WO2017018472A1 - Active-energy-ray curing adhesive composition for plastic film or plastic sheet - Google Patents
Active-energy-ray curing adhesive composition for plastic film or plastic sheet Download PDFInfo
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- WO2017018472A1 WO2017018472A1 PCT/JP2016/072107 JP2016072107W WO2017018472A1 WO 2017018472 A1 WO2017018472 A1 WO 2017018472A1 JP 2016072107 W JP2016072107 W JP 2016072107W WO 2017018472 A1 WO2017018472 A1 WO 2017018472A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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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
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.
- cellulose acetate resins such as triacetyl cellulose and cycloolefin polymers are widely used because of their excellent optical properties such as colorless transparency and optical isotropy.
- Non-patent Document 1 Non-patent Document 1
- 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).
- 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, irradiation with UV-B (near 310 nm) of 200 mJ / cm 2 or less, more preferably 100 mJ / cm 2 or less. There has been a demand for an active energy ray-curable adhesive that exhibits sufficient adhesive strength even in an amount.
- the present invention has been made in view of the above problems, has a low viscosity, excellent curability, excellent adhesion to plastic films such as cellulose acetate resins and cycloolefin polymers, and excellent colorless transparency.
- Another object of the present invention is to provide an active energy ray-curable adhesive composition for plastic films and the like.
- the present inventors have three or more (meth) acryloyl groups in one molecule, and a (meth) acryloyl group equivalent is 200 g / eq or less.
- the present inventors have found that an active energy ray-curable adhesive composition containing a polyglycidyl ether of a polyol having 2 to 10 carbon atoms and a photocationic polymerization initiator in a specific ratio can solve the above-mentioned problems. Completed.
- the present invention is a composition comprising the following components (A), (B) and (C), wherein the total amount of the component (A) is 15 to 45% by weight, and the component (B) is 10 to 75%.
- the present invention relates to an active energy ray-curable adhesive composition for plastic film or sheet containing 0.5% by weight and 0.5% to 10% by weight of component (C).
- Component (A) Compound (B) having 3 or more (meth) acryloyl groups in the molecule and having a (meth) acryloyl group equivalent of 200 g / eq or less: Polyol having 2 to 10 carbon atoms , Polyglycidyl ether (C) component: photocationic polymerization initiator
- component (A) a compound having 3 to 6 (meth) acryloyl groups in one molecule and having a (meth) acryloyl group equivalent of 150 g / eq or less is preferable.
- component (B) diglycidyl ether of a diol having 2 to 10 carbon atoms is preferable, and diglycidyl ether of a diol having 2 to 6 carbon atoms is more preferable.
- component (C) a sulfonium salt photocationic polymerization initiator is preferable.
- the composition of the present invention preferably contains 0.1 to 10% by weight of a radical photopolymerization initiator as component (D).
- a radical photopolymerization initiator as component (E)
- the component (F) preferably contains 1 to 40% by weight of a compound having two or more oxetanyl groups in one molecule and having a molecular weight of 500 or less.
- component (D) a hydrogen abstraction type photo radical polymerization initiator is preferable.
- component (E) a bisphenol type epoxy resin is preferable.
- component (F) a compound represented by the following formula (1) is preferable.
- the plastic film or sheet is a cellulose acetate resin or a cycloolefin polymer.
- the present invention is a laminate composed of a base material, a cured product of the above-mentioned active energy ray-curable adhesive composition for plastic film or sheet, and another base material
- the present invention relates to a laminate in which both or one of the substrate and the other substrate is a plastic film or sheet.
- a plastic film or sheet at least one of them is preferably a cellulose acetate resin or a cycloolefin polymer.
- this invention coats the said composition on a base material, bonds another base material to a coating surface, and irradiates an active energy ray from either the said base material or the said other base material side.
- a method of manufacturing a laminate The present invention relates to a method for producing a laminate in which both or one of the base material and the other base material is a plastic film or sheet.
- an active energy ray-curable adhesive composition having low viscosity, excellent curability, excellent adhesion to plastic films such as cellulose acetate and cycloolefin polymer, and excellent colorless transparency is obtained.
- plastic films such as cellulose acetate and cycloolefin polymer, and excellent colorless transparency.
- 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 a composition comprising the following components (A), (B) and (C), wherein the total amount of the component (A) is 15 to 45% by weight, and the component (B) is 10 to 75%.
- the present invention relates to an active energy ray-curable adhesive composition for plastic film or sheet containing 0.5% by weight and 0.5% to 10% by weight of component (C).
- Component (A) Compound (B) having 3 or more (meth) acryloyl groups in the molecule and having a (meth) acryloyl group equivalent of 200 g / eq or less: Polyol having 2 to 10 carbon atoms Polyglycidyl ether (C) component: photocationic polymerization initiator
- the components (A) to (C) will be described below.
- components (D) to (F) which are preferred blending components, other components, and preferred methods of using the composition of the present invention will be described in detail.
- Component (A) is a compound having 3 or more (meth) acryloyl groups in one molecule and having a (meth) acryloyl group equivalent of 200 g / eq or less.
- Component (A) has the effect of increasing the adhesive strength to the cellulose acetate base and the adhesive strength to the corona-treated cycloolefin polymer by blending an appropriate amount. Even if it is a compound having 3 or more (meth) acryloyl groups in one molecule, a compound having a (meth) acryloyl group equivalent exceeding 200 g / eq has a low adhesive force to a cellulose acetate substrate or the like. There is a problem.
- the (meth) acryloyl group equivalent in the present invention means the weight (g / eq) of component (A) per mole of (meth) acryloyl group, and is present in (A) molecular weight and 1 molecule ( It means a value obtained by calculation based on the number of (meth) acryloyl groups.
- the component (A) is preferably a compound having 3 to 6 (meth) acryloyl groups in one molecule and having a (meth) acryloyl group equivalent of 150 g / eq or less, and a (meth) acryloyl group equivalent of 80 More preferred are compounds that are ⁇ 150 g / eq. Further, a compound having 3 to 4 (meth) acryloyl groups in one molecule and having a (meth) acryloyl group equivalent of 80 to 150 g / eq is more preferable. Moreover, as (A) component, the compound which does not have an amino group and a urethane bond is preferable because it does not deteriorate cation curability, such as (B) component.
- component (A) examples include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin tri (meth) acrylate, diglycerin tetra (meth) acrylate, Polyol poly (meth) acrylates such as dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate; Tri (meth) acrylate of alkylene oxide adduct of trimethylolpropane, tetra (meth) acrylate of alkylene oxide adduct of pentaerythritol, hexa (meth) acrylate of alkylene oxide adduct of dipentaerythritol, alkylene oxide adduct of glycerol A poly (meth)
- the alkylene oxide in the alkylene oxide adduct ethylene oxide and propylene oxide are preferable.
- the poly (meth) acrylate of the alkylene oxide adduct of polyol and the polyester (meth) acrylate having 3 or more (meth) acryloyl groups need to have a (meth) acryloyl group equivalent of 200 g / eq or less.
- Preferred examples of the component (A) include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, and glycerin tri (meth) acrylate.
- component (A) the above-described compounds may be used alone, or two or more kinds may be used.
- the content of component (A) is 15 to 45% by weight based on the entire composition.
- the content ratio of the component (A) is less than 15% by weight, or conversely exceeds 45% by weight, the adhesive force to a plastic film such as cellulose acetate or a corona-treated cycloolefin polymer is lowered.
- the preferred content of component (A) is 15 to 40% by weight.
- 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.
- Component (B) has the effect of increasing the adhesive strength to the cellulose acetate base and the adhesive strength to the corona-treated cycloolefin polymer by blending an appropriate amount.
- a diglycidyl ether of a diol having 2 to 10 carbon atoms is preferable in that the viscosity of the composition can be reduced and the composition has excellent adhesion to a plastic substrate.
- Diglycidyl ethers of diols having 2 to 6 carbon atoms are more preferred, and diglycidyl ethers of alkane diols having 2 to 6 carbon atoms are more preferred.
- the component (B) preferably has a total chlorine content of 1% or less, more preferably 0.5% or less, in that the composition has excellent curability and adhesive strength. Those of 2% or less are more preferred, and those of 0.1% or less are particularly preferred.
- the total chlorine amount can be measured based on a quartz tube combustion-ion chromatography method.
- 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.
- Preferred examples of the component (B) include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether and the like. Can be mentioned.
- 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 10 to 75% by weight in the entire composition.
- the adhesive strength of the composition with respect to many plastic substrates is lowered.
