WO2015020099A1 - Active-energy-ray-curable adhesive composition for plastic film or sheet - Google Patents
Active-energy-ray-curable adhesive composition for plastic film or sheet Download PDFInfo
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- WO2015020099A1 WO2015020099A1 PCT/JP2014/070763 JP2014070763W WO2015020099A1 WO 2015020099 A1 WO2015020099 A1 WO 2015020099A1 JP 2014070763 W JP2014070763 W JP 2014070763W WO 2015020099 A1 WO2015020099 A1 WO 2015020099A1
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- 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
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
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- 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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
Definitions
- the present invention relates to an active energy ray-curable adhesive composition capable of bonding various plastic films or sheets by irradiation with active energy rays such as ultraviolet rays, visible light, or electron beams, and It is suitably used for the production of various optical films or sheets used for liquid crystal displays, organic EL displays and the like, and can be used in these technical fields.
- active energy rays such as ultraviolet rays, visible light, or electron beams
- active energy rays such as ultraviolet rays, visible light, or electron beams
- active energy rays such as ultraviolet rays, visible light, or electron beams
- acrylate and / or methacrylate is represented by (meth) acrylate
- acryloyl group and / or methacryloyl group is represented by (meth) acryloyl group
- acrylic acid and / or methacrylic acid is represented by (meth) acrylic acid.
- a plastic film or sheet is collectively expressed as “plastic film or the like”
- an ethylene-vinyl acetate copolymer is used in a laminating method in which a thin-layer adherend such as a plastic film or a thin-layer adherend such as a plastic film is bonded to a thin-layer adherend made of another material.
- a solvent-type adhesive composition containing a polymer or a polyurethane-based polymer is applied to the first thin-layer adherend and dried, and then the second thin-layer adherend is applied to the first thin-layer adherend using a nip roller or the like.
- the dry laminating method for pressure bonding is mainly performed.
- the adhesive composition used in this method generally contains a large amount of a solvent in order to make the coating amount of the composition uniform, but for this reason, a large amount of solvent vapor is volatilized during drying, resulting in toxicity, work safety and Environmental pollution is a problem.
- a solventless adhesive composition has been studied.
- a two-component adhesive composition and an adhesive composition that is cured by an active energy ray such as an ultraviolet ray or an electron beam are widely used.
- a so-called polyurethane adhesive composition is mainly used in which a polymer having a hydroxyl group at the terminal is a main agent and a polyisocyanate compound having an isocyanate group at the terminal is a curing agent.
- this composition has the disadvantage that it takes a long time to cure.
- the active energy ray-curable adhesive composition is excellent in productivity because of its high curing rate, and thus has been used in recent years.
- liquid crystal displays are widely used in mobile devices such as mobile phones, smartphones, and tablets because of their thinness, light weight, and power saving. It is also widely used in various displays for personal computers, televisions, and car navigation systems.
- organic EL display is increasing mainly in mobile devices. Active energy ray-curable adhesives are widely used for bonding various optical films used for liquid crystal displays and organic EL displays.
- a hard coat film provided with functionality such as anti-fingerprint and anti-glare, a touch panel front plate, a polarizing plate, a retardation film, a viewing angle compensation film, a brightness enhancement film, an anti-reflection film, an anti-glare film, A lens sheet, a diffusion sheet, etc. are mentioned, and various kinds of plastics are used for these.
- amorphous cycloolefin polymers and polymethyl methacrylate are widely used because of their excellent optical properties such as colorless transparency and optical isotropy.
- Non-patent Document 1 it is difficult to increase the peel adhesive strength by setting the film thickness of the adhesive to 3 ⁇ m or less.
- a photocationic curable adhesive containing a polyfunctional aliphatic epoxy monomer as a main component and containing an alicyclic epoxy monomer and / or an oxetane monomer is not limited to a cycloolefin polymer or triacetyl, even if the adhesive is thin. It has been disclosed that it has excellent adhesion to plastic materials such as cellulose (Patent Document 1).
- the composition disclosed in Patent Document 1 has a problem that the cationic curability is poor and the energy required for curing is large. For this reason, it was necessary to slow down the line speed of the bonding process or increase the number of light sources. Therefore, from the viewpoint of productivity, an active energy ray-curable adhesive having excellent curability, specifically, sufficient adhesive force is exhibited even at an irradiation dose of 1,000 mJ / cm 2 or less at UV-A (365 nm). Therefore, an active energy ray-curable adhesive has been desired. Furthermore, the composition disclosed in Patent Document 1 has a problem that adhesive strength to (meth) acrylic resins such as polymethyl methacrylate and alkyl (meth) acrylate polymers is insufficient. In addition, when the humidity of the atmosphere when applying and curing the adhesive is high, there is a problem that the adhesive strength is greatly reduced.
- the present invention has been made in view of the above problems, and has a low viscosity, excellent curability, and high atmospheric humidity during coating and curing, such as (meth) acrylic resins such as polymethyl methacrylate and cycloolefin.
- An object of the present invention is to provide an active energy ray-curable adhesive composition for plastic films and the like which is excellent in adhesive strength to various plastic films including polymers and is also colorless and transparent.
- the present inventors have found that specific polymers, diglycidyl ethers of diols having 2 to 10 carbon atoms, compounds having a molecular weight of 500 or less having two or more oxetanyl groups in the molecule, and The present inventors have found that an active energy ray-curable adhesive composition containing a photocationic polymerization initiator at a specific ratio can solve the above-described problems, and has completed the present invention.
- the present invention relates to an active energy ray-curable adhesive composition for plastic films or sheets comprising the following components (A) to (D) as essential components.
- the monomer (a2) preferably contains an alkyl (meth) acrylate having an alkyl group having 1 to 10 carbon atoms and / or an aromatic vinyl compound.
- the component (A) is an alkyl having an alkyl group having 1 to 10 carbon atoms as the monomer (a2) containing 10 to 80% by weight of the monomer (a1) in all constituent monomer units.
- a polymer containing 10 to 80% by weight of (meth) acrylate and 10 to 80% by weight of an aromatic vinyl compound and having a weight average molecular weight of 3,000 to 20,000 is preferred.
- the component (A) preferably contains glycidyl methacrylate as the monomer (a1) and contains methyl methacrylate and styrene as the monomer (a2). Furthermore, the component (A) is preferably a polymer obtained by high-temperature polymerization of the monomer (a1) and the monomer (a2), more preferably high-temperature polymerization at a temperature of 160 ° C. or higher. It is the obtained polymer.
- the component (B) is preferably diglycidyl ether of alkanediol having 4 to 6 carbon atoms.
- the component (C) is preferably an oxetane compound represented by the following formula (1).
- the component (D) is preferably a sulfonium salt photocationic polymerization initiator.
- the component (A) is 1 to 60% by weight
- the component (B) is 1 to 60% by weight
- the component (C) is 1 to 60% by weight
- the component (D) is 0.5 to 10% by weight.
- % Content is preferable.
- at least one of the plastic film or sheet is a cycloolefin polymer or a (meth) acrylic resin.
- the present invention also provides a laminate in which the above composition is applied to a substrate, another substrate is bonded to the coated surface, and active energy rays are irradiated from either side of the substrate.
- a method The present invention relates to a method for producing a laminate in which both or one of the substrates is a plastic film or sheet.
- low viscosity, excellent curability, and high adhesive strength to various plastic films including (meth) acrylic resins such as polymethyl methacrylate even when the atmospheric humidity during coating and curing is high.
- An active energy ray-curable adhesive composition that is excellent and excellent in colorless transparency can be provided. For this reason, it can use suitably for manufacture of the various optical films etc. which are used for a liquid crystal display, an organic EL display, etc.
- it can be suitably used for various applications requiring low viscosity, curability, adhesive strength, and transparency, for applications other than displays, such as windows and building materials.
- the present invention is an active energy ray-curable adhesive composition for plastic films or sheets comprising the following components (A) to (D) as essential components.
- the component (A) is a polymer obtained by polymerizing the monomer (a1) and the monomer (a2), and has a glass transition temperature (hereinafter referred to as “Tg”) of 20 ° C.
- Tg glass transition temperature
- Mw weight average molecular weight
- the component (A) is a polymer having an epoxy group and can be copolymerized with the components (B) and (C) that are cationically curable compounds.
- the Tg of the component (A) is 20 ° C. or higher, preferably 40 ° C. or higher, more preferably 40 to 100 ° C. If the polymer has a Tg of less than 20 ° C., the adhesive strength is insufficient.
- Tg means a value measured at a heating rate of 10 ° C./min using a differential scanning calorimeter (DSC).
- the Mw of the component (A) is 1,000 to 30,000, preferably 3,000 to 20,000, more preferably 5,000 to 15,000.
- Mw of (A) component is less than 1,000, the adhesive force with a plastic base material will fall.
- Mw of the component (A) exceeds 30,000, the viscosity becomes high, and solventless coating becomes difficult.
- Mw means what converted the molecular weight measured by GPC into polystyrene.
- the component (A) is a polymer having the monomer (a1) and the monomer (a2) as essential constituent monomer units.
- the monomer (a1) is a compound having an epoxy group and an ethylenically unsaturated group.
- examples of the ethylenically unsaturated group in the monomer (a1) include a vinyl group and a (meth) acryloyl group.
- Specific examples of the monomer (a1) include glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl (meth) acrylate.
- the monomer (a2) is a compound having an ethylenically unsaturated group and is a compound other than the monomer (a1).
- Examples of the ethylenically unsaturated group in the monomer (a2) include a vinyl group and a (meth) acryloyl group.
- As the monomer (a2) various compounds can be appropriately selected so that the obtained polymer satisfies the Tg.
- Preferable specific examples of the monomer (a2) include alkyl (meth) acrylate.
- alkyl (meth) acrylate examples include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, Hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate N-decyl (meth) acrylate, isodecyl (meth) acrylate, n-dodecyl (meth) acrylate, n-tridecyl (meth) acrylate,
- the alkyl (meth) acrylate is preferably an alkyl (meth) acrylate containing an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl (meth) acrylate having a lower alkyl group having 1 to 4 carbon atoms. preferable.
- methacrylates having an alkyl group having 1 to 4 carbon atoms is preferred.
- the monomer (a1) is contained in an amount of 10 to 80% by weight in all constituent monomer units, and the alkyl (meth) acrylate is used in an amount of 20 to 90% by weight as the monomer (a2). %, More preferably 10 to 60% by weight of monomer (a1), and 40 to 90% by weight of alkyl (meth) acrylate as monomer (a2).
- Another preferred specific example of the monomer (a2) is an aromatic vinyl compound.
- the aromatic vinyl compound include styrene and ⁇ -methylstyrene.
- the aromatic vinyl compound is preferably used in combination with an alkyl (meth) acrylate.
- glycidyl methacrylate is used as the monomer (a1), and an alkyl group having 1 to 4 carbon atoms such as methyl methacrylate as the monomer (a2).
- an alkyl methacrylate having styrene and styrene is preferred.
- the monomer (a1) is contained in an amount of 10 to 80% by weight in all constituent monomer units, and the alkyl (meth) acrylate is contained in an amount of 10 to 80% by weight as the monomer (a2).
- the aromatic vinyl compound is preferably 10 to 80% by weight, more preferably 10 to 60% by weight of the monomer (a1), and 20% alkyl (meth) acrylate as the monomer (a2). Containing 70 wt% and 10-60 wt% aromatic vinyl compound.
