viscoat #700 manufactured by Osaka Organic Chemical Industry, Ltd.
  • Kayarad R-604 DPCA-20, DPCA-30, DPCA-60, DPCA-120, HX-620, D-310, D-330 (manufactured by Nippon Kayaku Co., Ltd.), Aronix M-210, M-215, M-315, M-325 (manufactured by Toagosei Co., Ltd.), and the like can be given.
  • the monofunctional and polyfunctional polymerizable monomers other than the components A, B, C, and D are incorporated in the composition in an amount of preferably 0-70 wt%, and still more preferably 0-40 wt% from the viewpoint of the bond strength and the like.
  • Various additives such as coloring agents, light stabilizers, silane coupling agents, antioxidant, heat polymerization inhibitors, leveling agents, surfactants, preservatives, plasticizers, lubricants, solvents, fillers, aging preventives, wettability improvers, and coating surface improvers may optionally be added to the radiation-curable resin composition of the present invention in addition to the above components.
  • the radiation-curable resin composition of the present invention may be cured by applying radiation.
  • the radiation used herein refers to activated energy rays such as visible light, ultraviolet rays, electron beams, and X-rays.
  • a UV sensitive photoinitiator is preferably used.
  • UV sensitive photoinitiator 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, thioxanethone, diethylthioxanthone, 2- isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl
  • Irgacure 184, 651, 500, 907, CG 1369, CG 24-61 (manufactured by Ciba Geigy), Lucirine TPO (manufactured by BASF), Darocure 1116, 1173 (manufactured by Merck), Ubecryl P36 (manufactured by UCB), and the like can be given.
  • a visible-light sensitive photoinitiator such as camphorquinone.
  • the photopolymerization sensitivity may be improved by adding another additive having a sensitization effect.
  • the photosensitizer examples include triethylamine, diethylamine, N-methyldiethanoleamine, ethanolamine, 4- dimethylaminobenzoic acid, 4-methyl dimethylaminobenzoate, 4-ethyl dimethylaminobenzoate, and 4-isoamyl dimethylaminobenzoate, and commercially available products such as Ubecryl P102, 103, 104, 105 (manufactured by UCB), and the like.
  • the photoinitiator is incorporated in the composition in an amount of preferably 0.1-10 wt%.
  • the radiation-curable resin composition of the present invention may be produced by mixing the above components using a conventional method.
  • the viscosity of the composition of the present invention thus produced is usually 100- 20,000 cps/25°C, and preferably 200-10,000 cps/25°C.
  • Synthesis Example 1 of urethane (meth)acrylate A reaction vessel equipped with a stirrer was charged with 1552 g of polypropylene glycol with a number average molecular weight of 4000, 14.8 g of isophorone diisocyanate, 0.41 g of 2,6-di-t-butyl-p-cresol, and 0.14 g of phenothiazine. The mixture was then cooled to 15°C with stirring. After the addition of 1.4 g of dibutyltin dilaurate, the mixture was slowly heated to 35°C in one hour with stirring. The mixture was then heated to 50°C and allowed to react.
  • Synthesis Example 2 of urethane (meth)acrylate A reaction vessel equipped with a stirrer was charged with 1628 g of polypropylene glycol with 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. The mixture was cooled to 15°C with stirring. After the addition of 1.4 g of dibutyltin dilaurate, the mixture was slowly heated to 35°C in one hour with stirring. The mixture was then heated to 50°C and allowed to react.
  • Synthesis Example 3 of urethane (meth)acrylate A reaction vessel equipped with a stirrer was charged with 449.9 g of polypropylene glycol with 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 0.04 g of phenothiazine. The mixture was cooled to 15°C with stirring. After the addition of 0.39 g of dibutyltin dilaurate, the mixture was slowly heated to 35°C in one hour with stirring. The mixture was then heated to 50°C and allowed to react.
  • Synthesis Example 4 of urethane (meth)acrylate A reaction vessel equipped with a stirrer was charged with 1451 g of polypropylene glycol with 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. The mixture was cooled to 15°C with stirring. After the addition of 1.4 g of dibutyltin dilaurate, the mixture was slowly heated to 35°C in one hour with stirring. The mixture was then heated to 50°C and allowed to react.