- the content rate of (B) component exceeds 75 weight%, the sclerosis
- a preferred content ratio of the component (B) is 15 to 60% by weight, more preferably 15 to 50% by weight in the whole composition.
- Component (C) component is a photocationic polymerization initiator. That is, by irradiation with active energy rays such as ultraviolet rays and electron beams, cations or Lewis acids are generated, and polymerization of cationically curable components such as epoxy compounds and oxetane compounds other than the (A) component and the (A) component described later is performed. The compound to be initiated.
- Specific examples of the component (C) 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 (C) 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 (Nippon Kayaku Co., Ltd.), Irgacure 250 (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 of excellent storage stability as an adhesive, excellent active energy ray curability, and excellent colorless transparency.
- a triarylsulfonium salt is more preferable because of excellent storage stability as an adhesive, excellent active energy ray curability, and excellent colorless transparency.
- triarylsulfonium salts triphenylsulfonium hexafluorophosphate and diphenyl-4- (phenylthio) phenylsulfonium hexafluorophosphate are preferable.
- the content ratio of the component (C) is 0.5 to 10% by weight, preferably 1 to 7% by weight in the whole composition.
- the content ratio of the component (C) is less than 0.5% by weight, the curability of the composition deteriorates, and when it exceeds 10% by weight, the adhesive strength of the composition decreases or the cured product turns yellow. .
- composition of the other components present invention the (A) ⁇ (C) but it is an essential component, various components depending on the purpose (hereinafter referred to as "other components") be blended it can.
- component (D) a radical photopolymerization initiator
- component (D) an epoxy compound having two or more aromatic rings and two or more epoxy groups in one molecule
- component (F) a compound having a molecular weight of 500 or less
- Component (D) The radical curable component such as the component (A) contained in the composition of the present invention can be cured with radicals generated when the component (C) is decomposed by light, but with little irradiation. In order to obtain a sufficient reaction rate in an amount, the component (D) (photo radical polymerization initiator) is preferably blended.
- component (D) examples include 4′-phenoxy-2,2-dichloroacetophenone, 4′-tert-butyl-2,2-dichloroacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2 ′ -Methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 1-hydroxycyclohexyl phenyl ketone, ⁇ , ⁇ -diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane- 1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methylpropan-1-one, and 2-benzi Acetophenone photopolymerization initiators such as 2-dimethylamino-1- (4-morpholinophenyl
- An acylphosphine oxide photopolymerization initiator examples include oxime ester photopolymerization initiators such as 1,2-octanedione, 1- [4- (phenylthiophenyl)]-, 2- (O-benzoyloxime); and camphorquinone.
- the component (D) one type can be used alone, or two or more types can be blended and used according to desired performance.
- a hydrogen abstraction type radical polymerization initiator such as a thioxanthone photopolymerization initiator or a benzophenone photopolymerization initiator is preferable because it has an effect of increasing the adhesive force with a plastic substrate.
- thioxanthone-based photopolymerization initiators are particularly preferable because they have a high effect of increasing adhesive strength.
- the content is preferably 0.1 to 10% by weight, more preferably 0.1 to 5% by weight, based on the entire composition.
- curability is excellent, and when it is 10% by weight or less, yellowing of the cured product can be prevented.
- the component (E) is an epoxy compound having two or more aromatic rings and two or more epoxy groups in one molecule. However, the component (E) in the present invention does not include a polyglycidyl ether of a polyol having 10 or less carbon atoms such as diglycidyl ether of naphthalenediol. Component (E) has the effect of increasing the adhesive strength to the cellulose acetate base and the adhesive strength to the corona-treated cycloolefin polymer by blending an appropriate amount.
- the component (E) include bisphenol A type epoxy resin, bisphenol F type epoxy resin, brominated bisphenol A type epoxy resin, epoxy resin obtained by polycondensation of bisphenol A, bisphenol F and epichlorohydrin, phenol novolac type epoxy resin, Examples include a cresol novolac epoxy resin, a bisphenol A novolac epoxy resin, a bisphenol F novolac epoxy resin, and a biphenyl epoxy resin.
- the epoxy resin means a compound or polymer having an average of two or more epoxy groups in the molecule and cured by reaction.
- a monomer may be referred to as an epoxy resin as long as it has two or more curable epoxy groups in the molecule.
- a bisphenol type epoxy resin such as a bisphenol A type epoxy resin or a bisphenol F type epoxy resin is particularly preferable in terms of adhesive strength.
- the component (E) preferably has a total chlorine content of 0.5% or less, more preferably 0.3% or less, and still more preferably 0.2% or less in terms of adhesive strength. .
- an above described compound may be used independently, or 2 or more types may be used.
- the content is preferably 1 to 40% by weight, more preferably 5 to 30% by weight, and still more preferably 10 to 30% by weight, based on the entire composition.
- Component (F) is a compound having a molecular weight of 500 or less having two or more oxetanyl groups in one molecule. By blending an appropriate amount of the component (F), the curability of the composition can be improved, and the adhesive force between the cured product of the composition and the plastic substrate can be improved.
- component (F) 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 because 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.
- component (F) bis [(3-ethyloxetane-3-yl) methyl] ether, that is, an oxetane compound represented by the following formula (1) is particularly preferable.
- the adhesive strength with the cellulose acetate resin or the corona-treated cycloolefin polymer becomes stronger.
- the curability of the composition is improved, and the amount of the cationic photopolymerization initiator is small.
- the above-described compounds may be used alone, or two or more kinds may be used.
- the content is preferably 1 to 40% by weight, more preferably 5 to 35% by weight, and still more preferably 10 to 30% by weight, based on the entire composition.
- cationically curable compounds other than (B) component, (E) component, and (F) component mentioned above.
- other cationic curable components include epoxy group-containing compounds other than the (B) component and the (E) component, oxetanyl group-containing compounds other than the (F) component, and vinyl ether group-containing compounds.
- epoxy group-containing compound other than the component (B) and the component (E) include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate-modified caprolactone, esterified product of polycarboxylic acid and 3,4-epoxycyclohexylmethyl alcohol or caprolactone-modified product, dicyclopentadiene dioxide, limonene di Alicyclic epoxy compounds such as oxide, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane and 4-vinylcyclohexene dioxide Carbon such as polyethylene glycol (repeat number 6 or more
- oxetane compounds other than the component (F) include monofunctional oxetanes containing alkoxyalkyl groups such as 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3-phenoxymethyloxetane and the like.
- 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.
- the composition of the present invention preferably contains 0.05 to 3% by weight of water in the whole composition. Adhesive force can be improved by making the content rate of water 0.05% or more. On the other hand, when the water content is 3% by weight or less, it is possible to prevent a decrease in the curability of the composition.
- composition of the present invention may contain a radical curable component (hereinafter referred to as “other radical curable component”) other than the component (A).
- other radical curable components include (meth) acryloyl group-containing compounds.
- various molecular weights can be selected, and any of monomers, oligomers, and polymers may be used.
- Examples of the (meth) acryloyl group-containing compound include a compound having one (meth) acryloyl group in the molecule (hereinafter referred to as “monofunctional (meth) acrylate”), and two (meth) acryloyl groups in the molecule. And a compound having 3 or more (meth) acryloyl groups in the molecule and an equivalent (meth) acryloyl group exceeding 200 g / eq [hereinafter referred to as “( A) a polyfunctional (meth) acrylate other than the component ”.
- the monofunctional (meth) acrylate examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, 2- Ethylhexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate 4-hydroxybutyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, 1,4-cyclohexanedimethylol mono (meth) acrylate, dicyclopentani Of (meth) methyl
- bifunctional (meth) acrylate examples include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1 , 6-hexanediol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, cyclohexanedimethylol di (meth) acrylate, 2-butyl-2-ethyl-1,3-propanediol Di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (me ) Acrylate, esterification reaction product of
- polyfunctional (meth) acrylate other than the component (A) include polyester (meth) acrylate having a (meth) acryloyl group equivalent exceeding 200 g / eq, dendrimer type (meth) acrylate, 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.
- polymer examples include poly (meth) acrylic acid ester, polyvinyl acetate, polystyrene, polyether, and polyester.
- a polymer what contains cationic polymerizable groups, such as an epoxy group, an oxetanyl group, and a vinyl ether group, can also be used in a molecule
- radically polymerizable groups such as a (meth) acryloyl group and a vinyl group, can also be used in a molecule
- Active energy ray-curable adhesive composition for plastic film or sheet The present invention comprises the above-mentioned components (A) to (C) as essential components, and preferably a plastic film that also comprises components (D) to (F) Alternatively, the present invention relates to an active energy ray-curable adhesive composition for sheets.