- carboxyl group-containing monomers such as (meth) acrylic acid; sulfonic acid group-containing monomers such as acrylamide 2-methylpropane sulfonic acid and styrene sulfonic acid; phosphoric acid group-containing monomers; ) Cyano group-containing monomers such as acrylonitrile, vinyl esters; acid anhydride group-containing monomers; hydroxyalkyl (meth) such as hydroxyethyl (meth) acrylate, hydroxyethyl (meth) acrylate and hydroxybutyl (meth) acrylate Hydroxyl group-containing monomers such as acrylates; Amide group-containing monomers such as acrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide and (meth) acryloylmorpholine; N- (meth)
- the component (A) is a polymer obtained by polymerizing the monomer (a1) and the monomer (a2).
- a polymer obtained by high temperature polymerization is preferable.
- the component (A) is a polymer having a low Mw, and when a polymer having such a low Mw is produced by a normal polymerization method, it is produced by increasing the number of chain transfer agents and polymerization initiators. If a polymer using a large amount of chain transfer agent is used, the cation curability and adhesive strength of the composition are likely to decrease. If a polymer using a large amount of polymerization initiator is used, the composition may be stored. A polymer produced by high-temperature polymerization that does not require a large amount of chain transfer agent or polymerization initiator is preferred because stability may be easily lowered.
- the temperature of the high temperature polymerization is preferably 160 ° C. or higher, more preferably 160 to 350 ° C., and particularly preferably 180 to 300 ° C.
- high-temperature continuous polymerization not only has excellent productivity, but also has advantages such as excellent compatibility because it is difficult to achieve a composition distribution in the copolymer product.
- the high-temperature continuous polymerization can be carried out by a known method (for example, see JP-T-57-502171, JP-A-59-6207, JP-A-60-215007, etc.). Specifically, after filling a pressurizable reactor with a solvent and setting it to a predetermined temperature under pressure, a monomer or a monomer mixture consisting of a polymerization solvent and a polymerization initiator as needed is fixed. And a method of withdrawing the reaction solution in an amount commensurate with the supply amount of the monomer mixture.
- the above-described compounds may be used alone, or two or more kinds may be used.
- the content of component (A) is preferably 1 to 60% by weight in the entire composition. By setting this ratio, the coating property can be improved, and the adhesive strength can be improved even if the atmospheric humidity during coating and curing is high.
- a more preferable content ratio of the component (A) is 5 to 55% by weight, and more preferably 10 to 50% by weight in the entire composition.
- the component (B) is a polyglycidyl ether of a polyol having 2 to 10 carbon atoms.
- the “carbon number” in a polyol having 2 to 10 carbon atoms means the number of carbons constituting the site obtained by removing the hydroxyl group from the polyol.
- Examples of the component (B) include polyglycidyl ethers of alkane polyols and polyglycidyl ethers of aromatic polyols, and diglycidyl ethers of alkane diols and diglycidyl ethers of aromatic diols are preferred.
- component (B) examples include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, cyclohexane.
- diglycidyl ether of alkanediol having 4 to 6 carbon atoms such as 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether and the like.
- the obtained composition has a low viscosity, and the cured product is more preferable in that it has excellent adhesion and is colorless and transparent.
- 1,6-hexanediol diglycidyl ether is particularly preferable.
- component (B) As a component, an above described compound may be used independently, or 2 or more types may be used.
- the content of component (B) is preferably 1 to 60% by weight in the entire composition. By setting it as this ratio, even if the atmospheric humidity at the time of coating and hardening is high, adhesive force can be made favorable.
- a more preferable content ratio of the component (B) is 5 to 55% by weight in the whole composition, and more preferably 10 to 50% by weight.
- Component (C) is a compound having a molecular weight of 500 or less having two or more oxetanyl groups in one molecule.
- component (C) examples include bis [(3-ethyloxetane-3-yl) methyl] ether, bis [(3-methyloxetane-3-yl) methyl] ether, and bis [(oxetane-3-yl ) Methyl] ether, 1,4-bis [[(3-ethyloxetane-3-yl) methoxy] methyl] benzene, 1,4-bis [(3-ethyloxetane-3-yl) methoxy] benzene, 3-bis [(3-ethyloxetane-3-yl) methoxy] benzene, 1,2-bis [(3-ethyloxetane-3-yl) methoxy] benzene, 4,4′-bis [(3-ethyloxetane -3-yl) methoxy] biphenyl, 2,2′-bis [(3-ethyloxetane-3-yl) meth
- a compound having a molecular weight of 150 to 400 having two oxetanyl groups in one molecule is more preferable in that the resulting composition has a low viscosity and the cured product has excellent adhesive strength.
- a more preferred molecular weight is in the range of 150 to 300.
- bis [(3-ethyloxetane-3-yl) methyl] ether that is, an oxetane compound represented by the following formula (1) is particularly preferable.
- component (C) As a component, an above described compound may be used independently, or 2 or more types may be used.
- the content of component (C) is preferably 1 to 60% by weight in the entire composition. By setting it as this ratio, even if the atmospheric humidity at the time of coating and hardening is high, adhesive force can be made favorable.
- a more preferable content ratio of the component (C) is 5 to 55% by weight, and more preferably 10 to 50% by weight in the whole composition.
- Component (D) component is a photocationic polymerization initiator. That is, it is a compound that generates a cation or a Lewis acid upon irradiation with active energy rays such as ultraviolet rays and electron beams, and initiates polymerization of a cationically curable component such as an epoxy compound or an oxetane compound.
- Specific examples of the component (D) include sulfonium salt photocationic polymerization initiators, iodonium salt photocationic polymerization initiators, diazonium salt photocationic polymerization initiators, and the like.
- sulfonium salt photocationic polymerization initiators include, for example: Triphenylsulfonium hexafluorophosphate, Triphenylsulfonium hexafluoroantimonate, Triphenylsulfonium tetrakis (pentafluorophenyl) borate, Diphenyl-4- (phenylthio) phenylsulfonium hexafluorophosphate, Diphenyl-4- (phenylthio) phenylsulfonium hexafluoroantimonate, 4,4′-bis [diphenylsulfonio] diphenyl sulfide bishexafluorophosphate, 4,4′-bis [di ( ⁇ -hydroxyethoxy) phenylsulfonio] diphenyl sulfide bishexafluoroantimonate, 4,4′-bis [di ( ⁇ -hydroxyethoxy) phen
- iodonium salt-based photocationic polymerization initiators include, for example: Diphenyliodonium tetrakis (pentafluorophenyl) borate diphenyliodonium hexafluorophosphate, Diphenyliodonium hexafluoroantimonate, Di (4-t-butylphenyl) iodonium hexafluorophosphate, Di (4-t-butylphenyl) iodonium hexafluoroantimonate, Trilcumyl iodonium tetrakis (pentafluorophenyl) borate, (4-methylphenyl) [4- (2-methylpropyl) phenyl] -hexafluorophosphate, Di (4-nonylphenyl) iodonium hexafluorophosphate, Di (4-alkylphenyl) iodonium hexafluorophosphate
- diazonium salt photocationic polymerization initiators examples include benzenediazonium hexafluoroantimonate, Examples thereof include benzenediazonium hexafluorophosphate.
- Component (D) is commercially available, Adekaoptomer SP-100, SP-150, SP-152, SP-170, SP-172 (manufactured by ADEKA), photoinitiator 2074 (manufactured by Rhodia), Kayrad PCI-220, PCI-620 (manufactured by Nippon Kayaku Co., Ltd.), Irgacure 250 (manufactured by Ciba Japan), CPI-100P, CPI-110P, CPI-101A, CPI-200K, CPI-210S [San Apro ( Co., Ltd.), WPI-113, WPI-116 [Wako Pure Chemical Industries, Ltd.]), BBI-102, BBI-103, TPS-102, TPS-103, DTS-102, DTS-103 [Midori Chemical Etc.].
- a sulfonium salt-based photocationic polymerization initiator is preferable, and a triarylsulfonium salt is more preferable because it has excellent active energy ray curability and excellent colorless transparency.
- a triarylsulfonium salt is more preferable because it has excellent active energy ray curability and excellent colorless transparency.
- triarylsulfonium salts triphenylsulfonium hexafluorophosphate and diphenyl-4- (phenylthio) phenylsulfonium hexafluorophosphate are preferable.
- the above-described compounds may be used alone, or two or more kinds may be used.
- the content ratio of the component (D) is preferably 0.5 to 10% by weight, more preferably 1 to 6% by weight in the whole composition.
- the ratio of the component (D) is 0.5% by weight or more, the curability can be excellent, and when it is 10% by weight or less, the cured product can have excellent colorless transparency. .
- composition of the present invention essentially comprises the components (A) to (D), but various components (referred to as “other components”) can be blended depending on the purpose.
- the other cationic curable component is preferably contained in an amount of 40% by weight or less, more preferably 20% by weight or less, in 100% by weight of the total amount of the cationic curable component.
- the cationic curable component include an epoxy group-containing compound other than the component (B), an oxetanyl group-containing compound other than the component (C), and a vinyl ether group-containing compound.
- epoxy group-containing compound other than the component (B) examples include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxy.
- epoxidized vegetable oil 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, polybutadiene internal epoxidized product, styrene-butadiene copolymer double bond partially epoxidized Compound (for example, “Epofriend” manufactured by Daicel Chemical Industries, Ltd.) and a compound in which the isoprene unit of the block copolymer of ethylene-butylene copolymer and polyisoprene is partially epoxidized (for example, manufactured by KRATON) "L-207”) and the like.
- oxetane compound other than the component (C) include alkoxyalkyl group-containing monofunctional oxetanes such as 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane and 3-ethyl-3-phenoxymethyloxetane.
- vinyl ether compound examples include cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, dodecyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, triethylene glycol divinyl ether, cyclohexane dimethanol divinyl ether, and the like.
- composition of the present invention may contain various additives other than the curable component as long as the effects of the present invention are not impaired.
- additives include thermal cationic polymerization initiator, photosensitizer, UV absorber, light stabilizer, antioxidant, polymerization inhibitor, silane coupling agent, polyol compound, polymer, tackifier, filler, metal Examples thereof include fine particles, metal oxide fine particles, ion trapping agents, antifoaming agents, leveling agents, dyes and pigments.
- Plastic films or sheets for radiation-curable adhesive composition The present invention relates to the (A) ⁇ (D) of plastic film or sheet for the active energy ray-curable adhesive composition comprising a component as an essential component.
- the total chlorine content in the composition is preferably 0.1% by weight or less.
- a method for reducing the total chlorine content in the composition for example, a distilled purified product is used as all or part of the glycidyl ether compound other than the component (B) and the components (A) and (B). Methods and the like.
- the method for producing the composition of the present invention may be in accordance with a conventional method, and the components (A) to (D) may be produced by stirring and mixing the other components, if necessary, according to a conventional method. Can do. In this case, it can be heated or heated as necessary.
- the viscosity at 25 ° C. should be 3,000 mPa ⁇ s or less. It is preferably 10 to 1,500 mPa ⁇ s. More preferably, it is 50 to 1,000 mPa ⁇ s.
- the viscosity of the composition at 25 ° C. is a value measured by an E-type viscometer.
- composition of the present invention can be used for adhesion between plastic films and the like, and adhesion between plastic films and the like and various other substrates (hereinafter referred to as “other substrates”). That is, it can be used for bonding two substrates, at least one of which is a plastic film or the like.
- base material when simply described as “base material”, it means a general term for plastic films and other base materials.
- Other examples of the substrate include glass, metal oxide, metal, wood and paper.