  • Examples 1-7 and Comparative Examples 1-3 A reaction vessel equipped with a stirrer was charged with the urethane acrylate oligomer, the components B, C, and D, a reactive diluent, and a polymerization initiator, and the like 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.
  • Vis150 Tetrahydrofurfuryl acrylate
  • Vis150D Tetrahydrofurfuryl acrylate
  • Component C ACMO N-Acryloylmorpholine (Tg: 145°C) N-Vinylcaprolactam (Tg: 178°C)
  • IBXA Isobornyl acrylate (manufactured by Osaka Organic Chemical Industry, Ltd.) (Tg: 94°C)
  • SH6062 ⁇ -Mercaptotrimethoxysilane (manufactured by Toray-Dow Corning Silicone Co., Ltd.)
  • Lucirin TPO 2,4,6-Trimethylbenzoyldiphenylphosphine oxide (manufactured by BASF)
  • Irg. 184 1-Hydroxycyclohexyl phenyl ketone (manufactured by Ciba Specialty Chemicals Co., Ltd.)
  • Reactive diluent M113 Nonylphenyl EO-modified acrylate (manufactured by Toagosei Co., Ltd.)
  • the liquid composition was cured by applying ultraviolet rays at a dose of 1.0 J/cm 2 from the side of the transparent PET film.
  • the cured specimen was allowed to stand at a temperature of 23°C and a relative humidity of 50% for 24 hours to prepare a bond strength evaluation specimen.
  • the specimen using Arton was allowed to stand at 100°C for five days in a dry oven, and was allowed to stand at a temperature of 23°C and a relative humidity of 50% for 24 hours to prepare a bond strength evaluation specimen after the heat resistance test.
  • the bond strength between the PET films and the bond strength between the PET film and TAC film were measured using a T-peel method, and the bond strength between the PET film and the Arton plate was measured using a 180-degree peel method.
  • the bond strength between the PET film and the Arton plate was measured using a 180- degree peeling method according to JIS K 6854 at a temperature of 23°C and a relative humidity of 50% using a tensile tester at a tensile rate of 50 mm/min.
  • the compositions of the present invention exhibited excellent bond strength for each substrate, whereas the compositions of Comparative Examples 1-3 exhibited insufficient bond strength for TAC and Arton due to the absence of the component (A) or (B) of the present invention.
  • the effect of simultaneously using the components (A) and (B) of the present invention is clearly demonstrated from the comparison between Example 1 and Comparative example 1 , the comparison between Example 3 and Comparative example 2, and the comparison between Examples 1-3 and Comparative example 3 as shown in Table 1.
  • the component (C) in an amount equal to or greater than a predetermined amount, the bond strength was adequately maintained after the heat resistance test.
  • the radiation-curable resin composition of the present invention excels in adhesiveness, heat resistance, water resistance, and formability and is useful as an adhesive composition.
  • the radiation-curable resin composition of the present invention exhibits excellent adhesiveness for glass and a plastic substrate, in particular, for TAC and an Arton film
  • the radiation-curable resin composition is suitably used to laminate PET, TAC, or an Arton film on an optical glass or an optical plastic substrate.
  • the radiation-curable resin composition of the present invention is useful in the fields of display materials, electronic/electric part materials, optical part materials, liquid crystal panels, building materials, packaging materials, printing materials, and the like.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'objectif de l'invention est de produire une composition en résine durcissable par rayonnement, présentant une résistance des liaisons excellente pour le PET, le TAC, l'Arton et analogues, une transformabilité excellente, une bonne résistance à la chaleur et à l'eau, et un pouvoir durcissant très rapide. L'invention concerne une composition en résine durcissable par rayonnement, comprenant : (A) 30 à 70 % en poids d'un uréthanne (méth)acrylate présentant un poids moléculaire moyen compris entre 10000 et 40000 ; et (B) 0,1 à 70 % en poids d'un monomère non saturé en éthylène comprenant un éther cyclique.
PCT/NL2005/000185 2004-03-11 2005-03-11 Composition durcissable par rayonnement WO2005087886A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JPJP2004-069216 2004-03-11
JP2004069216A JP2005255844A (ja) 2004-03-11 2004-03-11 放射性硬化性組成物