- 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, there is a method of using a distilled purified product as all or part of the component (B), the component (E), and / or the component (F). Can be mentioned.
- each compounding component can be produced by stirring and mixing according to a conventional method. In this case, it can be heated or heated as necessary.
- the viscosity at 25 ° C. is preferably 200 mPa ⁇ s or less. It is more preferably 10 to 100 mPa ⁇ s, and particularly preferably 20 to 70 mPa ⁇ s.
- the viscosity of the composition means a measured value measured with 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 for the plastic film include triacetyl cellulose, cellulose acetate butyrate, cycloolefin polymer, (meth) acrylic resin, polystyrene, acrylic / styrene copolymer, 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 cellulose acetate 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 10 to 500 mJ / cm 2 , more preferably 20 to 300 mJ / cm 2 , and further preferably 30 to 200 mJ / cm 2 in the UV-B region (near 310 nm).
- an EB irradiation device that can be used, such as a Cockcroft-Walton type, a bandegraph type, and a resonance transformer type device, and an electron beam of 50 to 1000 eV. Those having energy are preferable, and more preferably 100 to 300 eV.
- the composition of this invention can be preferably used for manufacture of a laminated body.
- the structure of the laminate is a laminate composed of a base material, a cured product of the above-described composition, and another base material, and both or one of the base material and the other base material is a plastic film. Or it is a sheet.
- the plastic film or the like it is preferable that at least one is a cellulose acetate resin or a cycloolefin polymer.
- the above-described composition is applied to a base material, and another base material is bonded to the coated surface, and either the base material or the other base material is used.
- a method of irradiating active energy rays from the side of the surface a plastic film or the like is used as both the base material and the other base material, or at least one of the base materials.
- 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.
- hard coat films and touch panels provided with functionality such as anti-fingerprint and anti-glare Front plate, polarizing plate, retardation film, viewing angle compensation film, brightness enhancement film, antireflection film, antiglare film, lens sheet and diffusion sheet.
- part means parts by weight
- % means weight%
- numerical value indicating the blending ratio in the table means weight%
- each component used for the preparation of the composition is as follows and is abbreviated as follows.
- Component (A) M-305 A mixture of pentaerythritol triacrylate (acrylic equivalent 99 g / eq) and pentaerythritol tetraacrylate (acrylic equivalent 88 g / eq), “Aronix M-305” manufactured by Toagosei Co., Ltd.
- Component (B) BD-DGE: 1,4-butanediol diglycidyl ether (distilled product, total chlorine content 0.1% by weight or less), “SR-14BJ” manufactured by Sakamoto Pharmaceutical Co., Ltd.
- HD-DGE 1,6-hexanediol diglycidyl ether (distilled product, total chlorine amount 0.1 wt% or less), “Epo Gosei HD (D)” manufactured by Yokkaichi Gosei Co., Ltd.
- Component (C) 110P Triarylsulfonium hexafluorophosphate (active ingredient 100%), “CPI-110P” manufactured by San Apro Co., Ltd. 100P-net: an active ingredient in a propylene carbonate (hereinafter referred to as “PC”) solution of triarylsulfonium hexafluorophosphate (hereinafter referred to as “PC”) [active ingredient 50%, “CPI-100P” manufactured by San Apro Co., Ltd.] Substantially the same component as the above "110P”. PCs in CPI-100P are listed separately in the table as described later.
- PCs in CPI-100P are listed separately in the table as described later.
- Component (D) DETX 2,4-diethylthioxanthone (hydrogen abstraction type photo radical polymerization initiator), “DETX-S” manufactured by Nippon Kayaku Co., Ltd.
- Component (E) J-828US: Bisphenol A type epoxy resin (low chlorine grade, total chlorine amount 0.1 to 0.2% by weight), "jER-828US” manufactured by Mitsubishi Chemical Corporation
- OXT-221 Bis [(3-ethyloxetane-3-yl) methyl] ether (molecular weight 214), “Aron oxetane OXT-221” manufactured by Toagosei Co., Ltd.
- Component (A ′) [(meth) acrylate compound not corresponding to component (A)] 4HBA: 4-hydroxybutyl acrylate (monofunctional acrylate), “4-HBA” manufactured by Osaka Organic Chemical Industry Co., Ltd. HDDA: 1,6-hexanediol diacrylate (bifunctional acrylate), “Biscoat # 230” manufactured by Osaka Organic Chemical Industry Co., Ltd. M-321: triacrylate of propylene oxide 6 mol adduct of trimethylolpropane (acrylic equivalent 215 g / eq), “Aronix M-321” manufactured by Toagosei Co., Ltd.
- an ultraviolet ray irradiation device using a metal halide lamp
- 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 70 mJ / cm 2 (UV-B).
- UV-B an integrated light amount of 70 mJ / cm 2
- the end of the laminate was peeled off by hand, and the curability was evaluated according to the following criteria.
- 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. The results are shown in Tables 1 and 2.
- Evaluation methods 1) Evaluation of curability Immediately after the ultraviolet irradiation, the end of the laminate was peeled off by hand and judged according to the following criteria. In addition, if it is more than B determination, it will be evaluated that there is no problem in actual use. A: The adhesive was not liquid and was not weak enough to peel easily. B: Although the adhesive was not liquid, it was weak enough to peel easily. C: The adhesive was liquid.
- compositions of Examples 1 to 4 which are the compositions of the present invention, had a low viscosity and were excellent in colorless transparency and adhesive strength.
- the composition of Example 1 had a slightly low curability at B.
- the curing property is not so low that the adhesive is liquid immediately after the ultraviolet irradiation, it is considered that there is no problem depending on the application.
- Example 2 in which a part of the component (B) in the composition of Example 1 was allocated to the component (E), the curability was improved as compared with Example 1. This adhesive force was not “material breakage”, but was 9.5 N / inch and was strong.
- Example 3 in which a part of the component (B) of the composition of Example 2 was allocated to the component (F), the adhesive force was improved as compared with Example 2, and “material breakage” was observed.
- the composition of Example 4 is obtained by slightly changing the composition of the composition of Example 3. However, while having excellent curability, colorless transparency and adhesive strength equivalent to Example 3, the viscosity is Was further reduced.
- the composition of Comparative Example 1 containing the component (A) in excess of the upper limit of 45% by weight of the present invention had clearly lower adhesive strength than the compositions of Examples 1 to 4.
- the composition of Comparative Example 2 containing no component (A) had poor curability and low adhesion.
- Most of M-305 in the composition of Example 3 was distributed to 4HBA, and the composition of Comparative Example 3 in which the component (A) was less than 15% by weight of the present invention had very low adhesive strength.
- the composition of Comparative Example 6 in which the component (B) was less than the lower limit of 10% by weight of the present invention had very low adhesive strength.
- 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.
(A)成分:1分子中に3個以上の(メタ)アクリロイル基を有し、(メタ)アクリロイル基当量が200g/eq以下である化合物
(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:光カチオン重合開始剤 The present invention is a composition comprising the following components (A), (B) and (C), wherein the total amount of the component (A) is 15 to 45% by weight, and the component (B) is 10 to 75%. The present invention relates to an active energy ray-curable adhesive composition for plastic film or sheet containing 0.5% by weight and 0.5% to 10% by weight of component (C).
Component (A): Compound (B) having 3 or more (meth) acryloyl groups in the molecule and having a (meth) acryloyl group equivalent of 200 g / eq or less: Polyol having 2 to 10 carbon atoms , Polyglycidyl ether (C) component: photocationic polymerization initiator
(B)成分としては、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が好ましく、炭素数2~6個を有するジオールの、ジグリシジルエーテルがより好ましい。
(C)成分としては、スルホニウム塩系光カチオン重合開始剤が好ましい。 As the component (A), a compound having 3 to 6 (meth) acryloyl groups in one molecule and having a (meth) acryloyl group equivalent of 150 g / eq or less is preferable.
As the component (B), diglycidyl ether of a diol having 2 to 10 carbon atoms is preferable, and diglycidyl ether of a diol having 2 to 6 carbon atoms is more preferable.
As the component (C), a sulfonium salt photocationic polymerization initiator is preferable.
(E)成分としては、ビスフェノール型エポキシ樹脂が好ましい。
(F)成分としては、下記式(1)に示す化合物が好ましい。 As the component (D), a hydrogen abstraction type photo radical polymerization initiator is preferable.