- Examples of the material in the plastic film include cycloolefin polymer, (meth) acrylic resin, polystyrene, acrylic / styrene copolymer, triacetyl cellulose, cellulose acetate butyrate, polyvinyl chloride, polyvinylidene chloride, polyethylene, polypropylene, Examples include ABS resin, polyamide, polyester, polycarbonate, polyurethane, and chlorinated polypropylene.
- Examples of the (meth) acrylic resin include (meth) acrylic resin which is a copolymer mainly composed of polymethyl methacrylate and methyl methacrylate, and (meth) acrylic resin which does not contain methyl methacrylate as a polymerization monomer.
- the composition of the present invention can be preferably applied to cycloolefin polymers and (meth) acrylic resins.
- the metal oxide examples include tin oxide, indium oxide, titanium oxide, and zinc oxide.
- the metal examples include gold, silver, copper, aluminum, iron, nickel, and titanium.
- the transparency that is one of the characteristics of the composition of the present invention is often required, so that it is more preferably applied.
- an activation treatment can be performed on one or both surfaces before applying the composition of the present invention.
- the surface activation treatment include plasma treatment, corona discharge treatment, chemical treatment, surface roughening treatment and etching treatment, and flame treatment, and these may be used in combination.
- Method of use As a method of using the composition of the present invention, it is sufficient to follow a conventional method, and after applying the composition to a substrate, it is bonded to the other substrate and irradiated with an active energy ray. It is done.
- the composition of the present invention is suitable for bonding a thin layer adherend as a substrate.
- the method of use for adhering the thin-layer adherend may be in accordance with a method usually used in the production of laminates. For example, a method in which the composition is applied to a first thin-layer adherend, a second thin-layer adherend is bonded to the composition, and irradiation with active energy rays is performed.
- Coating on the substrate may be performed by a conventionally known method, natural coater, knife belt coater, floating knife, knife over roll, knife on blanket, spray, dip, kiss roll, squeeze roll, reverse roll, air blade , Curtain flow coater, comma coater, gravure coater, micro gravure coater, die coater and curtain coater.
- the coating thickness of the composition of the present invention may be selected according to the substrate to be used and the application, but is preferably 0.1 to 10 ⁇ m, more preferably 1 to 5 ⁇ m.
- active energy rays examples include visible light, ultraviolet rays, X-rays, and electron beams, but ultraviolet rays are preferable because inexpensive devices can be used.
- Various light sources can be used as the light source when cured by ultraviolet rays, and examples thereof include a pressurized or high pressure mercury lamp, a metal halide lamp, a xenon lamp, an electrodeless discharge lamp, a carbon arc lamp, and an LED. Among these, a high pressure mercury lamp and a metal halide lamp are particularly preferable.
- the irradiation amount of ultraviolet rays is preferably 100 to 2,000 mJ / cm 2 in the UV-A region (near 365 nm), more preferably 200 to 1,500 mJ / cm 2 , still more preferably 300 to 1,000 mJ. / Cm 2 .
- an EB irradiation device that can be used, such as a Cockloft-Waltsin type, a bandegraph type, and a resonance transformer type device.
- Those having an energy of 1000 eV are preferred, and more preferably 100 to 300 eV.
- the composition of this invention can be preferably used for manufacture of a laminated body. Specifically, the above-described composition is applied to a substrate, another substrate is bonded to the coated surface, and an active energy ray is irradiated from either side of the substrate. . In this case, a plastic film or the like is used as both base materials or at least one base material. Specific examples and preferred examples of the substrate are as described above.
- the coating method of the composition, the film thickness of the composition, the irradiation conditions of the type of active energy ray, etc. are also as described above.
- parts means parts by weight
- numerical values indicating the blending ratios in the table mean% by weight
- each component used for the preparation of the composition is as follows, and is abbreviated as follows.
- Component (B) HD-DGE 1,6-hexanediol diglycidyl ether (distilled product), “Epogosei HD (D)” manufactured by Yokkaichi Gosei Co., Ltd.
- Component (C) OXT-221 bis [(3-ethyloxetane-3-yl) methyl] ether, “Aron oxetane OXT-221” manufactured by Toagosei Co., Ltd.
- Component (D) CPI-110P Triarylsulfonium hexafluorophosphate (active ingredient 100%), “CPI-110P” manufactured by San Apro Co., Ltd.
- Production Example 1 The jacket temperature of a 1000 mL capacity pressurized stirred tank reactor equipped with an oil jacket was maintained at 190 ° C. Next, while maintaining the reactor pressure constant, glycidyl methacrylate (hereinafter referred to as “GMA”) (30 parts), methyl methacrylate (hereinafter referred to as “MMA”) (45 parts), styrene (25 parts), polymerization solvent A monomer mixture consisting of methyl ethyl ketone (hereinafter referred to as “MEK”) (18 parts) and di-t-butyl peroxide (hereinafter referred to as “DBP”) (0.25 parts) as a polymerization initiator Continuous supply from the raw material tank to the reactor was started at a supply rate (48 g / min, residence time: 12 minutes), and a reaction liquid corresponding to the supply amount of the monomer mixture was continuously extracted from the outlet.
- GMA glycidyl methacrylate
- MMA methyl methacrylate
- the polystyrene-equivalent number average molecular weight (Mn) was 3,500
- the weight average molecular weight (Mw) was 9,900
- Tg DSC measurement, heating rate 10 ° C./min
- the internal temperature of the reactor was maintained at 182 to 184 ° C.
- the time point after 36 minutes from the stabilization of the reactor internal temperature was taken as the starting point for collecting the reaction liquid, and the reaction was continued for 25 minutes.
- 1.2 kg of the monomer mixture was supplied, The reaction solution was collected.
- the reaction solution was introduced into a thin film evaporator to separate volatile components such as unreacted monomers, and volatile components such as unreacted monomers were removed to obtain a polymer “polymer X2”.
- Mn was 3,200
- Mw was 8,500
- Tg was 53 ° C.
- the polystyrene-equivalent number average molecular weight (Mn) was 3,460
- the weight average molecular weight (Mw) was 9,700
- Tg DSC measurement, heating rate 10 ° C./min
- the viscosity was 12,200 mPa ⁇ s at 80 ° C.
- Cycloolefin polymer having a thickness of 100 ⁇ m (trade name ZEONOR ZF-14, manufactured by Nippon Zeon Co., Ltd., hereinafter referred to as “ZEONOR”), and acrylic resin with UV absorber having a thickness of 75 ⁇ m [trade name HI50 -75 KT-UV (manufactured by Kuraray Co., Ltd., hereinafter referred to as “acrylic resin”) was subjected to corona treatment as an easy adhesion treatment.
- the corona-treated surface of the acrylic resin was coated with the obtained composition with a bar coater to a thickness of 3 ⁇ m, and then ZEONOR was laminated.
- compositions of Examples 1 and 2 were both excellent in transparency and were tested under severe conditions of 80% humidity, the composition of Example 1 had a strong adhesive strength of 10 N / inch or more. At the same time, the substrate was broken and could not be peeled off, and the composition of Example 2 was also excellent in adhesive strength.
- the compositions of Comparative Example 1 and Comparative Example 2 that did not contain the component (A) were both excellent in transparency, the adhesive strength was greatly reduced.
- the composition of Comparative Example 2 is produced by continuous polymerization, and the constituent monomer and Mw correspond to the component (A), but the Tg is changed to the polymer Y which is a polymer that does not satisfy the upper limit of 20 ° C.
- the adhesive strength was greatly reduced.
- the composition of Comparative Example 3 not containing the component (B) was excellent in transparency, the adhesive strength was greatly reduced.
- the composition of the comparative example 4 which does not contain (C) component and the composition of the comparative example 5 which changed (B) component into the (B) 'component are all excellent in transparency, the composition of an Example The adhesive strength was reduced compared to the product.
- composition of the present invention can be used as an adhesive for plastic films and the like, and can be particularly suitably used for bonding optical films used in liquid crystal displays and organic EL displays.
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Abstract
Description
尚、本明細書においては、アクリレート及び/又はメタクリレートを(メタ)アクリレートと、アクリロイル基及び/又はメタクリロイル基を(メタ)アクリロイル基と、アクリル酸及び/又はメタクリル酸を(メタ)アクリル酸と表す。
又、以下において、特に明示する必要がない場合は、プラスチック製フィルム又はシートをまとめて「プラスチックフィルム等」と表し、フィルム又はシートをまとめて「フィルム等」と表す。 The present invention relates to an active energy ray-curable adhesive composition capable of bonding various plastic films or sheets by irradiation with active energy rays such as ultraviolet rays, visible light, or electron beams, and It is suitably used for the production of various optical films or sheets used for liquid crystal displays, organic EL displays and the like, and can be used in these technical fields.
In the present specification, acrylate and / or methacrylate is represented by (meth) acrylate, acryloyl group and / or methacryloyl group is represented by (meth) acryloyl group, and acrylic acid and / or methacrylic acid is represented by (meth) acrylic acid. .
In the following description, unless otherwise specified, a plastic film or sheet is collectively expressed as “plastic film or the like”, and a film or sheet is collectively expressed as “film or the like”.
この方法で使用される接着剤組成物は、一般に組成物の塗布量を均一にするため溶剤を多く含むものであるが、このため乾燥時に多量の溶剤蒸気が揮散してしまい、毒性、作業安全性及び環境汚染性が問題となっている。
これらの問題を解決する接着剤組成物として、無溶剤系の接着剤組成物が検討されている。 Conventionally, in a laminating method in which a thin-layer adherend such as a plastic film or a thin-layer adherend such as a plastic film is bonded to a thin-layer adherend made of another material, an ethylene-vinyl acetate copolymer is used. A solvent-type adhesive composition containing a polymer or a polyurethane-based polymer is applied to the first thin-layer adherend and dried, and then the second thin-layer adherend is applied to the first thin-layer adherend using a nip roller or the like. The dry laminating method for pressure bonding is mainly performed.
The adhesive composition used in this method generally contains a large amount of a solvent in order to make the coating amount of the composition uniform, but for this reason, a large amount of solvent vapor is volatilized during drying, resulting in toxicity, work safety and Environmental pollution is a problem.
As an adhesive composition for solving these problems, a solventless adhesive composition has been studied.
2液型接着剤組成物としては、主に末端に水酸基を有するポリマーを主剤とし、末端にイソシアネート基を有するポリイソシアネート化合物を硬化剤とする、いわゆるポリウレタン系接着剤組成物が用いられている。しかしながら該組成物は、硬化に長時間を要するという欠点がある。
これに対して、活性エネルギー線硬化型接着剤組成物は、硬化速度が速いことから生産性に優れるため、近年使用される場面が増えてきている。 As the solventless adhesive composition, a two-component adhesive composition and an adhesive composition that is cured by an active energy ray such as an ultraviolet ray or an electron beam are widely used.
As the two-component adhesive composition, a so-called polyurethane adhesive composition is mainly used in which a polymer having a hydroxyl group at the terminal is a main agent and a polyisocyanate compound having an isocyanate group at the terminal is a curing agent. However, this composition has the disadvantage that it takes a long time to cure.
On the other hand, the active energy ray-curable adhesive composition is excellent in productivity because of its high curing rate, and thus has been used in recent years.