Publications (1)

Publication Number Publication Date
WO2005087886A1 true WO2005087886A1 (fr) 2005-09-22

Family

ID=34961794

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/NL2005/000185 WO2005087886A1 (fr) 2004-03-11 2005-03-11 Composition durcissable par rayonnement

Country Status (3)

Country Link
JP (1) JP2005255844A (fr)
CN (1) CN1997718A (fr)
WO (1) WO2005087886A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120071579A1 (en) * 2009-04-20 2012-03-22 Bridgestone Corporation Thiol group- containing adhesive resin composition
JP5997405B1 (ja) * 2016-04-06 2016-09-28 大日精化工業株式会社 粘着剤組成物及び積層体

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008127429A (ja) * 2006-11-17 2008-06-05 Denki Kagaku Kogyo Kk 光硬化性樹脂組成物
JP5182465B2 (ja) * 2007-01-30 2013-04-17 株式会社ブリヂストン プラスチック基板接着用紫外線硬化樹脂組成物
JPWO2008111581A1 (ja) * 2007-03-12 2010-06-24 東亞合成株式会社 光学フィルム積層体およびそれを用いた表示装置
JP4848996B2 (ja) * 2007-03-30 2011-12-28 東亞合成株式会社 活性エネルギー線硬化型光学材料用組成物
JP4744496B2 (ja) * 2007-04-16 2011-08-10 日東電工株式会社 偏光板、光学フィルムおよび画像表示装置
US8859634B2 (en) 2007-12-27 2014-10-14 Bridgestone Corporation Adherent resin composition
US20090181242A1 (en) * 2008-01-11 2009-07-16 Enniss James P Exterior window film
JP2010059244A (ja) * 2008-09-01 2010-03-18 Fujifilm Corp インク組成物及びインクジェット記録方法
WO2012077329A1 (fr) * 2010-12-08 2012-06-14 株式会社ブリヂストン Composition adhésive
JP6155778B2 (ja) * 2013-04-08 2017-07-05 日立化成株式会社 接着剤組成物
WO2015194487A1 (fr) * 2014-06-18 2015-12-23 ポリマテック・ジャパン株式会社 Composition de résine durcissable par rayonnement d'énergie active, ainsi que produit durci et produit moulé associés
JP6897047B2 (ja) * 2016-09-30 2021-06-30 昭和電工マテリアルズ株式会社 粘着フィルム及び硬化性組成物

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6337118B1 (en) * 1998-08-20 2002-01-08 Jsr Corporation Adhesive for optical disks

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6337118B1 (en) * 1998-08-20 2002-01-08 Jsr Corporation Adhesive for optical disks

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120071579A1 (en) * 2009-04-20 2012-03-22 Bridgestone Corporation Thiol group- containing adhesive resin composition
JP5997405B1 (ja) * 2016-04-06 2016-09-28 大日精化工業株式会社 粘着剤組成物及び積層体
JP2017186450A (ja) * 2016-04-06 2017-10-12 大日精化工業株式会社 粘着剤組成物及び積層体

Also Published As

Publication number Publication date
CN1997718A (zh) 2007-07-11
JP2005255844A (ja) 2005-09-22

Similar Documents

Publication Publication Date Title
KR100838132B1 (ko) 액상 경화성 수지 조성물
WO2005087886A1 (fr) Composition durcissable par rayonnement
JP3292348B2 (ja) 液状硬化性樹脂組成物
JP3196269B2 (ja) 液状硬化性樹脂組成物
JP4590893B2 (ja) 接着剤用液状硬化性樹脂組成物
WO2006046864A1 (fr) Composition de resine photodurcissable et adhesif pour disque optique
JP3605848B2 (ja) 液状硬化性粘・接着剤組成物
EP0785961A1 (fr) Composition d'enrobage pour fibres de verre optique
JP3958201B2 (ja) 液状硬化性樹脂組成物
JP3220221B2 (ja) 液状硬化性樹脂組成物
JP2009227988A (ja) 液状硬化性樹脂組成物
WO2006022545A1 (fr) Formulation de résine liquide durcissable
JP2003277453A (ja) 液状硬化性樹脂組成物
JP2001181359A (ja) 液状硬化性樹脂組成物およびその硬化物
JPH10204250A (ja) 液状硬化性樹脂組成物
JP2002097235A (ja) 液状硬化性樹脂組成物およびその硬化物
JP4866042B2 (ja) 液状硬化性樹脂組成物
JP5420272B2 (ja) 液状硬化性樹脂組成物
JP3607748B2 (ja) 多層被覆
KR20070023667A (ko) 방사선 경화성 조성물
JP3292326B2 (ja) 液状硬化性樹脂組成物
JP3324710B2 (ja) 液状硬化性樹脂組成物
JP3373661B2 (ja) 床材被覆用光硬化性樹脂組成物
JP4448355B2 (ja) 液状硬化性樹脂組成物
JP2004067866A (ja) 放射線硬化型樹脂組成物

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SM SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): BW GH GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 1020067018385

Country of ref document: KR

WWE Wipo information: entry into national phase

Ref document number: 200580007701.7

Country of ref document: CN

NENP Non-entry into the national phase

Ref country code: DE

WWW Wipo information: withdrawn in national office

Country of ref document: DE

WWP Wipo information: published in national office

Ref document number: 1020067018385

Country of ref document: KR

122 Ep: pct application non-entry in european phase