As the component (E), a bisphenol type epoxy resin is preferable.
As the component (F), a compound represented by the following formula (1) is preferable.
又、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、セルロースアセテート系樹脂又はシクロオレフィンポリマーであることが好ましい。 Further, it is preferable that 0.05 to 3% by weight of water is contained in the whole composition.
Moreover, it is preferable that at least one of the plastic film or sheet is a cellulose acetate resin or a cycloolefin polymer.
前記基材及び前記他の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に関する。
プラスチック製フィルム又はシートとしては、その少なくとも一方が、セルロースアセテート系樹脂又はシクロオレフィンポリマーであるものが好ましい。 Further, the present invention is a laminate composed of a base material, a cured product of the above-mentioned active energy ray-curable adhesive composition for plastic film or sheet, and another base material,
The present invention relates to a laminate in which both or one of the substrate and the other substrate is a plastic film or sheet.
As a plastic film or sheet, at least one of them is preferably a cellulose acetate resin or a cycloolefin polymer.
前記基材及び前記他の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。 Moreover, this invention coats the said composition on a base material, bonds another base material to a coating surface, and irradiates an active energy ray from either the said base material or the said other base material side. A method of manufacturing a laminate,
The present invention relates to a method for producing a laminate in which both or one of the base material and the other base material is a plastic film or sheet.
(A)成分:1分子中に3個以上の(メタ)アクリロイル基を有し、(メタ)アクリロイル基当量が200g/eq以下である化合物
(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:光カチオン重合開始剤
以下、(A)~(C)成分について説明する。次いで、好ましい配合成分である(D)~(F)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 a composition comprising the following components (A), (B) and (C), wherein the total amount of the component (A) is 15 to 45% by weight, and the component (B) is 10 to 75%. The present invention relates to an active energy ray-curable adhesive composition for plastic film or sheet containing 0.5% by weight and 0.5% to 10% by weight of component (C).
Component (A): Compound (B) having 3 or more (meth) acryloyl groups in the molecule and having a (meth) acryloyl group equivalent of 200 g / eq or less: Polyol having 2 to 10 carbon atoms Polyglycidyl ether (C) component: photocationic polymerization initiator The components (A) to (C) will be described below. Next, components (D) to (F), which are preferred blending components, other components, and preferred methods of using the composition of the present invention will be described in detail.
(A)成分は、1分子中に3個以上の(メタ)アクリロイル基を有し、(メタ)アクリロイル基当量が200g/eq以下である化合物である。
(A)成分は、適量配合することで、セルロースアセテート系基材への接着力や、コロナ処理したシクロオレフィンポリマーへの接着力を高める効果を有する。
1分子中に3個以上の(メタ)アクリロイル基を有する化合物であっても、(メタ)アクリロイル基当量が200g/eqを超過する化合物は、セルロースアセテート系基材等への接着力が低くなるという問題がある。
本発明における(メタ)アクリロイル基当量とは、(メタ)アクリロイル基1モル当たりの(A)成分の重量(g/eq)を意味し、(A)成の分子量及び1分子中に存在する(メタ)アクリロイル基の数に基づき、計算によって求められる値を意味する。 1. Component (A) The component (A) is a compound having 3 or more (meth) acryloyl groups in one molecule and having a (meth) acryloyl group equivalent of 200 g / eq or less.
Component (A) has the effect of increasing the adhesive strength to the cellulose acetate base and the adhesive strength to the corona-treated cycloolefin polymer by blending an appropriate amount.
Even if it is a compound having 3 or more (meth) acryloyl groups in one molecule, a compound having a (meth) acryloyl group equivalent exceeding 200 g / eq has a low adhesive force to a cellulose acetate substrate or the like. There is a problem.
The (meth) acryloyl group equivalent in the present invention means the weight (g / eq) of component (A) per mole of (meth) acryloyl group, and is present in (A) molecular weight and 1 molecule ( It means a value obtained by calculation based on the number of (meth) acryloyl groups.
又、(A)成分としては、アミノ基及びウレタン結合を有さない化合物が、(B)成分等のカチオン硬化性を悪化させないという理由で好ましい。 The component (A) is preferably a compound having 3 to 6 (meth) acryloyl groups in one molecule and having a (meth) acryloyl group equivalent of 150 g / eq or less, and a (meth) acryloyl group equivalent of 80 More preferred are compounds that are ˜150 g / eq. Further, a compound having 3 to 4 (meth) acryloyl groups in one molecule and having a (meth) acryloyl group equivalent of 80 to 150 g / eq is more preferable.
Moreover, as (A) component, the compound which does not have an amino group and a urethane bond is preferable because it does not deteriorate cation curability, such as (B) component.
トリメチロールプロパンのアルキレンオキサイド付加物のトリ(メタ)アクリレート、ペンタエリスリトールのアルキレンオキサイド付加物のテトラ(メタ)アクリレート、ジペンタエリスリトールのアルキレンオキサイド付加物のヘキサ(メタ)アクリレート、グリセリンのアルキレンオキサイド付加物のトリ(メタ)アクリレート、ジグリセリンのアルキレンオキサイド付加物のテトラ(メタ)アクリレート等のポリオールのアルキレンオキサイド付加物のポリ(メタ)アクリレート;
イソシアヌル酸アルキレンオキサイド付加物のトリ(メタ)アクリレート;
並びに3個以上の(メタ)アクリロイル基を有するポリエステル(メタ)アクリレート等が挙げられる。
アルキレンオキサイド付加物におけるアルキレンオキサイドとしては、エチレンオキサイド及びプロプレンオキサイドが好ましい。又、ポリオールのアルキレンオキサイド付加物のポリ(メタ)アクリレート及び3個以上の(メタ)アクリロイル基を有するポリエステル(メタ)アクリレートは、(メタ)アクリロイル基当量200g/eq以下である必要がある。 Specific examples of the component (A) include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin tri (meth) acrylate, diglycerin tetra (meth) acrylate, Polyol poly (meth) acrylates such as dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate;
Tri (meth) acrylate of alkylene oxide adduct of trimethylolpropane, tetra (meth) acrylate of alkylene oxide adduct of pentaerythritol, hexa (meth) acrylate of alkylene oxide adduct of dipentaerythritol, alkylene oxide adduct of glycerol A poly (meth) acrylate of an alkylene oxide adduct of a polyol, such as a tri (meth) acrylate of a diglycerin, and a tetra (meth) acrylate of an alkylene oxide adduct of diglycerin;
Tri (meth) acrylates of isocyanuric acid alkylene oxide adducts;
And polyester (meth) acrylate having 3 or more (meth) acryloyl groups.
As the alkylene oxide in the alkylene oxide adduct, ethylene oxide and propylene oxide are preferable. Moreover, the poly (meth) acrylate of the alkylene oxide adduct of polyol and the polyester (meth) acrylate having 3 or more (meth) acryloyl groups need to have a (meth) acryloyl group equivalent of 200 g / eq or less.
(A)成分の含有割合は、組成物全体を基準として、15~45重量%である。
(A)成分の含有割合が15重量%未満であったり、逆に45重量%を超えたりすると、セルロースアセテートや、コロナ処理したシクロオレフィンポリマー等、プラスチックフィルムへの接着力が低下する。この点で、(A)成分の好ましい含有割合は、15~40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 15 to 45% by weight based on the entire composition.
When the content ratio of the component (A) is less than 15% by weight, or conversely exceeds 45% by weight, the adhesive force to a plastic film such as cellulose acetate or a corona-treated cycloolefin polymer is lowered. In this respect, the preferred content of component (A) is 15 to 40% by weight.
(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)成分は、適量配合することで、セルロースアセテート系基材への接着力や、コロナ処理したシクロオレフィンポリマーへの接着力を高める効果を有する。 2. Component (B) 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.
Component (B) has the effect of increasing the adhesive strength to the cellulose acetate base and the adhesive strength to the corona-treated cycloolefin polymer by blending an appropriate amount.
又、(B)成分としては、組成物が硬化性と接着力に優れるものとなる点で、全塩素量が1%以下のものが好ましく、0.5%以下のものがより好ましく、0.2%以下のものがさらに好ましく、0.1%以下のものが特に好ましい。
上記全塩素量は、石英管燃焼-イオンクロマトグラフィ法に基づいて測定することができる。 As the component (B), a diglycidyl ether of a diol having 2 to 10 carbon atoms is preferable in that the viscosity of the composition can be reduced and the composition has excellent adhesion to a plastic substrate. Diglycidyl ethers of diols having 2 to 6 carbon atoms are more preferred, and diglycidyl ethers of alkane diols having 2 to 6 carbon atoms are more preferred.