さらに、特許文献1に開示されている組成物は、ポリメチルメタクリレート及びアルキル(メタ)アクリレートポリマー等の(メタ)アクリル樹脂への接着力が不十分であるという問題があった。
しかも、接着剤を塗工・硬化する際の雰囲気の湿度が高いと、接着力が大きく低下するという問題があった。 However, the composition disclosed in Patent Document 1 has a problem that the cationic curability is poor and the energy required for curing is large. For this reason, it was necessary to slow down the line speed of the bonding process or increase the number of light sources. Therefore, from the viewpoint of productivity, an active energy ray-curable adhesive having excellent curability, specifically, sufficient adhesive force is exhibited even at an irradiation dose of 1,000 mJ / cm 2 or less at UV-A (365 nm). Therefore, an active energy ray-curable adhesive has been desired.
Furthermore, the composition disclosed in Patent Document 1 has a problem that adhesive strength to (meth) acrylic resins such as polymethyl methacrylate and alkyl (meth) acrylate polymers is insufficient.
In addition, when the humidity of the atmosphere when applying and curing the adhesive is high, there is a problem that the adhesive strength is greatly reduced.
(A)成分:(a1)エポキシ基及びエチレン性不飽和基を有する化合物〔以下、「単量体(a1)」という〕及び(a2)エチレン性不飽和基を有する化合物であって、単量体(a1)以外の化合物〔以下、「単量体(a2)」という〕を重合して得られた重合体であって、ガラス転移温度が20℃以上であり、重量平均分子量が1,000~30,000である重合体
(B)成分:炭素数2~10個を有するジオールのジグリシジルエーテル
(C)成分:1分子中に2個以上のオキセタニル基を有する分子量500以下の化合物
(D)成分:光カチオン重合開始剤 The present invention relates to an active energy ray-curable adhesive composition for plastic films or sheets comprising the following components (A) to (D) as essential components.
Component (A): (a1) a compound having an epoxy group and an ethylenically unsaturated group [hereinafter referred to as “monomer (a1)”] and (a2) a compound having an ethylenically unsaturated group, each having a single amount A polymer obtained by polymerizing a compound other than the body (a1) [hereinafter referred to as “monomer (a2)”], having a glass transition temperature of 20 ° C. or higher and a weight average molecular weight of 1,000. Polymer (B) component having a molecular weight of ˜30,000: Diglycidyl ether (C) component of a diol having 2 to 10 carbon atoms: Compound having a molecular weight of 500 or less having two or more oxetanyl groups in one molecule (D ) Component: Photocationic polymerization initiator
又、(A)成分が、全構成単量体単位中に、単量体(a1)を10~80重量%含み、単量体(a2)として、炭素数1~10のアルキル基を有するアルキル(メタ)アクリレートを10~80重量%及び芳香族ビニル化合物を10~80重量%含み、且つ、重量平均分子量が3,000~20,000の重合体であることが好ましい。
又、(A)成分が、単量体(a1)としてグリシジルメタクリレートを含み、単量体(a2)としてメチルメタクリレート及びスチレンを含むことが好ましい。
更に、(A)成分が、単量体(a1)及び単量体(a2)を高温重合して得られた重合体であることが好ましく、より好ましくは160℃以上の温度で高温重合して得られた重合体である。 In the component (A), the monomer (a2) preferably contains an alkyl (meth) acrylate having an alkyl group having 1 to 10 carbon atoms and / or an aromatic vinyl compound.
In addition, the component (A) is an alkyl having an alkyl group having 1 to 10 carbon atoms as the monomer (a2) containing 10 to 80% by weight of the monomer (a1) in all constituent monomer units. A polymer containing 10 to 80% by weight of (meth) acrylate and 10 to 80% by weight of an aromatic vinyl compound and having a weight average molecular weight of 3,000 to 20,000 is preferred.
The component (A) preferably contains glycidyl methacrylate as the monomer (a1) and contains methyl methacrylate and styrene as the monomer (a2).
Furthermore, the component (A) is preferably a polymer obtained by high-temperature polymerization of the monomer (a1) and the monomer (a2), more preferably high-temperature polymerization at a temperature of 160 ° C. or higher. It is the obtained polymer.
(C)成分が、後記式(1)に示すオキセタン化合物であることが好ましい。
(D)成分が、スルホニウム塩系光カチオン重合開始剤であることが好ましい。 The component (B) is preferably diglycidyl ether of alkanediol having 4 to 6 carbon atoms.
The component (C) is preferably an oxetane compound represented by the following formula (1).
The component (D) is preferably a sulfonium salt photocationic polymerization initiator.
また、プラスチック製フィルム又はシートの少なくとも一方が、シクロオレフィンポリマー又は(メタ)アクリル樹脂であることが好ましい。 In the whole composition, the component (A) is 1 to 60% by weight, the component (B) is 1 to 60% by weight, the component (C) is 1 to 60% by weight, and the component (D) is 0.5 to 10% by weight. % Content is preferable.
Moreover, it is preferable that at least one of the plastic film or sheet is a cycloolefin polymer or a (meth) acrylic resin.
前記基材の両方又は一方が、プラスチック製フィルム又はシートである積層体の製造方法に関する。 The present invention also provides a laminate in which the above composition is applied to a substrate, another substrate is bonded to the coated surface, and active energy rays are irradiated from either side of the substrate. A method,
The present invention relates to a method for producing a laminate in which both or one of the substrates is a plastic film or sheet.
(A)成分:単量体(a1)及び単量体(a2)を重合して得られた重合体であって、ガラス転移温度が20℃以上であり、重量平均分子量が1,000~30,000である重合体
(B)成分:炭素数2~10個を有するポリオールのポリグリシジルエーテル
(C)成分:1分子中に2個以上のオキセタニル基を有する分子量500以下の化合物
(D)成分:光カチオン重合開始剤
以下、(A)~(D)成分、その他の成分、及び本発明の組成物の好ましい使用方法について、詳細に説明する。 The present invention is an active energy ray-curable adhesive composition for plastic films or sheets comprising the following components (A) to (D) as essential components.
Component (A): a polymer obtained by polymerizing the monomer (a1) and the monomer (a2), having a glass transition temperature of 20 ° C. or higher and a weight average molecular weight of 1,000 to 30 Polymer (B) component of 1,000,000: Polyglycidyl ether (C) component of a polyol having 2 to 10 carbon atoms: Compound (D) component having a molecular weight of 500 or less having two or more oxetanyl groups in one molecule : Photocationic polymerization initiator Hereinafter, components (A) to (D), other components, and preferred methods of using the composition of the present invention will be described in detail.
(A)成分は、単量体(a1)及び単量体(a2)を重合して得られた重合体であって、ガラス転移温度(以下、「Tg」という)が20℃以上であり、重量平均分子量(以下、「Mw」という)が1,000~30,000である重合体である。
(A)成分は、エポキシ基を有する重合体であり、カチオン硬化性化合物である(B)及び(C)成分と共重合することができる。 1. Component (A) The component (A) is a polymer obtained by polymerizing the monomer (a1) and the monomer (a2), and has a glass transition temperature (hereinafter referred to as “Tg”) of 20 ° C. The polymer having a weight average molecular weight (hereinafter referred to as “Mw”) of 1,000 to 30,000.
The component (A) is a polymer having an epoxy group and can be copolymerized with the components (B) and (C) that are cationically curable compounds.
Tgが20℃に満たない重合体では接着力が不十分となってしまう。
尚、本発明においてTgとは、示差走査熱量計(DSC)を用いて、10℃/分の昇温速度で測定した値を意味する。 The Tg of the component (A) is 20 ° C. or higher, preferably 40 ° C. or higher, more preferably 40 to 100 ° C.
If the polymer has a Tg of less than 20 ° C., the adhesive strength is insufficient.
In the present invention, Tg means a value measured at a heating rate of 10 ° C./min using a differential scanning calorimeter (DSC).
尚、本発明において、Mwとは、GPCにより測定した分子量をポリスチレン換算したものを意味する。 The Mw of the component (A) is 1,000 to 30,000, preferably 3,000 to 20,000, more preferably 5,000 to 15,000. When Mw of (A) component is less than 1,000, the adhesive force with a plastic base material will fall. When the Mw of the component (A) exceeds 30,000, the viscosity becomes high, and solventless coating becomes difficult.
In addition, in this invention, Mw means what converted the molecular weight measured by GPC into polystyrene.
単量体(a1)は、エポキシ基及びエチレン性不飽和基を有する化合物である。
単量体(a1)におけるエチレン性不飽和基としては、ビニル基及び(メタ)アクリロイル基等が挙げられる。
単量体(a1)の具体例としては、グリシジル(メタ)アクリレート及び3,4-エポキシシクロヘキシルメチル(メタ)アクリレート等が挙げられる。 The component (A) is a polymer having the monomer (a1) and the monomer (a2) as essential constituent monomer units.
The monomer (a1) is a compound having an epoxy group and an ethylenically unsaturated group.
Examples of the ethylenically unsaturated group in the monomer (a1) include a vinyl group and a (meth) acryloyl group.
Specific examples of the monomer (a1) include glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl (meth) acrylate.
単量体(a2)におけるエチレン性不飽和基としては、ビニル基及び(メタ)アクリロイル基等が挙げられる。
単量体(a2)は、得られる重合体が前記Tgを満たすように種々の化合物を適宜選択することができる。 The monomer (a2) is a compound having an ethylenically unsaturated group and is a compound other than the monomer (a1).
Examples of the ethylenically unsaturated group in the monomer (a2) include a vinyl group and a (meth) acryloyl group.
As the monomer (a2), various compounds can be appropriately selected so that the obtained polymer satisfies the Tg.
芳香族ビニル化合物としては、スチレン及びα-メチルスチレン等が挙げられる。
芳香族ビニル化合物は、アルキル(メタ)アクリレートと併用して使用することが好ましい。 Another preferred specific example of the monomer (a2) is an aromatic vinyl compound.
Examples of the aromatic vinyl compound include styrene and α-methylstyrene.
The aromatic vinyl compound is preferably used in combination with an alkyl (meth) acrylate.
具体的には、(メタ)アクリル酸等のカルボキシル基含有単量体;アクリルアミド2-メチルプロパンスルホン酸及びスチレンスルホン酸等のスルホン酸基含有単量体;リン酸基含有単量体;(メタ)アクリロニトリル等のシアノ基含有単量体、ビニルエステル;酸無水物基含有単量体;ヒドロキシエチル(メタ)アクリレート、ヒドロキシエチル(メタ)アクリレート及びヒドロキシブチル(メタ)アクリレート等のヒドロキシアルキル(メタ)アクリレート等のヒドロキシル基含有単量体;アクリルアミド、N,N-ジメチルアクリルアミド、N,N-ジエチルアクリルアミド及び(メタ)アクリロイルモルホリン等のアミド基含有単量体;N-(メタ)アクリロイルオキシエチルヘキサヒドロフタルイミド、N-(メタ)アクリロイルオキシエチルテトラヒドロフタルイミド等のイミド基含有単量体;並びにビニルエーテル等が挙げられる。 As the monomer (a2), in addition to the above, compounds having various ethylenically unsaturated groups can be used depending on the purpose.
Specifically, carboxyl group-containing monomers such as (meth) acrylic acid; sulfonic acid group-containing monomers such as acrylamide 2-methylpropane sulfonic acid and styrene sulfonic acid; phosphoric acid group-containing monomers; ) Cyano group-containing monomers such as acrylonitrile, vinyl esters; acid anhydride group-containing monomers; hydroxyalkyl (meth) such as hydroxyethyl (meth) acrylate, hydroxyethyl (meth) acrylate and hydroxybutyl (meth) acrylate Hydroxyl group-containing monomers such as acrylates; Amide group-containing monomers such as acrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide and (meth) acryloylmorpholine; N- (meth) acryloyloxyethylhexahydro Phthalimide, N- (meth) acryloyl Imide group-containing monomers such as carboxyethyl tetrahydrophthalimide; and vinyl ether.
