WO2014065350A1 - 活性エネルギー線硬化型粘接着剤組成物及び積層体の製造方法 - Google Patents

活性エネルギー線硬化型粘接着剤組成物及び積層体の製造方法 Download PDF

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WO2014065350A1
WO2014065350A1 PCT/JP2013/078765 JP2013078765W WO2014065350A1 WO 2014065350 A1 WO2014065350 A1 WO 2014065350A1 JP 2013078765 W JP2013078765 W JP 2013078765W WO 2014065350 A1 WO2014065350 A1 WO 2014065350A1
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component
active energy
group
energy ray
meth
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PCT/JP2013/078765
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English (en)
French (fr)
Japanese (ja)
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一樹 大房
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東亞合成株式会社
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Priority to JP2014543336A priority Critical patent/JP6319088B2/ja
Priority to KR1020157012638A priority patent/KR20150079692A/ko
Publication of WO2014065350A1 publication Critical patent/WO2014065350A1/ja

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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
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/04—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonamides, polyesteramides or polyimides
    • 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
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/08—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/536—Hardness
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/748—Releasability
    • 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
    • B32B2457/00—Electrical equipment

Definitions

  • the present invention relates to an active energy ray-curable adhesive composition, an active energy ray-curable adhesive film or sheet obtained therefrom, and a method for producing the same, and a laminate including a cured product of the composition and a method for producing the same.
  • an active energy ray-curable adhesive composition an active energy ray-curable adhesive film or sheet obtained therefrom, and a method for producing the same, and a laminate including a cured product of the composition and a method for producing the same.
  • the pressure-sensitive adhesive is also called a pressure-sensitive adhesive, and is a kind of adhesive having adhesiveness (also referred to as tackiness) at normal temperature.
  • adhesiveness also referred to as tackiness
  • Adhesives are widely used for adhesive tapes, adhesive labels, adhesive films, and the like because adherends can be bonded together in a short time.
  • the pressure-sensitive adhesive is mainly composed of a polymer having a low glass transition temperature, and a small amount of a crosslinking agent is often used in order to improve cohesion.
  • the adhesive is to be used in applications where the adherend may be exposed to high temperatures, such as for automobiles and displays, it is necessary to increase the cohesive strength at high temperatures, so high crosslink density and glass transition Measures such as temperature increase and high molecular weight are required.
  • high crosslink density and glass transition Measures such as temperature increase and high molecular weight are required.
  • adhesive strength and heat resistance are generally in a trade-off relationship, and trying to improve cohesive strength at high temperatures sacrifices peel strength, so that an adhesive that balances both at a high level can be obtained. was extremely difficult.
  • the adhesive has adhesiveness at room temperature
  • the adherend is a flexible base material such as a film or paper
  • when an external force is applied a dent is formed and the appearance is deteriorated, cutting processing, punching processing, etc.
  • problems such as adhesion of the adhesive to the blade and the tendency to deform the adherend are likely to occur.
  • Patent Document 1 includes a) a polymer of an unsaturated monomer having a carboxyl group, a hydroxyl group or an amino group, b) a crosslinking agent selected from an isocyanate group-containing compound, an epoxy group-containing compound or an aziridinyl group-containing compound, c) a photocurable pressure-sensitive adhesive composition having at least one (meth) acryloyl group and containing a photopolymerizable compound that does not react with a) and b) and a photosensitizer.
  • a photocurable pressure-sensitive adhesive molded product formed into a film or the like has been proposed.
  • Patent Document 2 includes a polymer (A) having any of a carboxyl group, a hydroxyl group, a glycidyl group, an isocyanate group or an amide group on a base sheet or a release sheet, and an unsaturated group capable of reacting with the functional group.
  • An adhesive sheet provided with a pressure-sensitive adhesive layer by applying and drying a mixture containing the compound (B) and the photopolymerization initiator (C) has been proposed.
  • Patent Document 3 includes (a) a polymer having a weight average molecular weight of 10,000 to 2,000,000 and a glass transition temperature of ⁇ 100 ° C. to 100 ° C., (b) a monomer having one or more carbon-carbon double bonds, and (C) An adhesive composition for optical recording media containing an initiator has been proposed.
  • Patent Document 4 contains an adhesive polymer and a radiation curable component as main components, and contains 30 to 150 parts by weight of the radiation curable component with respect to 100 parts by weight of the adhesive polymer.
  • An adhesive radiation curable pressure-sensitive adhesive sheet is proposed.