The component (B) preferably has a total chlorine content of 1% or less, more preferably 0.5% or less, in that the composition has excellent curability and adhesive strength. Those of 2% or less are more preferred, and those of 0.1% or less are particularly preferred.
The total chlorine amount can be measured based on a quartz tube combustion-ion chromatography method.
(B)成分の含有割合は、組成物全体中に10~75重量%である。
(B)成分が10重量%未満であると、多くのプラスチック基材に対して組成物の接着力が低下してしまう。又、(B)成分の含有割合が75重量%を超えると、組成物の硬化性が悪化し、接着力も悪化する。
(B)成分の好ましい含有割合は、組成物全体中に15~60重量%であり、より好ましくは15~50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 10 to 75% by weight in the entire composition.
When the component (B) is less than 10% by weight, the adhesive strength of the composition with respect to many plastic substrates is lowered. Moreover, when the content rate of (B) component exceeds 75 weight%, the sclerosis | hardenability of a composition will deteriorate and adhesive force will also deteriorate.
A preferred content ratio of the component (B) is 15 to 60% by weight, more preferably 15 to 50% by weight in the whole composition.
(C)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、(A)成分や後記する(A)成分以外の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。
(C)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。 3. (C) Component (C) component is a photocationic polymerization initiator. That is, by irradiation with active energy rays such as ultraviolet rays and electron beams, cations or Lewis acids are generated, and polymerization of cationically curable components such as epoxy compounds and oxetane compounds other than the (A) component and the (A) component described later is performed. The compound to be initiated.
Specific examples of the component (C) 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.
(C)成分の含有割合は、組成物全体中に0.5~10重量%であり、好ましくは1~7重量%である。(C)成分の含有割合が0.5重量%未満であると組成物の硬化性が悪化し、10重量%を超えると組成物の接着力が低下したり、硬化物が黄変したりする。 (C) As a component, an above described compound may be used independently, or 2 or more types may be used.
The content ratio of the component (C) is 0.5 to 10% by weight, preferably 1 to 7% by weight in the whole composition. When the content ratio of the component (C) is less than 0.5% by weight, the curability of the composition deteriorates, and when it exceeds 10% by weight, the adhesive strength of the composition decreases or the cured product turns yellow. .
本発明の組成物は、前記(A)~(C)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(以下、「その他の成分」という)を配合することができる。 4). The composition of the other components present invention, the (A) ~ (C) but it is an essential component, various components depending on the purpose (hereinafter referred to as "other components") be blended it can.
以下、(D)、(E)及び(F)成分について説明する。 Preferred examples of other components include a radical photopolymerization initiator (hereinafter referred to as “component (D)”), an epoxy compound having two or more aromatic rings and two or more epoxy groups in one molecule (hereinafter referred to as “component (D)”). And a compound having a molecular weight of 500 or less (hereinafter referred to as “component (F)”) having two or more oxetanyl groups in one molecule.
Hereinafter, the components (D), (E), and (F) will be described.
本発明の組成物に含まれる(A)成分等のラジカル硬化性成分は、(C)成分が光で分解する際に発生するラジカルで硬化させることが可能であるが、少ない照射量で十分な反応率を得るために、(D)成分(光ラジカル重合開始剤)を配合することが好ましい。 4-1. Component (D) The radical curable component such as the component (A) contained in the composition of the present invention can be cured with radicals generated when the component (C) is decomposed by light, but with little irradiation. In order to obtain a sufficient reaction rate in an amount, the component (D) (photo radical polymerization initiator) is preferably blended.
ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、及びベンゾインイソブチルエーテル等のベンゾインエーテル系光重合開始剤;
ベンゾフェノン、o-ベンゾイル安息香酸メチル、4-フェニルベンゾフェノン、4-ベンゾイル-4′-メチルジフェニルサルファイド、及び2,4,6-トリメチルベンゾフェノン等のベンゾフェノン系光重合開始剤;
2-イソプロピルチオキサントン、2,4-ジエチルチオキサントン、2,4-ジクロロチオキサントン、及び1-クロロ-4-プロポキシチオキサントン等のチオキサントン系光重合開始剤;
2,4,6-トリメチルベンゾイルジフェニルホスフィンオキサイド、ビス(2,6-ジメトキシベンゾイル)-2,4,4-トリメチルペンチルホスフィンオキサイド、及びビス(2,4,6-トリメチルベンゾイル)フェニルホスフィンオキサイド等のアシルホスフィンオキサイド系光重合開始剤;
1,2-オクタンジオン,1-〔4-(フェニルチオフェニル)〕-,2-(O-ベンゾイルオキシム)等のオキシム・エステル系光重合開始剤;並びに
カンファーキノン等が挙げられる。 Specific examples of the component (D) include 4′-phenoxy-2,2-dichloroacetophenone, 4′-tert-butyl-2,2-dichloroacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2 ′ -Methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 1-hydroxycyclohexyl phenyl ketone, α, α-diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane- 1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methylpropan-1-one, and 2-benzi Acetophenone photopolymerization initiators such as 2-dimethylamino-1- (4-morpholinophenyl) butan-1-one;
Benzoin ether photopolymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether;
Benzophenone photopolymerization initiators such as benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, and 2,4,6-trimethylbenzophenone;
Thioxanthone photopolymerization initiators such as 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone;
2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, etc. An acylphosphine oxide photopolymerization initiator;
Examples include oxime ester photopolymerization initiators such as 1,2-octanedione, 1- [4- (phenylthiophenyl)]-, 2- (O-benzoyloxime); and camphorquinone.
(D)成分としては、チオキサントン系光重合開始剤や、ベンゾフェノン系光重合開始剤等の、水素引抜型ラジカル重合開始剤が、プラスチック基材との接着力を高める効果もあるため好ましい。これらの中でも、チオキサントン系光重合開始剤は、接着力を高める効果が高く、特に好ましい。
(D)成分を配合する場合、その含有割合は、組成物全体を基準として、好ましくは0.1~10重量%、より好ましくは0.1~5重量%である。(D)の含有量を0.1重量%以上とすることで硬化性が優れたものになり、10重量%以下とすることで硬化物の黄変を防止する事ができる。 As the component (D), one type can be used alone, or two or more types can be blended and used according to desired performance.
As the component (D), a hydrogen abstraction type radical polymerization initiator such as a thioxanthone photopolymerization initiator or a benzophenone photopolymerization initiator is preferable because it has an effect of increasing the adhesive force with a plastic substrate. Among these, thioxanthone-based photopolymerization initiators are particularly preferable because they have a high effect of increasing adhesive strength.
When the component (D) is blended, the content is preferably 0.1 to 10% by weight, more preferably 0.1 to 5% by weight, based on the entire composition. When the content of (D) is 0.1% by weight or more, curability is excellent, and when it is 10% by weight or less, yellowing of the cured product can be prevented.
(E)成分は、1分子中に2個以上の芳香環と2個以上のエポキシ基とを有するエポキシ化合物である。但し、本発明における(E)成分は、ナフタレンジオールのジグリシジルエーテル等の、炭素数10以下のポリオールの、ポリグリシジルエーテルは、(E)成分に含まれないものとする。
(E)成分は、適量配合することで、セルロースアセテート系基材への接着力や、コロナ処理したシクロオレフィンポリマーへの接着力を高める効果を有する。 4-2. Component (E) The component (E) is an epoxy compound having two or more aromatic rings and two or more epoxy groups in one molecule. However, the component (E) in the present invention does not include a polyglycidyl ether of a polyol having 10 or less carbon atoms such as diglycidyl ether of naphthalenediol.
Component (E) has the effect of increasing the adhesive strength to the cellulose acetate base and the adhesive strength to the corona-treated cycloolefin polymer by blending an appropriate amount.
ここで、エポキシ樹脂とは、分子中に平均2個以上のエポキシ基を有し、反応により硬化する化合物又はポリマーをいう。この分野での慣例に従い、本明細書では、硬化性のエポキシ基を分子内に2個以上有するものであれば、モノマーであってもエポキシ樹脂と呼ぶことがある。 Specific examples of the component (E) include bisphenol A type epoxy resin, bisphenol F type epoxy resin, brominated bisphenol A type epoxy resin, epoxy resin obtained by polycondensation of bisphenol A, bisphenol F and epichlorohydrin, phenol novolac type epoxy resin, Examples include a cresol novolac epoxy resin, a bisphenol A novolac epoxy resin, a bisphenol F novolac epoxy resin, and a biphenyl epoxy resin.