(A)成分としては、高温重合で得られた重合体が好ましい。
(A)成分はMwが低い重合体であり、このようなMwが低い重合体を通常の重合方法で製造する場合には、連鎖移動剤や重合開始剤を多くして製造する。連鎖移動剤を多量に使用した重合体を使用すると、組成物のカチオン硬化性や接着力が低下し易くなったり、又、重合開始剤を多量に使用した重合体を使用すると、組成物の保存安定性が低下し易くなる場合があるため、多量の連鎖移動剤や重合開始剤を必要としない高温重合により製造された重合体が好ましい。 The component (A) is a polymer obtained by polymerizing the monomer (a1) and the monomer (a2).
As the component (A), a polymer obtained by high temperature polymerization is preferable.
The component (A) is a polymer having a low Mw, and when a polymer having such a low Mw is produced by a normal polymerization method, it is produced by increasing the number of chain transfer agents and polymerization initiators. If a polymer using a large amount of chain transfer agent is used, the cation curability and adhesive strength of the composition are likely to decrease. If a polymer using a large amount of polymerization initiator is used, the composition may be stored. A polymer produced by high-temperature polymerization that does not require a large amount of chain transfer agent or polymerization initiator is preferred because stability may be easily lowered.
高温連続重合は、公知の方法で実施することができる(例えば、特表昭57-502171号公報、特開昭59-6207号公報及び特開昭60-215007号公報等参照)。
具体的には、加圧可能な反応器を溶媒で満たし、加圧下で所定温度に設定した後、単量体、又は必要に応じて重合溶媒、重合開始剤とからなる単量体混合物を一定の供給速度で反応器へ供給し、単量体混合物の供給量に見合う量の反応液を抜き出す方法が挙げられる。 Among high-temperature polymerizations, high-temperature continuous polymerization not only has excellent productivity, but also has advantages such as excellent compatibility because it is difficult to achieve a composition distribution in the copolymer product.
The high-temperature continuous polymerization can be carried out by a known method (for example, see JP-T-57-502171, JP-A-59-6207, JP-A-60-215007, etc.).
Specifically, after filling a pressurizable reactor with a solvent and setting it to a predetermined temperature under pressure, a monomer or a monomer mixture consisting of a polymerization solvent and a polymerization initiator as needed is fixed. And a method of withdrawing the reaction solution in an amount commensurate with the supply amount of the monomer mixture.
(A)成分の含有割合は、組成物全体中に1~60重量%が好ましい。この割合とすることで、塗工性を良好にすることができ、又塗工・硬化時の雰囲気湿度が高くても接着力を良好にすることができる。
(A)成分のより好ましい含有割合は、組成物全体中に5~55重量%であり、さらに好ましくは10~50重量%である。 As the component (A), the above-described compounds may be used alone, or two or more kinds may be used.
The content of component (A) is preferably 1 to 60% by weight in the entire composition. By setting this ratio, the coating property can be improved, and the adhesive strength can be improved even if the atmospheric humidity during coating and curing is high.
A more preferable content ratio of the component (A) is 5 to 55% by weight, and more preferably 10 to 50% by weight in the entire composition.
(B)成分は、炭素数2~10個を有するポリオールのポリグリシジルエーテルである。
尚、炭素数2~10個を有するポリオールにおける「炭素数」とは、ポリオールから水酸基を除いた部位を構成する炭素の数を意味する。
(B)成分としては、アルカンポリオールのポリグリシジルエーテル及び芳香族ポリオールのポリグリシジルエーテル等が挙げられ、アルカンジオールのジグリシジルエーテル及び芳香族ジオールのジグリシジルエーテルが好ましい。 2. Component (B) The component (B) is a polyglycidyl ether of a polyol having 2 to 10 carbon atoms.
The “carbon number” in a polyol having 2 to 10 carbon atoms means the number of carbons constituting the site obtained by removing the hydroxyl group from the polyol.
Examples of the component (B) include polyglycidyl ethers of alkane polyols and polyglycidyl ethers of aromatic polyols, and diglycidyl ethers of alkane diols and diglycidyl ethers of aromatic diols are preferred.
(B)成分の含有割合は、組成物全体中に1~60重量%が好ましい。この割合とすることで、塗工・硬化時の雰囲気湿度が高くても、接着力を良好にすることができる。
(B)成分のより好ましい含有割合は、組成物全体中に5~55重量%であり、さらに好ましくは10~50重量%である。 (B) As a component, an above described compound may be used independently, or 2 or more types may be used.
The content of component (B) is preferably 1 to 60% by weight in the entire composition. By setting it as this ratio, even if the atmospheric humidity at the time of coating and hardening is high, adhesive force can be made favorable.
A more preferable content ratio of the component (B) is 5 to 55% by weight in the whole composition, and more preferably 10 to 50% by weight.
(C)成分は、1分子中に2個以上のオキセタニル基を有する分子量500以下の化合物である。 3. Component (C) The component (C) is a compound having a molecular weight of 500 or less having two or more oxetanyl groups in one molecule.
(C)成分としては、ビス〔(3-エチルオキセタン-3-イル)メチル〕エーテル、すなわち下記式(1)に示すオキセタン化合物が、特に好ましい。 As the component (C), a compound having a molecular weight of 150 to 400 having two oxetanyl groups in one molecule is more preferable in that the resulting composition has a low viscosity and the cured product has excellent adhesive strength. A more preferred molecular weight is in the range of 150 to 300.
As the component (C), bis [(3-ethyloxetane-3-yl) methyl] ether, that is, an oxetane compound represented by the following formula (1) is particularly preferable.
(C)成分の含有割合は、組成物全体中に1~60重量%が好ましい。この割合とすることで、塗工・硬化時の雰囲気湿度が高くても、接着力を良好にすることができる。
(C)成分のより好ましい含有割合は、組成物全体中に5~55重量%であり、さらに好ましくは10~50重量%である。 (C) As a component, an above described compound may be used independently, or 2 or more types may be used.
The content of component (C) is preferably 1 to 60% by weight in the entire composition. By setting it as this ratio, even if the atmospheric humidity at the time of coating and hardening is high, adhesive force can be made favorable.
A more preferable content ratio of the component (C) is 5 to 55% by weight, and more preferably 10 to 50% by weight in the whole composition.
(D)成分は、光カチオン重合開始剤である。即ち、紫外線や電子線等の活性エネルギー線の照射によって、カチオン又はルイス酸を発生し、エポキシ化合物やオキセタン化合物等のカチオン硬化性成分の重合を開始させる化合物である。
(D)成分の具体例としては、スルホニウム塩系光カチオン重合開始剤、ヨードニウム塩系光カチオン重合開始剤及びジアゾニウム塩系光カチオン重合開始剤等が挙げられる。 4). (D) Component (D) component is a photocationic polymerization initiator. That is, it is a compound that generates a cation or a Lewis acid upon irradiation with active energy rays such as ultraviolet rays and electron beams, and initiates polymerization of a cationically curable component such as an epoxy compound or an oxetane compound.
Specific examples of the component (D) include sulfonium salt photocationic polymerization initiators, iodonium salt photocationic polymerization initiators, diazonium salt photocationic polymerization initiators, and the like.
トリフェニルスルホニウム ヘキサフルオロホスフェート、
トリフェニルスルホニウム ヘキサフルオロアンチモネート、
トリフェニルスルホニウム テトラキス(ペンタフルオロフェニル)ボレート、
ジフェニル-4-(フェニルチオ)フェニルスルホニウム ヘキサフルオロホスフェート、
ジフェニル-4-(フェニルチオ)フェニルスルホニウム ヘキサフルオロアンチモネート、
4,4’-ビス〔ジフェニルスルホニオ〕ジフェニルスルフィド ビスヘキサフルオロホスフェート、
4,4’-ビス〔ジ(β-ヒドロキシエトキシ)フェニルスルホニオ〕ジフェニルスルフィド ビスヘキサフルオロアンチモネート、
4,4’-ビス〔ジ(β-ヒドロキシエトキシ)フェニルスルホニオ〕ジフェニルスルフィド ビスヘキサフルオロホスフェート、
7-〔ジ(p-トルイル)スルホニオ〕-2-イソプロピルチオキサントン ヘキサフルオロアンチモネート、
7-〔ジ(p-トルイル)スルホニオ〕-2-イソプロピルチオキサントン テトラキス(ペンタフルオロフェニル)ボレート、
4-フェニルカルボニル-4’-ジフェニルスルホニオ-ジフェニルスルフィド ヘキサフルオロホスフェート、
4-(p-tert-ブチルフェニルカルボニル)-4’-ジフェニルスルホニオ-ジフェニルスルフィド ヘキサフルオロアンチモネート、
4-(p-tert-ブチルフェニルカルボニル)-4’-ジ(p-トルイル)スルホニオ-ジフェニルスルフィド テトラキス(ペンタフルオロフェニル)ボレート等のトリアリールスルホニウム塩が挙げられる。 Examples of sulfonium salt photocationic polymerization initiators include, for example:
Triphenylsulfonium hexafluorophosphate,
Triphenylsulfonium hexafluoroantimonate,
Triphenylsulfonium tetrakis (pentafluorophenyl) borate,
Diphenyl-4- (phenylthio) phenylsulfonium hexafluorophosphate,
Diphenyl-4- (phenylthio) phenylsulfonium hexafluoroantimonate,
4,4′-bis [diphenylsulfonio] diphenyl sulfide bishexafluorophosphate,
4,4′-bis [di (β-hydroxyethoxy) phenylsulfonio] diphenyl sulfide bishexafluoroantimonate,
4,4′-bis [di (β-hydroxyethoxy) phenylsulfonio] diphenyl sulfide bishexafluorophosphate,
7- [di (p-toluyl) sulfonio] -2-isopropylthioxanthone hexafluoroantimonate,
7- [di (p-toluyl) sulfonio] -2-isopropylthioxanthone tetrakis (pentafluorophenyl) borate,
4-phenylcarbonyl-4′-diphenylsulfonio-diphenyl sulfide hexafluorophosphate,
4- (p-tert-butylphenylcarbonyl) -4′-diphenylsulfonio-diphenyl sulfide hexafluoroantimonate,
Examples include triarylsulfonium salts such as 4- (p-tert-butylphenylcarbonyl) -4′-di (p-toluyl) sulfonio-diphenyl sulfide tetrakis (pentafluorophenyl) borate.
ジフェニルヨードニウムテトラキス(ペンタフルオロフェニル)ボレート
ジフェニルヨードニウムヘキサフルオロホスフェート、
ジフェニルヨードニウムヘキサフルオロアンチモネート、
ジ(4-t-ブチルフェニル)ヨードニウム ヘキサフルオロホスフェート、
ジ(4-t-ブチルフェニル)ヨードニウム ヘキサフルオロアンチモネート、
トリルクミルヨードニウム テトラキス(ペンタフルオロフェニル)ボレート、
(4-メチルフェニル)[4-(2-メチルプロピル)フェニル]-ヘキサフロオロホスフェート、
ジ(4-ノニルフェニル)ヨードニウムヘキサフルオロホスフェート、
ジ(4-アルキルフェニル)ヨードニウムヘキサフルオロホスフェート、
等のジアリールヨードニウム塩が挙げられる。 Examples of iodonium salt-based photocationic polymerization initiators include, for example:
Diphenyliodonium tetrakis (pentafluorophenyl) borate diphenyliodonium hexafluorophosphate,
Diphenyliodonium hexafluoroantimonate,
Di (4-t-butylphenyl) iodonium hexafluorophosphate,
Di (4-t-butylphenyl) iodonium hexafluoroantimonate,
Trilcumyl iodonium tetrakis (pentafluorophenyl) borate,
(4-methylphenyl) [4- (2-methylpropyl) phenyl] -hexafluorophosphate,
Di (4-nonylphenyl) iodonium hexafluorophosphate,
Di (4-alkylphenyl) iodonium hexafluorophosphate,
And diaryl iodonium salts.
ベンゼンジアゾニウム ヘキサフルオロアンチモネート、
ベンゼンジアゾニウム ヘキサフルオロホスフェート
等が挙げられる。 Examples of diazonium salt photocationic polymerization initiators include benzenediazonium hexafluoroantimonate,
Examples thereof include benzenediazonium hexafluorophosphate.
本発明の組成物は、前記(A)~(D)成分を必須とするものであるが、目的に応じて種々の成分(「その他の成分」という)を配合することができる。 5. Other Components The composition of the present invention essentially comprises the components (A) to (D), but various components (referred to as “other components”) can be blended depending on the purpose.
その他のカチオン硬化性成分は、カチオン硬化性成分の合計量100重量%中に、40重量%以下含むことが好ましく、20重量%以下含むことがより好ましい。カチオン硬化性成分としては、(B)成分以外のエポキシ基含有化合物、(C)成分以外のオキセタニル基含有化合物、及びビニルエーテル基含有化合物等が挙げられる。 As other components, you may contain cationically curable compounds (henceforth "other cation-curable components") other than the (B) component and (C) component mentioned above.
The other cationic curable component is preferably contained in an amount of 40% by weight or less, more preferably 20% by weight or less, in 100% by weight of the total amount of the cationic curable component. Examples of the cationic curable component include an epoxy group-containing compound other than the component (B), an oxetanyl group-containing compound other than the component (C), and a vinyl ether group-containing compound.
トリメチロールプロパントリグリシジルエーテル、イソシアヌル酸エチレンオキサイド付加物のジ又はトリグリシジルエーテル及びペンタエリスリトールトリ又はテトラグリシジルエーテル等の3価以上のポリオールのポリグリシジルエーテル;
ビスフェノールAのジグリシジルエーテル、ビスフェノールFのジグリシジルエーテル、臭素化ビスフェノールAのジグリシジルエーテル、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ビフェニル型エポキシ樹脂、テレフタル酸ジグリシジルエステル、フタル酸ジグリシジルエステル及び、末端カルボン酸ポリブタジエンとビスフェノールA型エポキシ樹脂の付加反応物等の芳香族エポキシ化合物;並びに
ポリエチレングリコール(繰返し数6以上)ジグリシジルエーテル、ポリプロピレングリコール(繰返し数4以上)ジグリシジルエーテル、ポリテトラメチレングリコール(繰返し数3以上)ジグリシジルエーテル、水添ビスフェノールAジグリシジルエーテル、両末端水酸基のポリブタジエンジグリシジルエーテル等の炭素数11以上のジオールのジグリシジルエーテル等が挙げられる。
これら以外にも、エポキシ化植物油、3-グリシドキシプロピルトリメトキシシラン、3-グリシドキシプロピルメチルジメトキシシラン、ポリブタジエンの内部エポキシ化物、スチレン-ブタジエン共重合体の二重結合が一部エポキシ化された化合物〔例えば、ダイセル化学工業(株)製の“エポフレンド”〕、及びエチレン-ブチレン共重合体とポリイソプレンのブロックコポリマーのイソプレン単位が一部エポキシ化された化合物(例えば、KRATON社製の“L-207”)等が挙げられる。 Specific examples of the epoxy group-containing compound other than the component (B) include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxy. Caprolactone-modified product of cyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, esterified product of polycarboxylic acid and 3,4-epoxycyclohexylmethyl alcohol or caprolactone-modified product, dicyclopentadiene dioxide, limonene dioxide, 2- ( Cycloaliphatic epoxy compounds such as 3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane and 4-vinylcyclohexenedioxide;
A polyglycidyl ether of a tri- or higher valent polyol such as trimethylolpropane triglycidyl ether, di- or triglycidyl ether of isocyanuric acid ethylene oxide adduct and pentaerythritol tri- or tetraglycidyl ether;
Diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, diglycidyl ether of brominated bisphenol A, phenol novolac type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, diglycidyl terephthalate, diglycidyl phthalate Ester and aromatic epoxy compounds such as addition reaction product of terminal carboxylic acid polybutadiene and bisphenol A type epoxy resin; and polyethylene glycol (repeat number 6 or more) diglycidyl ether, polypropylene glycol (repeat number 4 or more) diglycidyl ether, poly Tetramethylene glycol (repeat number 3 or more) diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, polybutadiene diglycol with hydroxyl groups at both ends Diglycidyl ethers having 11 or more diols carbon atoms, such as Gilles ether.
In addition to these, epoxidized vegetable oil, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, polybutadiene internal epoxidized product, styrene-butadiene copolymer double bond partially epoxidized Compound (for example, “Epofriend” manufactured by Daicel Chemical Industries, Ltd.) and a compound in which the isoprene unit of the block copolymer of ethylene-butylene copolymer and polyisoprene is partially epoxidized (for example, manufactured by KRATON) "L-207") and the like.
本発明は、前記(A)~(D)成分を必須成分として含むプラスチック製フィルム又はシート用活性エネルギー線硬化型接着剤組成物に関する。 6). Plastic films or sheets for radiation-curable adhesive composition The present invention relates to the (A) ~ (D) of plastic film or sheet for the active energy ray-curable adhesive composition comprising a component as an essential component.
プラスチックフィルム等を使用した積層体の製造工程で使用可能な塗布性、即ち薄膜でも平滑性に優れた塗布面を得るために、25℃に於ける粘度が3,000mPa・s以下であることが好ましく、10~1,500mPa・sであることがより好ましい。さらに好ましくは、50~1,000mPa・sである。
尚、本発明において、上記組成物の25℃における粘度は、E型粘度計により測定される値である。 What is necessary is just to set suitably as a viscosity of the composition of this invention according to the intended purpose.
In order to obtain a coating surface that can be used in the production process of a laminate using a plastic film or the like, that is, a thin film with excellent smoothness, the viscosity at 25 ° C. should be 3,000 mPa · s or less. It is preferably 10 to 1,500 mPa · s. More preferably, it is 50 to 1,000 mPa · s.
In the present invention, the viscosity of the composition at 25 ° C. is a value measured by an E-type viscometer.
本発明の組成物は、これらプラスチックフィルム等の中でも、シクロオレフィンポリマー及び(メタ)アクリル樹脂に好ましく適用できるものである。 Examples of the material in the plastic film include cycloolefin polymer, (meth) acrylic resin, polystyrene, acrylic / styrene copolymer, triacetyl cellulose, cellulose acetate butyrate, polyvinyl chloride, polyvinylidene chloride, polyethylene, polypropylene, Examples include ABS resin, polyamide, polyester, polycarbonate, polyurethane, and chlorinated polypropylene. Examples of the (meth) acrylic resin include (meth) acrylic resin which is a copolymer mainly composed of polymethyl methacrylate and methyl methacrylate, and (meth) acrylic resin which does not contain methyl methacrylate as a polymerization monomer.
Among these plastic films and the like, the composition of the present invention can be preferably applied to cycloolefin polymers and (meth) acrylic resins.
本発明の組成物の使用方法としては、常法に従えば良く、基材に組成物を塗工した後、もう一方の基材と貼り合せ、活性エネルギー線を照射する方法等が挙げられる。
本発明の組成物は、基材として薄層被着体を接着する場合に好適である。薄層被着体を接着する場合の使用方法は、ラミネートの製造において通常行われている方法に従えばよい。例えば、組成物を第1の薄層被着体に塗工し、これに第2の薄層被着体を貼り合わせ、活性エネルギー線の照射を行う方法等が挙げられる。 7). Method of use As a method of using the composition of the present invention, it is sufficient to follow a conventional method, and after applying the composition to a substrate, it is bonded to the other substrate and irradiated with an active energy ray. It is done.
The composition of the present invention is suitable for bonding a thin layer adherend as a substrate. The method of use for adhering the thin-layer adherend may be in accordance with a method usually used in the production of laminates. For example, a method in which the composition is applied to a first thin-layer adherend, a second thin-layer adherend is bonded to the composition, and irradiation with active energy rays is performed.
本発明の組成物は、積層体の製造に好ましく使用することができる。
具体的には、基材に前記した組成物を塗工し、当該塗工面に他の基材を貼合し、前記基材のいずれかの側から活性エネルギー線を照射する方法等が挙げられる。
この場合、両方の基材、又は少なくとも一方の基材として、プラスチックフィルム等を使用する。基材の具体例及び好ましい例は前記した通りである。
組成物の塗工方法、組成物の膜厚、活性エネルギー線の種類の照射条件等も前記した通りである。 8). Manufacturing method of laminated body The composition of this invention can be preferably used for manufacture of a laminated body.
Specifically, the above-described composition is applied to a substrate, another substrate is bonded to the coated surface, and an active energy ray is irradiated from either side of the substrate. .
In this case, a plastic film or the like is used as both base materials or at least one base material. Specific examples and preferred examples of the substrate are as described above.
The coating method of the composition, the film thickness of the composition, the irradiation conditions of the type of active energy ray, etc. are also as described above.
尚、以下において「部」とは重量部を意味し、表中の配合割合を示す数値は、重量%を意味する。 Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to these examples.
In the following, “parts” means parts by weight, and the numerical values indicating the blending ratios in the table mean% by weight.
・ポリマーX1:後述する製造例1で得られる重合体。
・ポリマーX2:後述する製造例2で得られる重合体。 (A) Component / Polymer X1: Polymer obtained in Production Example 1 described later.
Polymer X2: A polymer obtained in Production Example 2 described later.
・HD-DGE:1,6-ヘキサンジオールジグリシジルエーテル(蒸留精製品)、四日市合成(株)製の"エポゴーセーHD(D)" Component (B) HD-DGE: 1,6-hexanediol diglycidyl ether (distilled product), “Epogosei HD (D)” manufactured by Yokkaichi Gosei Co., Ltd.
・OXT-221:ビス〔(3-エチルオキセタン-3-イル)メチル〕エーテル、東亞合成(株)製の“アロンオキセタンOXT-221”。 Component (C) OXT-221: bis [(3-ethyloxetane-3-yl) methyl] ether, “Aron oxetane OXT-221” manufactured by Toagosei Co., Ltd.
・CPI-110P:トリアリールスルホニウムヘキサフルオロホスフェート(有効成分100%)、サンアプロ(株)製の"CPI-110P"。 Component (D) CPI-110P: Triarylsulfonium hexafluorophosphate (active ingredient 100%), “CPI-110P” manufactured by San Apro Co., Ltd.
・ポリマーY:後述する製造例3で得られる重合体。
(B)’〔(B)成分以外のエポキシ化合物〕
・LD:リモネンジオキサイド、アルケマ社製。 (A) '[polymer other than component (A)]
Polymer Y: a polymer obtained in Production Example 3 described later.