Here, the epoxy resin means a compound or polymer having an average of two or more epoxy groups in the molecule and cured by reaction. In accordance with the custom in this field, in this specification, a monomer may be referred to as an epoxy resin as long as it has two or more curable epoxy groups in the molecule.
又、(E)成分としては、接着力の点で、全塩素量が0.5%以下のものが好ましく、0.3%以下のものがより好ましく、0.2%以下のものがさらに好ましい。 As the component (E), a bisphenol type epoxy resin such as a bisphenol A type epoxy resin or a bisphenol F type epoxy resin is particularly preferable in terms of adhesive strength.
The component (E) preferably has a total chlorine content of 0.5% or less, more preferably 0.3% or less, and still more preferably 0.2% or less in terms of adhesive strength. .
(E)成分を配合する場合、その含有割合は、組成物全体を基準として、好ましくは1~40重量%、より好ましくは5~30重量%、さらに好ましくは10~30重量%である。 (E) As a component, an above described compound may be used independently, or 2 or more types may be used.
When the component (E) is blended, the content is preferably 1 to 40% by weight, more preferably 5 to 30% by weight, and still more preferably 10 to 30% by weight, based on the entire composition.
(F)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。(F)成分を適量配合することで、組成物の硬化性を向上させ、組成物の硬化物とプラスチック基材との接着力を向上させることができる。 4-3. Component (F) The component (F) is a compound having a molecular weight of 500 or less having two or more oxetanyl groups in one molecule. By blending an appropriate amount of the component (F), the curability of the composition can be improved, and the adhesive force between the cured product of the composition and the plastic substrate can be improved.
(F)成分を配合する場合、その含有割合は、組成物全体を基準として、好ましくは1~40重量%、より好ましくは5~35重量%、さらに好ましくは10~30重量%である。 As the component (F), the above-described compounds may be used alone, or two or more kinds may be used.
When the component (F) is blended, the content is preferably 1 to 40% by weight, more preferably 5 to 35% by weight, and still more preferably 10 to 30% by weight, based on the entire composition.
前記にその他の成分の好ましい例である(D)~(F)成分について説明したが、目的に応じてこれら以外の種々の成分を配合することができる。 4-4. Other Components Other than the above The components (D) to (F), which are preferred examples of the other components, have been described above, but various components other than these can be blended depending on the purpose.
その他のカチオン硬化性成分を含む場合、それらの含有割合の合計は、組成物全体を基準として30重量%以下であることが好ましく、20重量%以下とすることがより好ましく、10重量%以下とすることがさらに好ましい。
その他のカチオン硬化性成分としては、(B)成分及び(E)成分以外のエポキシ基含有化合物、(F)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 said other component, you may contain cationically curable compounds (henceforth "other cation-curable components") other than (B) component, (E) component, and (F) component mentioned above.
When other cationic curable components are included, the total content thereof is preferably 30% by weight or less, more preferably 20% by weight or less based on the whole composition, and 10% by weight or less. More preferably.
Examples of other cationic curable components include epoxy group-containing compounds other than the (B) component and the (E) component, oxetanyl group-containing compounds other than the (F) component, and vinyl ether group-containing compounds.
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、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等が挙げられる。 Specific examples of the epoxy group-containing compound other than the component (B) and the component (E) include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate-modified caprolactone, esterified product of polycarboxylic acid and 3,4-epoxycyclohexylmethyl alcohol or caprolactone-modified product, dicyclopentadiene dioxide, limonene di Alicyclic epoxy compounds such as oxide, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane and 4-vinylcyclohexene dioxide Carbon such as polyethylene glycol (repeat number 6 or more) diglycidyl ether, polypropylene glycol (repeat number 4 or more) diglycidyl ether, polytetramethylene glycol (repeat number 3 or more) diglycidyl ether, polybutadiene diglycidyl ether of hydroxyl groups at both ends The diglycidyl ether etc. of the diol of several 11 or more are mentioned.
In addition to these, epoxidized vegetable oil, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, internal epoxidized products of polybutadiene, and the like can be mentioned.
その他のラジカル硬化性成分としては、(メタ)アクリロイル基含有化合物等が挙げられる。又、それらの分子量としては、種々のものが選択でき、モノマー、オリゴマー、及びポリマーのいずれであってもよい。 The composition of the present invention may contain a radical curable component (hereinafter referred to as “other radical curable component”) other than the component (A).
Examples of other radical curable components include (meth) acryloyl group-containing compounds. In addition, various molecular weights can be selected, and any of monomers, oligomers, and polymers may be used.
ポリマーとしては、分子中に、エポキシ基、オキセタニル基、及びビニルエーテル基等のカチオン重合性基を含むものも使用できる。又、分子内に、(メタ)アクリロイル基やビニル基等の、ラジカル重合性基を含むものも使用できる。 Examples of the polymer include poly (meth) acrylic acid ester, polyvinyl acetate, polystyrene, polyether, and polyester.
As a polymer, what contains cationic polymerizable groups, such as an epoxy group, an oxetanyl group, and a vinyl ether group, can also be used in a molecule | numerator. Moreover, what contains radically polymerizable groups, such as a (meth) acryloyl group and a vinyl group, can also be used in a molecule | numerator.
本発明は、前記(A)~(C)成分を必須成分として含み、好ましくは(D)~(F)成分をも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。 5). Active energy ray-curable adhesive composition for plastic film or sheet The present invention comprises the above-mentioned components (A) to (C) as essential components, and preferably a plastic film that also comprises components (D) to (F) Alternatively, the present invention relates to an active energy ray-curable adhesive composition for sheets.
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は、25℃に於ける粘度が200mPa・s以下であることが好ましく、10~100mPa・sであることがより好ましく、20~70mPa・sであることが特に好ましい。
本発明において、組成物の粘度とは、E型粘度計により測定した測定値を意味する。 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. is preferably 200 mPa · s or less. It is more preferably 10 to 100 mPa · s, and particularly preferably 20 to 70 mPa · s.
In the present invention, the viscosity of the composition means a measured value measured with 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セルロースアセテート系樹脂に好ましく適用できるものである。 Examples of the material for the plastic film include triacetyl cellulose, cellulose acetate butyrate, cycloolefin polymer, (meth) acrylic resin, polystyrene, acrylic / styrene copolymer, 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 cellulose acetate 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。 6). 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。
積層体の構成としては、基材、前記した組成物の硬化物及び、他の基材から構成される積層体であって、前記基材及び他の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ものである。
プラスチックフィルム等としては、少なくとも一方が、セルロースアセテート系樹脂、又はシクロオレフィンポリマーであるものが好ましい。
積層体の製造方法としては、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、前記基材又は前記他の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、前記基材及び前記他の基材の両方の基材、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。 7). Manufacturing method of laminated body The composition of this invention can be preferably used for manufacture of a laminated body.
The structure of the laminate is a laminate composed of a base material, a cured product of the above-described composition, and another base material, and both or one of the base material and the other base material is a plastic film. Or it is a sheet.
As the plastic film or the like, it is preferable that at least one is a cellulose acetate resin or a cycloolefin polymer.
As a method for producing a laminate, specifically, the above-described composition is applied to a base material, and another base material is bonded to the coated surface, and either the base material or the other base material is used. And a method of irradiating active energy rays from the side of the surface.
In this case, a plastic film or the like is used as both the base material and the other base material, or at least one of the base materials. 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、「%」とは重量%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, “%” means weight%, and the numerical value indicating the blending ratio in the table means weight%.
・M-305:ペンタエリスリトールトリアクリレート(アクリル当量99g/eq)とペンタエリスリトールテトラアクリレート(アクリル当量88g/eq)の混合物、東亞合成(株)製の"アロニックスM-305" Component (A) M-305: A mixture of pentaerythritol triacrylate (acrylic equivalent 99 g / eq) and pentaerythritol tetraacrylate (acrylic equivalent 88 g / eq), “Aronix M-305” manufactured by Toagosei Co., Ltd.
・BD-DGE:1,4-ブタンジオールジグリシジルエーテル(蒸留精製品、全塩素量0.1重量%以下)、阪本薬品工業(株)製の"SR-14BJ"
・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、全塩素量0.1重量%以下)、四日市合成(株)製の"エポゴーセーHD(D)" Component (B) : BD-DGE: 1,4-butanediol diglycidyl ether (distilled product, total chlorine content 0.1% by weight or less), “SR-14BJ” manufactured by Sakamoto Pharmaceutical Co., Ltd.