(B) '[epoxy compound other than component (B)]
LD: Limonene dioxide, manufactured by Arkema.
1)製造例1
オイルジャケットを備えた容量1000mLの加圧式攪拌槽型反応器のジャケット温度を190℃に保った。次いで、反応器の圧力を一定に保ちながら、グリシジルメタクリレート(以下、「GMA」という)(30部)、メチルメタクリレート(以下、「MMA」という)(45部)、スチレン(25部)、重合溶媒として、メチルエチルケトン(以下、「MEK」という)(18部)、重合開始剤としてジt-ブチルパーオキサイド(以下、「DBP」という)(0.25部)からなる単量体混合物を、一定の供給速度(48g/分、滞留時間:12分)で原料タンクから反応器に連続供給を開始し、単量体混合物の供給量に相当する反応液を出口から連続的に抜き出した。反応開始直後に、一旦反応温度が低下した後、重合熱による温度上昇が認められたが、オイルジャケット温度を制御することにより、反応器の内温を192~194℃に保持した。
反応器内温が安定してから36分後の時点を、反応液の採取開始点とし、これから25分間反応を継続した結果、1.2kgの単量体混合液を供給し、1.2kgの反応液を回収した。
その後反応液を薄膜蒸発器に導入して、未反応モノマー等の揮発成分を分離して、未反応モノマー等の揮発成分を除去し、重合体「ポリマーX1」を得た。GPCを測定した結果、ポリスチレン換算の数平均分子量(Mn)が3,500、重量平均分子量(Mw)が9,900であり、Tg(DSC測定、昇温速度10℃/分)は65℃であった。 1. Production example
1) Production Example 1
The jacket temperature of a 1000 mL capacity pressurized stirred tank reactor equipped with an oil jacket was maintained at 190 ° C. Next, while maintaining the reactor pressure constant, glycidyl methacrylate (hereinafter referred to as “GMA”) (30 parts), methyl methacrylate (hereinafter referred to as “MMA”) (45 parts), styrene (25 parts), polymerization solvent A monomer mixture consisting of methyl ethyl ketone (hereinafter referred to as “MEK”) (18 parts) and di-t-butyl peroxide (hereinafter referred to as “DBP”) (0.25 parts) as a polymerization initiator Continuous supply from the raw material tank to the reactor was started at a supply rate (48 g / min, residence time: 12 minutes), and a reaction liquid corresponding to the supply amount of the monomer mixture was continuously extracted from the outlet. Immediately after the start of the reaction, once the reaction temperature decreased, a temperature increase due to the heat of polymerization was observed, but the internal temperature of the reactor was maintained at 192 to 194 ° C. by controlling the oil jacket temperature.
The time point 36 minutes after the reactor internal temperature was stabilized was taken as the reaction collection start point, and the reaction was continued for 25 minutes. As a result, 1.2 kg of the monomer mixture was supplied, The reaction solution was collected.
Thereafter, the reaction solution was introduced into a thin film evaporator to separate volatile components such as unreacted monomers, and volatile components such as unreacted monomers were removed to obtain a polymer “polymer X1”. As a result of measuring GPC, the polystyrene-equivalent number average molecular weight (Mn) was 3,500, the weight average molecular weight (Mw) was 9,900, and Tg (DSC measurement, heating rate 10 ° C./min) was 65 ° C. there were.
オイルジャケットを備えた容量1000mLの加圧式攪拌槽型反応器のジャケット温度を180℃に保った。
次いで、反応器の圧力を一定に保ちながら、GMA(30部)、MMA(60部)、メチルアクリレート(10部)、重合溶媒としてMEK(18部)、重合開始剤としてDBP(0.25部)からなる単量体混合物を、製造例1と同じ一定の供給速度で原料タンクから反応器に連続供給を開始し、単量体混合物の供給量に相当する反応液を出口から連続的に抜き出した。反応開始直後に、一旦反応温度が低下した後、重合熱による温度上昇が認められたが、オイルジャケット温度を制御することにより、反応器の内温を182~184℃に保持した。
反応器内温が安定してから36分後の時点を、反応液の採取開始点とし、これから25分間反応を継続した結果、1.2kgの単量体混合液を供給し、1.2kgの反応液を回収した。
その後反応液を薄膜蒸発器に導入して、未反応モノマー等の揮発成分を分離して、未反応モノマー等の揮発成分を除去し、重合体「ポリマーX2」を得た。
得られたポリマーX2について製造例1と同様の方法で評価した結果、Mnが3,200、Mwが8,500であり、Tgが53℃であった。 2) Production Example 2
The jacket temperature of a 1000 mL capacity pressurized stirred tank reactor equipped with an oil jacket was kept at 180 ° C.
Next, while maintaining the reactor pressure constant, GMA (30 parts), MMA (60 parts), methyl acrylate (10 parts), MEK (18 parts) as a polymerization solvent, DBP (0.25 parts) as a polymerization initiator ) Is continuously fed from the raw material tank to the reactor at the same constant feed rate as in Production Example 1, and the reaction liquid corresponding to the amount of monomer mixture fed is continuously withdrawn from the outlet. It was. Immediately after the start of the reaction, once the reaction temperature dropped, a temperature increase due to the heat of polymerization was observed. By controlling the oil jacket temperature, the internal temperature of the reactor was maintained at 182 to 184 ° C.
The time point after 36 minutes from the stabilization of the reactor internal temperature was taken as the starting point for collecting the reaction liquid, and the reaction was continued for 25 minutes. As a result, 1.2 kg of the monomer mixture was supplied, The reaction solution was collected.
Thereafter, the reaction solution was introduced into a thin film evaporator to separate volatile components such as unreacted monomers, and volatile components such as unreacted monomers were removed to obtain a polymer “polymer X2”.
As a result of evaluating the obtained polymer X2 by the same method as in Production Example 1, Mn was 3,200, Mw was 8,500, and Tg was 53 ° C.
オイルジャケットを備えた容量1000mLの加圧式攪拌槽型反応器のジャケット温度を187℃に保った。次いで、反応器の圧力を一定に保ちながら、GMA(50部)、ブチルアクリレート(50部)、重合溶媒として、MEK(18部)、重合開始剤としてDBP(0.25部)からなる単量体混合物を、一定の供給速度(48g/分、滞留時間:12分)で原料タンクから反応器に連続供給を開始し、単量体混合物の供給量に相当する反応液を出口から連続的に抜き出した。反応開始直後に、一旦反応温度が低下した後、重合熱による温度上昇が認められたが、オイルジャケット温度を制御することにより、反応器の内温を189~191℃に保持した。
反応器内温が安定してから36分後の時点を、反応液の採取開始点とし、これから25分間反応を継続した結果、1.2kgの単量体混合液を供給し、1.2kgの反応液を回収した。
その後反応液を薄膜蒸発器に導入して、未反応モノマー等の揮発成分を分離して、未反応モノマー等の揮発成分を除去し、重合体「ポリマーY」を得た。GPCを測定した結果、ポリスチレン換算の数平均分子量(Mn)が3,460、重量平均分子量(Mw)が9,700であり、Tg(DSC測定、昇温速度10℃/分)は-10℃であり、粘度は80℃において12,200mPa・sであった。 3) Production Example 3
The jacket temperature of a 1000 mL capacity pressurized stirred tank reactor equipped with an oil jacket was kept at 187 ° C. Next, while maintaining the reactor pressure constant, a single amount comprising GMA (50 parts), butyl acrylate (50 parts), MEK (18 parts) as a polymerization solvent, and DBP (0.25 parts) as a polymerization initiator. The body mixture is continuously fed from the raw material tank to the reactor at a constant feed rate (48 g / min, residence time: 12 minutes), and a reaction liquid corresponding to the feed amount of the monomer mixture is continuously fed from the outlet. Extracted. Immediately after the start of the reaction, once the reaction temperature decreased, a temperature increase due to the heat of polymerization was observed, but the internal temperature of the reactor was maintained at 189 to 191 ° C. by controlling the oil jacket temperature.
The time point after 36 minutes from the stabilization of the reactor internal temperature was taken as the starting point for collecting the reaction liquid, and the reaction was continued for 25 minutes. As a result, 1.2 kg of the monomer mixture was supplied, The reaction solution was collected.
Thereafter, the reaction liquid was introduced into a thin film evaporator to separate volatile components such as unreacted monomers, and volatile components such as unreacted monomers were removed to obtain a polymer “polymer Y”. As a result of GPC measurement, the polystyrene-equivalent number average molecular weight (Mn) was 3,460, the weight average molecular weight (Mw) was 9,700, and Tg (DSC measurement, heating rate 10 ° C./min) was −10 ° C. The viscosity was 12,200 mPa · s at 80 ° C.
1)組成物の製造
表1に示す各成分をそれぞれの割合で配合し、常法に従って攪拌混合して、活性エネルギー線硬化型接着剤組成物を調製した。
得られた組成物の25℃に於ける粘度は、東機産業(株)製のE型粘度計により測定した。 2. Examples 1 and 2 and Comparative Examples 1 to 5
1) Manufacture of composition Each component shown in Table 1 was blended in respective proportions and stirred and mixed according to a conventional method to prepare an active energy ray-curable adhesive composition.
The viscosity at 25 ° C. of the obtained composition was measured with an E-type viscometer manufactured by Toki Sangyo Co., Ltd.
厚さ100μmのシクロオレフィンポリマー〔商品名ゼオノアZF-14、日本ゼオン(株)製、以下「ゼオノア」という〕、及び厚さ75μmのUV吸収剤入りアクリル樹脂〔商品名HI50-75KT-UV、(株)クラレ製、以下「アクリル樹脂」という〕上に、易接着処理としてコロナ処理を実施した。
次いで、アクリル樹脂のコロナ処理面に、得られた組成物を、バーコータで3μm厚に塗工した後、ゼオノアをラミネートした。このとき、ゼオノアのコロナ処理面が塗工面に接するよう配置した。
最後に、アイグラフィックス(株)製のベルトコンベア付き紫外線照射装置(メタルハライドランプ使用)により、ゼオノアの表面から、積算光量600mJ/cm2(UV-A)で紫外線を照射し、接着剤組成物を硬化させた。
この実験を、23℃、相対湿度80%の条件下で実施した。
又、得られた積層体は、23℃、相対湿度50%の条件下で1日放置した後、下記方法に従い、無色透明性及び接着力を評価した。 2) Production of laminate: Cycloolefin polymer having a thickness of 100 μm (trade name ZEONOR ZF-14, manufactured by Nippon Zeon Co., Ltd., hereinafter referred to as “ZEONOR”), and acrylic resin with UV absorber having a thickness of 75 μm [trade name HI50 -75 KT-UV (manufactured by Kuraray Co., Ltd., hereinafter referred to as “acrylic resin”) was subjected to corona treatment as an easy adhesion treatment.
Next, the corona-treated surface of the acrylic resin was coated with the obtained composition with a bar coater to a thickness of 3 μm, and then ZEONOR was laminated. At this time, it was arranged so that the corona-treated surface of ZEONOR was in contact with the coated surface.
Finally, an ultraviolet ray irradiation device (using a metal halide lamp) with a belt conveyor manufactured by iGraphics Co., Ltd. was used to irradiate ultraviolet rays from the surface of ZEONOR with an integrated light amount of 600 mJ / cm 2 (UV-A), and an adhesive composition Was cured.
This experiment was carried out under conditions of 23 ° C. and a relative humidity of 80%.