HD-DGE: 1,6-hexanediol diglycidyl ether (distilled product, total chlorine amount 0.1 wt% or less), “Epo Gosei HD (D)” manufactured by Yokkaichi Gosei Co., Ltd.
・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"
・100P-net: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のプロピレンカーボネート(以下、「PC」という)溶液〔有効成分50%、サンアプロ(株)製の"CPI-100P"〕中の有効成分。上記「110P」と実質的には殆ど同じ成分。CPI-100P中のPCは、後記の通り表中では分けて記載した。 Component (C) 110P: Triarylsulfonium hexafluorophosphate (active ingredient 100%), “CPI-110P” manufactured by San Apro Co., Ltd.
100P-net: an active ingredient in a propylene carbonate (hereinafter referred to as “PC”) solution of triarylsulfonium hexafluorophosphate (hereinafter referred to as “PC”) [active ingredient 50%, “CPI-100P” manufactured by San Apro Co., Ltd.] Substantially the same component as the above "110P". PCs in CPI-100P are listed separately in the table as described later.
・DETX:2,4-ジエチルチオキサントン(水素引抜型光ラジカル重合開始剤)、日本化薬(株)製の"DETX-S" Component (D) DETX: 2,4-diethylthioxanthone (hydrogen abstraction type photo radical polymerization initiator), “DETX-S” manufactured by Nippon Kayaku Co., Ltd.
・J-828US:ビスフェノールA型エポキシ樹脂(低塩素グレード、全塩素量0.1~0.2重量%)、三菱化学(株)製の"jER-828US" Component (E) : J-828US: Bisphenol A type epoxy resin (low chlorine grade, total chlorine amount 0.1 to 0.2% by weight), "jER-828US" manufactured by Mitsubishi Chemical Corporation
・OXT-221:ビス〔(3-エチルオキセタン-3-イル)メチル〕エーテル(分子量214)、東亞合成(株)製の“アロンオキセタンOXT-221” Component (F) • OXT-221: Bis [(3-ethyloxetane-3-yl) methyl] ether (molecular weight 214), “Aron oxetane OXT-221” manufactured by Toagosei Co., Ltd.
・4HBA:4-ヒドロキシブチルアクリレート(単官能アクリレート)、大阪有機化学工業(株)製の“4-HBA”。
・HDDA:1,6-ヘキサンジオールジアクリレート(二官能アクリレート)、大阪有機化学工業(株)製の“ビスコート#230”。
・M-321:トリメチロールプロパンのプロピレンオキサイド6モル付加物のトリアクリレート(アクリル当量215g/eq)、東亞合成(株)製の"アロニックスM-321" Component (A ′) [(meth) acrylate compound not corresponding to component (A)]
4HBA: 4-hydroxybutyl acrylate (monofunctional acrylate), “4-HBA” manufactured by Osaka Organic Chemical Industry Co., Ltd.
HDDA: 1,6-hexanediol diacrylate (bifunctional acrylate), “Biscoat # 230” manufactured by Osaka Organic Chemical Industry Co., Ltd.
M-321: triacrylate of propylene oxide 6 mol adduct of trimethylolpropane (acrylic equivalent 215 g / eq), “Aronix M-321” manufactured by Toagosei Co., Ltd.
・PC:CPI-100Pに含まれるプロピレンカーボネート
・水:イオン交換水 (Other) [Other ingredients]
・ PC: Propylene carbonate contained in CPI-100P ・ Water: Ion exchange water
1.組成物の製造
表1及び表2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。
得られた組成物について、25℃に於ける粘度を、東機産業(株)製のE型粘度計により測定した。結果を表1及び表2に示す。 Examples 1 to 4 and Comparative Examples 1 to 6
1. Production of compositions Each component shown in Tables 1 and 2 was blended in the respective proportions and stirred and mixed according to a conventional method to prepare an active energy ray-curable adhesive composition.
About the obtained composition, the viscosity in 25 degreeC was measured with the Toki Sangyo Co., Ltd. E-type viscosity meter. The results are shown in Tables 1 and 2.
厚さ100μmのシクロオレフィンポリマーフィルム〔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80μmのセルロースアセテート系樹脂フィルム〔商品名フジTAC、富士フイルム(株)製、以下「TAC」という〕に、易接着処理としてコロナ処理を実施した。
次いで、TAC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70mJ/cm2(UV-B)で紫外線を照射し、接着剤組成物を硬化させた(23℃50%雰囲気)。
ここで、紫外線照射直後に積層体の端を手で剥離し、下記の基準で硬化性を評価した。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。それらの結果を表1及び表2に示す。 2. Production of laminate: Cycloolefin polymer film having a thickness of 100 μm (trade name ZEONOR ZF-14, manufactured by Nippon Zeon Co., Ltd., hereinafter referred to as “ZEONOR”), and cellulose acetate resin film having a thickness of 80 μm [trade name: FujiTAC, Corona treatment was performed as an easy adhesion treatment on FUJIFILM Corporation's “TAC”.
Next, the obtained composition was applied to a TAC corona-treated surface 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 70 mJ / cm 2 (UV-B). Was cured (at 23 ° C., 50% atmosphere).
Here, immediately after ultraviolet irradiation, the end of the laminate was peeled off by hand, and the curability was evaluated according to the following criteria. 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. The results are shown in Tables 1 and 2.
1)硬化性の評価
紫外線照射直後に積層体の端を手で剥離し、以下の基準で判定した。尚、B判定以上であれば、実使用において問題ないと評価される。
A:接着剤は液状ではなく、又容易に剥離するほど弱くはなかった。
B:接着剤は液状ではないが、容易に剥離するほど弱かった。
C:接着剤が液状であった。 3. Evaluation methods
1) Evaluation of curability Immediately after the ultraviolet irradiation, the end of the laminate was peeled off by hand and judged according to the following criteria. In addition, if it is more than B determination, it will be evaluated that there is no problem in actual use.
A: The adhesive was not liquid and was not weak enough to peel easily.
B: Although the adhesive was not liquid, it was weak enough to peel easily.
C: The adhesive was liquid.
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。
A:濁りや黄変が感じられない。
B:濁りや黄変が少し感じられた。
C:濁りや黄変が明らかに感じられた。 2) Evaluation of colorless transparency Five layers of the obtained laminate were visually observed and judged according to the following criteria.
A: Turbidity and yellowing are not felt.
B: Turbidity and yellowing were slightly felt.
C: Turbidity and yellowing were clearly felt.
得られた積層体を、幅1インチ、長さ15cmに切り出し、TACをアルミ板に両面テープで貼り付けた。次いで、ゼオノアを、剥離速度200mm/分で180°剥離し、接着力を測定した。このとき、接着力が非常に強く、フィルムが破れて測定できなかったものを「材破」と評価した。 3) Evaluation of adhesive strength The obtained laminate was cut into a 1 inch width and a length of 15 cm, and TAC was attached to an aluminum plate with a double-sided tape. Next, ZEONOR was peeled 180 ° at a peeling speed of 200 mm / min, and the adhesive force was measured. At this time, the adhesive strength was very strong, and the film was torn and could not be measured was evaluated as “material breakage”.
これらの中で、実施例1の組成物は、硬化性がBでやや低かった。しかし、紫外線照射直後に接着剤が液状であるほど硬化性が低い訳ではないため、用途によっては問題ないと考えられる。
実施例1の組成物における(B)成分の一部を(E)成分に振り分けた実施例2は、実施例1に比べて、硬化性が向上していた。この接着力は、「材破」ではなかったが、9.5N/インチであり、強かった。
実施例2の組成物の(B)成分の一部を(F)成分に振り分けた実施例3は、実施例2より接着力が向上しており、「材破」であった。
実施例4の組成物は、実施例3の組成物の組成を少し変更したものであるが、実施例3と同等の優れた硬化性、無色透明性及び接着力を有しておりながら、粘度がさらに低減されていた。 The compositions of Examples 1 to 4, which are the compositions of the present invention, had a low viscosity and were excellent in colorless transparency and adhesive strength.
Among these, the composition of Example 1 had a slightly low curability at B. However, since the curing property is not so low that the adhesive is liquid immediately after the ultraviolet irradiation, it is considered that there is no problem depending on the application.