Further, the obtained laminate was allowed to stand for 1 day under conditions of 23 ° C. and 50% relative humidity, and then evaluated for colorless transparency and adhesive strength according to the following methods.
1)無色透明性の評価
得られた積層体を5枚重ねて目視観察し、以下の基準で判定した。その結果を表1に示す。
A:濁りや黄変が全く感じられない
B:濁りや黄変が僅かに感じられた
C:濁りや黄変が明らかに感じられた 3. Evaluation methods
1) Evaluation of colorless transparency Five obtained laminates were visually observed and judged according to the following criteria. The results are shown in Table 1.
A: No turbidity or yellowing is felt B: Turbidity or yellowing is slightly felt C: Turbidity or yellowing is clearly felt
得られた積層体を、幅1インチ、長さ10cmに切り出し、T字剥離試験、剥離速度200mm/分で剥離接着力を評価した。それらの結果を表1に示す。 2) Evaluation of adhesive strength The obtained laminate was cut into a 1 inch width and a length of 10 cm, and the peel adhesive strength was evaluated by a T-shaped peeling test and a peeling speed of 200 mm / min. The results are shown in Table 1.
これに対して、(A)成分を含まない比較例1及び比較例2の組成物は、いずれも透明性に優れるものの、接着力が大きく低下した。
比較例2の組成物は、連続重合で製造され、構成単量体及びMwは(A)成分に該当するがTgが(A)成分の上限20℃に満たない重合体であるポリマーYに変更した組成物の結果であるが、接着力が大きく低下した。
(B)成分を含まない比較例3の組成物は、透明性に優れるものの、接着力が大きく低下した。又、(C)成分を含まない比較例4の組成物と、(B)成分を(B)’成分に変えた比較例5の組成物は、いずれも透明性に優れるものの、実施例の組成物と比較して接着力が低下した。 Although the compositions of Examples 1 and 2 were both excellent in transparency and were tested under severe conditions of 80% humidity, the composition of Example 1 had a strong adhesive strength of 10 N / inch or more. At the same time, the substrate was broken and could not be peeled off, and the composition of Example 2 was also excellent in adhesive strength.
On the other hand, although the compositions of Comparative Example 1 and Comparative Example 2 that did not contain the component (A) were both excellent in transparency, the adhesive strength was greatly reduced.
The composition of Comparative Example 2 is produced by continuous polymerization, and the constituent monomer and Mw correspond to the component (A), but the Tg is changed to the polymer Y which is a polymer that does not satisfy the upper limit of 20 ° C. As a result of the composition, the adhesive strength was greatly reduced.
Although the composition of Comparative Example 3 not containing the component (B) was excellent in transparency, the adhesive strength was greatly reduced. Moreover, although the composition of the comparative example 4 which does not contain (C) component and the composition of the comparative example 5 which changed (B) component into the (B) 'component are all excellent in transparency, the composition of an Example The adhesive strength was reduced compared to the product.
Claims (12)
- 下記(A)~(D)成分を必須成分として含む、プラスチック製フィルム又はシート用活性エネルギー線硬化型接着剤組成物。
(A)成分:(a1)エポキシ基及びエチレン性不飽和基を有する化合物〔以下、「単量体(a1)」という〕及び(a2)エチレン性不飽和基を有する化合物であって、単量体(a1)以外の化合物〔以下、「単量体(a2)」という〕を重合して得られた重合体であって、ガラス転移温度が20℃以上であり、重量平均分子量が1,000~30,000である重合体
(B)成分:炭素数2~10個を有するポリオールのポリグリシジルエーテル
(C)成分:1分子中に2個以上のオキセタニル基を有する分子量500以下の化合物
(D)成分:光カチオン重合開始剤 An active energy ray-curable adhesive composition for plastic film or sheet, comprising the following components (A) to (D) as essential components.
Component (A): (a1) a compound having an epoxy group and an ethylenically unsaturated group [hereinafter referred to as “monomer (a1)”] and (a2) a compound having an ethylenically unsaturated group, each having a single amount A polymer obtained by polymerizing a compound other than the body (a1) [hereinafter referred to as “monomer (a2)”], having a glass transition temperature of 20 ° C. or higher and a weight average molecular weight of 1,000. Polymer (B) component having a molecular weight of ˜30,000: Polyglycidyl ether (C) component of a polyol having 2 to 10 carbon atoms: Compound having a molecular weight of 500 or less having two or more oxetanyl groups in one molecule (D ) Component: Photocationic polymerization initiator - (A)成分において、単量体(a2)が、炭素数1~10のアルキル基を有するアルキル(メタ)アクリレート及び/又は芳香族ビニル化合物を含む、請求項1に記載のプラスチック製フィルム又はシート用活性エネルギー線硬化型接着剤組成物。 The plastic film or sheet according to claim 1, wherein in component (A), the monomer (a2) comprises an alkyl (meth) acrylate having an alkyl group having 1 to 10 carbon atoms and / or an aromatic vinyl compound. Active energy ray-curable adhesive composition for use.
- (A)成分が、全構成単量体単位中に、単量体(a1)を10~80重量%含み、単量体(a2)として、炭素数1~10のアルキル基を有するアルキル(メタ)アクリレートを10~80重量%及び芳香族ビニル化合物を10~80重量%含み、且つ、重量平均分子量が3,000~20,000の重合体である、請求項1又は請求項2に記載のプラスチック製フィルム又はシート用活性エネルギー線硬化型接着剤組成物。 Component (A) contains 10 to 80% by weight of monomer (a1) in all constituent monomer units, and an alkyl (meta) having an alkyl group having 1 to 10 carbon atoms as monomer (a2). The polymer according to claim 1 or 2, which is a polymer containing 10 to 80% by weight of acrylate and 10 to 80% by weight of an aromatic vinyl compound and having a weight average molecular weight of 3,000 to 20,000. An active energy ray-curable adhesive composition for a plastic film or sheet.
- (A)成分が、単量体(a1)としてグリシジルメタクリレートを含み、単量体(a2)としてメチルメタクリレート及びスチレンを含む重合体である、請求項2又は請求項3に記載のプラスチック製フィルム又はシート用活性エネルギー線硬化型接着剤組成物。 The plastic film according to claim 2 or 3, wherein the component (A) is a polymer containing glycidyl methacrylate as the monomer (a1) and methyl methacrylate and styrene as the monomer (a2). An active energy ray-curable adhesive composition for a sheet.
- (A)成分が、単量体(a1)及び単量体(a2)を高温重合して得られた重合体である、請求項1~請求項4のいずれか1項に記載のプラスチック製フィルム又はシート用活性エネルギー線硬化型接着剤組成物。 The plastic film according to any one of claims 1 to 4, wherein component (A) is a polymer obtained by high-temperature polymerization of monomer (a1) and monomer (a2). Or the active energy ray hardening-type adhesive composition for sheets.
- (A)成分が、単量体(a1)及び単量体(a2)を160℃以上の温度で高温重合して得られた重合体である、請求項5に記載のプラスチック製フィルム又はシート用活性エネルギー線硬化型接着剤組成物。 The component (A) is a polymer obtained by high-temperature polymerization of the monomer (a1) and the monomer (a2) at a temperature of 160 ° C. or higher. An active energy ray-curable adhesive composition.
- (B)成分が、炭素数4~6のアルカンジオールのジグリシジルエーテルである、請求項1~請求項6のいずれか1項に記載のプラスチック製フィルム又はシート用活性エネルギー線硬化型接着剤組成物。 The active energy ray-curable adhesive composition for plastic films or sheets according to any one of claims 1 to 6, wherein the component (B) is a diglycidyl ether of an alkanediol having 4 to 6 carbon atoms. object.
- (D)成分が、スルホニウム塩系光カチオン重合開始剤である、請求項1~請求項8のいずれか1項に記載のプラスチック製フィルム又はシート用活性エネルギー線硬化型接着剤組成物。 The active energy ray-curable adhesive composition for plastic film or sheet according to any one of claims 1 to 8, wherein the component (D) is a sulfonium salt photocationic polymerization initiator.
- 組成物全体中に、(A)成分を1~60重量%、(B)成分を1~60重量%、(C)成分を1~60重量%、(D)成分を0.5~10重量%含有する、請求項1~請求項9のいずれか1項に記載のプラスチック製フィルム又はシート用活性エネルギー線硬化型接着剤組成物。 In the whole composition, the component (A) is 1 to 60% by weight, the component (B) is 1 to 60% by weight, the component (C) is 1 to 60% by weight, and the component (D) is 0.5 to 10% by weight. The active energy ray-curable adhesive composition for a plastic film or sheet according to any one of claims 1 to 9, wherein the composition is contained in%.
- プラスチック製フィルム又はシートの少なくとも一方が、シクロオレフィンポリマー又は(メタ)アクリル樹脂である、請求項1~請求項10のいずれか1項に記載のプラスチック製フィルム又はシート用活性エネルギー線硬化型接着剤組成物。 The active energy ray-curable adhesive for plastic film or sheet according to any one of claims 1 to 10, wherein at least one of the plastic film or sheet is a cycloolefin polymer or a (meth) acrylic resin. Composition.
- 基材に、請求項1~請求項11のいずれか1項に記載の組成物を塗工し、前記塗工面に他の基材を貼合し、前記基材のいずれかの側から活性エネルギー線を照射する積層体の製造方法であって、
前記基材の両方又は一方が、プラスチック製フィルム又はシートである積層体の製造方法。 A base material is coated with the composition according to any one of claims 1 to 11, and another base material is bonded to the coated surface, and active energy is applied from either side of the base material. A method of manufacturing a laminate that irradiates a line,
A method for producing a laminate, wherein both or one of the substrates is a plastic film or sheet.
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KR20170125019A (en) * | 2015-03-04 | 2017-11-13 | 도아고세이가부시키가이샤 | Active energy ray curable adhesive composition for plastic film or sheet |
CN107406740A (en) * | 2015-03-04 | 2017-11-28 | 东亚合成株式会社 | For plastics film or the active energy ray curable adhesive compound of piece |
JPWO2016140308A1 (en) * | 2015-03-04 | 2017-12-21 | 東亞合成株式会社 | Active energy ray-curable adhesive composition for plastic film or sheet |
TWI681028B (en) * | 2015-03-04 | 2020-01-01 | 日商東亞合成股份有限公司 | Active energy ray hardening type adhesive composition for plastic film or sheet |
TWI692515B (en) * | 2015-03-04 | 2020-05-01 | 日商東亞合成股份有限公司 | Active energy ray hardening type adhesive composition for plastic film or sheet |
KR102403032B1 (en) | 2015-03-04 | 2022-05-27 | 도아고세이가부시키가이샤 | Active energy ray-curable adhesive composition for plastic film or sheet |
KR101790973B1 (en) * | 2016-01-20 | 2017-11-20 | 한국화학연구원 | Preparation Method of epoxy functionalized acrylate polymers having low molecular weight and low polydispersity |
JP2017179202A (en) * | 2016-03-31 | 2017-10-05 | 株式会社Adeka | Curable composition, manufacturing method of cured article and the cured article |
JP7008398B2 (en) | 2016-03-31 | 2022-01-25 | 株式会社Adeka | Curable composition, method for producing cured product, and cured product thereof |
Also Published As
Publication number | Publication date |
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TWI637034B (en) | 2018-10-01 |
JP6160697B2 (en) | 2017-07-12 |
KR20160040251A (en) | 2016-04-12 |
TW201512357A (en) | 2015-04-01 |
JPWO2015020099A1 (en) | 2017-03-02 |
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