In Example 2, in which a part of the component (B) in the composition of Example 1 was allocated to the component (E), the curability was improved as compared with Example 1. This adhesive force was not “material breakage”, but was 9.5 N / inch and was strong.
In Example 3 in which a part of the component (B) of the composition of Example 2 was allocated to the component (F), the adhesive force was improved as compared with Example 2, and “material breakage” was observed.
The composition of Example 4 is obtained by slightly changing the composition of the composition of Example 3. However, while having excellent curability, colorless transparency and adhesive strength equivalent to Example 3, the viscosity is Was further reduced.
(A)成分を含まない比較例2の組成物は、硬化性が悪く、接着力も低かった。
実施例3の組成物におけるM-305の大部分を4HBAに振り分け、(A)成分が本発明の下限15重量%に満たない比較例3の組成物は、接着力が非常に低かった。
実施例3の組成物におけるM-305を、(A)成分に該当しないHDDAに振り替えた比較例4の組成物と、(A)成分に該当しないM-321に振り替えた比較例5の組成物は、どちらも接着力が非常に低かった。
(B)成分が本発明の下限10重量%に満たない比較例6の組成物は、接着力が非常に低かった。 On the other hand, the composition of Comparative Example 1 containing the component (A) in excess of the upper limit of 45% by weight of the present invention had clearly lower adhesive strength than the compositions of Examples 1 to 4.
The composition of Comparative Example 2 containing no component (A) had poor curability and low adhesion.
Most of M-305 in the composition of Example 3 was distributed to 4HBA, and the composition of Comparative Example 3 in which the component (A) was less than 15% by weight of the present invention had very low adhesive strength.
The composition of Comparative Example 4 in which M-305 in the composition of Example 3 was transferred to HDDA not corresponding to component (A), and the composition of Comparative Example 5 transferred to M-321 not corresponding to component (A) Both had very low adhesion.
The composition of Comparative Example 6 in which the component (B) was less than the lower limit of 10% by weight of the present invention had very low adhesive strength.
Claims (16)
- 下記(A)、(B)及び(C)成分を含む組成物であって、組成物全体中に、(A)成分を15~45重量%、(B)成分を10~75重量%及び(C)成分を0.5~10重量%含有する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:1分子中に3個以上の(メタ)アクリロイル基を有し、(メタ)アクリロイル基当量が200g/eq以下である化合物
(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:光カチオン重合開始剤 A composition comprising the following components (A), (B) and (C), wherein the total amount of component (A) is 15 to 45% by weight, component (B) is 10 to 75% by weight and ( C) An active energy ray-curable adhesive composition for plastic films or sheets containing 0.5 to 10% by weight of the component.
Component (A): Compound (B) having 3 or more (meth) acryloyl groups in the molecule and having a (meth) acryloyl group equivalent of 200 g / eq or less: Polyol having 2 to 10 carbon atoms , Polyglycidyl ether (C) component: photocationic polymerization initiator - 前記(A)成分が、1分子中に3~6個の(メタ)アクリロイル基を有し、(メタ)アクリロイル基当量が150g/eq以下の化合物である請求項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 according to claim 1, wherein the component (A) is a compound having 3 to 6 (meth) acryloyl groups in one molecule and having a (meth) acryloyl group equivalent of 150 g / eq or less. An active energy ray-curable adhesive composition for a sheet.
- 前記(B)成分が炭素数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。 3. The active energy ray-curable adhesive composition for plastic film or sheet according to claim 1, wherein the component (B) is a diglycidyl ether of a diol having 2 to 10 carbon atoms.
- 前記(B)成分が、炭素数2~6個を有する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 active energy ray-curable adhesive composition for plastic films or sheets according to claim 3, wherein the component (B) is a diglycidyl ether of an alkanediol having 2 to 6 carbon atoms.
- 前記(C)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 active energy ray-curable adhesive composition for plastic film or sheet according to any one of claims 1 to 4, wherein the component (C) is a sulfonium salt photocationic polymerization initiator.
- さらに、(D)成分として、光ラジカル重合開始剤を組成物全体中に0.1~10重量%含有する請求項1~請求項5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 or sheet activity according to any one of claims 1 to 5, further comprising 0.1 to 10 wt% of a radical photopolymerization initiator as a component (D) in the whole composition. Energy ray curable adhesive composition.
- 前記(D)成分が、水素引抜型光ラジカル重合開始剤である請求項6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 claim 6, wherein the component (D) is a hydrogen abstraction type photo radical polymerization initiator.
- さらに、(E)成分として、1分子中に2個以上の芳香環と2個以上のエポキシ基とを有するエポキシ化合物を組成物全体中に1~40重量%含有する請求項1~請求項7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。 Further, as the component (E), 1 to 40% by weight of an epoxy compound having two or more aromatic rings and two or more epoxy groups in one molecule is contained in the whole composition. The active energy ray hardening-type adhesive composition for plastic films or sheets of any one of these.
- 前記(E)成分が、ビスフェノール型エポキシ樹脂である請求項8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 claim 8, wherein the component (E) is a bisphenol-type epoxy resin.
- さらに、(F)成分として、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以下の化合物を、組成物全体中に1~40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。 Furthermore, as component (F), 1 to 40% by weight of a compound having a molecular weight of 500 or less having two or more oxetanyl groups in one molecule is contained in the whole composition. The active energy ray-curable adhesive composition for a plastic film or sheet according to the item.
- 組成物全体中に、水を0.05~3重量%含有する請求項1~請求項11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 11, wherein 0.05 to 3% by weight of water is contained in the whole composition.
- 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、セルロースアセテート系樹脂、又はシクロオレフィンポリマーである請求項1~請求項12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 a plastic film or sheet according to any one of claims 1 to 12, wherein at least one of the plastic film or sheet is a cellulose acetate resin or a cycloolefin polymer. object.
- 基材、請求項1~請求項12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の硬化物、及び他の基材から構成される積層体であって、
前記基材及び前記他の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。 A laminate comprising a substrate, a cured product of the active energy ray-curable adhesive composition for plastic film or sheet according to any one of claims 1 to 12, and another substrate. And
A laminate in which both or one of the substrate and the other substrate is a plastic film or sheet. - 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、セルロースアセテート系樹脂、又はシクロオレフィンポリマーである請求項14に記載の積層体。 The laminate according to claim 14, wherein at least one of the plastic film or sheet is a cellulose acetate resin or a cycloolefin polymer.
- 基材に、請求項1~請求項12のいずれか1項に記載の組成物を塗工し、塗工面に他の基材を貼合し、前記基材又は前記他の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、
前記基材及び前記他の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 12, and another base material is bonded to the coated surface, and either the base material or the other base material is applied. A method for producing a laminate in which active energy rays are irradiated from the side of
The manufacturing method of the laminated body whose both or one of the said base material and said other base materials is a plastic film or sheet.
Priority Applications (3)
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JP2017530917A JP6555350B2 (en) | 2015-07-29 | 2016-07-28 | Active energy ray-curable adhesive composition for plastic film or sheet |
CN201680044332.7A CN107849420A (en) | 2015-07-29 | 2016-07-28 | Plastics are film-made or piece active energy ray curable adhesive compound |
KR1020187000700A KR20180030508A (en) | 2015-07-29 | 2016-07-28 | Active energy ray curable adhesive composition for plastic film or sheet |
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JP2015-149991 | 2015-07-29 | ||
JP2015149991 | 2015-07-29 |
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PCT/JP2016/072107 WO2017018472A1 (en) | 2015-07-29 | 2016-07-28 | Active-energy-ray curing adhesive composition for plastic film or plastic sheet |
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JP (1) | JP6555350B2 (en) |
KR (1) | KR20180030508A (en) |
CN (1) | CN107849420A (en) |
TW (1) | TW201716526A (en) |
WO (1) | WO2017018472A1 (en) |
Cited By (1)
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JP2017179168A (en) * | 2016-03-30 | 2017-10-05 | 株式会社Adeka | Curable composition, cured article thereof, and production method of the cured article |
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WO2024135756A1 (en) * | 2022-12-22 | 2024-06-27 | 東亞合成株式会社 | Curable adhesive composition |
WO2024135755A1 (en) * | 2022-12-22 | 2024-06-27 | 東亞合成株式会社 | Curable adhesive agent composition |
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KR20180030508A (en) | 2018-03-23 |
JP6555350B2 (en) | 2019-08-07 |
CN107849420A (en) | 2018-03-27 |
TW201716526A (en) | 2017-05-16 |
JPWO2017018472A1 (en) | 2018-06-07 |
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