  • Patent Document 5 discloses a urethane (meth) obtained by reacting an ethylenically unsaturated group-containing acrylic polymer (A), a polyol containing at least one (meth) acrylic polyol, a polyisocyanate, and a hydroxyl group-containing (meth) acrylate.
  • a curable resin composition comprising an acrylate oligomer (B), a photopolymerization initiator (C), and a crosslinking agent (E) has been proposed.
  • Patent Documents 1 to 3 cannot increase the cross-linking density after irradiation with active energy rays because the main polymer itself is not photosensitive. The heat resistance of the adhesive was insufficient. Furthermore, the compositions described in Patent Documents 2 and 3 have a problem that the adhesive agent protrudes from the sheet when the adhesive sheet is produced and stored. In addition, the adhesive described in Patent Document 4 uses a polymer having tackiness at room temperature (preferably having a glass transition temperature of ⁇ 100 to 0 ° C.), and thus has excellent adhesion to an adherend. There is an advantage.
  • the adhesive described in Patent Document 5 has photosensitivity because the polymer itself as a main component contains an ethylenically unsaturated group. Therefore, there is an advantage that the crosslinking density after irradiation with active energy rays can be increased, and the heat resistance of the adhesive can be increased.
  • this adhesive has a problem that it is difficult to achieve both heat resistance and adhesion because shrinkage during curing increases as the crosslinking density is increased.
  • the present invention has a tackiness at the time of bonding with an adherend and can be temporarily bonded, can react firmly by irradiating active energy rays, and can adhere firmly to the adherend, and has heat resistance after irradiation with active energy rays. It aims at providing the active energy ray hardening-type adhesive composition and adhesive sheet which are excellent in film
  • the inventors of the present invention have an activity mainly composed of a polymer having a maleimide group and a polar group and having a glass transition temperature of more than 0 ° C. and not more than 40 ° C.
  • the present inventors have found that an energy ray curable adhesive composition can solve the above-mentioned problems and have completed the present invention.
  • ⁇ 1> The following (A) component, (B) component, (D) component, (E) component, and optionally (C) component, and the following (A) to (C) components (hereinafter these are summarized)
  • the component (A) is 40 to 90% by weight
  • the component (B) is 10 to 60% by weight
  • the component (C) is 0 to 20% by weight.
  • Active energy comprising 0.05 to 10 parts by weight of component (D) and 0.01 to 3 parts by weight of component (E) for 100 parts by weight of the total amount of components A) to (C) Wire curable adhesive composition,
  • composition (B) Component: a compound having two or more ethylenically unsaturated groups in the molecule (C) Component: Compound having one ethylenically unsaturated group in the molecule (D) Component: Photopolymerization initiator and / or sensitizer (E) Component: Thermosetting crosslinking agent ⁇ 2> (A) The active energy ray-curable adhesive composition according to the above ⁇ 1>, wherein the maleimide group of the component is a group represented by the following formula (1):
  • R 1 and R 2 each independently represent a hydrogen atom, a halogen atom, an alkyl group or an aryl group, or R 1 and R 2 are combined to form a 5-membered ring or a 6-membered ring. Represents a hydrocarbon group forming a ring.
  • ⁇ 3> Compound (a) in which component (A) has an ethylenically unsaturated group other than maleimide group and maleimide group [hereinafter also referred to as monomer (a). And a compound (b) having a hydroxyl group or a carboxyl group and an ethylenically unsaturated group [hereinafter also referred to as a monomer (b).
  • R 1 and R 2 each independently represent a hydrogen atom, a halogen atom, an alkyl group or an aryl group, or R 1 and R 2 are combined to form a 5-membered ring or a 6-membered ring. And represents a hydrocarbon group forming a ring, R 3 represents an alkylene group, R 4 represents a hydrogen atom or a methyl group, and n represents an integer of 1 to 6.
  • the monomer (b) has (meth) acrylate having 1 or more hydroxyl groups or carboxyl groups in the molecule: 1 to 30% by weight
  • the monomer (c) is alkyl (meth) acrylate: 20 to 94% by weight ⁇ 7>
  • Adhesive composition ⁇ 8> The active energy ray-curable adhesive composition according to any one of the above ⁇ 1> to ⁇ 7>, further comprising an organic solvent, ⁇ 9> The active energy ray-curable adhesive composition according to any one of the above ⁇ 1> to ⁇ 8>, further comprising a silane coupling agent, ⁇ 10> The active energy ray-curable adhesive composition according to any one of the above ⁇ 1> to ⁇ 9>, further comprising a deterioration inhibitor, ⁇ 11> Adhesive surface obtained by applying the active energy ray-curable adhesive composition according to any one of ⁇ 1> to ⁇ 10> above to a base material and drying to form a film.
  • An active energy ray-curable adhesive sheet obtained by bonding another substrate to ⁇ 12> The active energy ray-curable adhesive sheet according to the above ⁇ 11>, wherein the arithmetic average roughness Ra of at least one of the substrates is 30 nm or less, ⁇ 13>
  • the adherend at the time of joining with an adherend, the adherend can be temporarily adhered, and the adherend can be firmly adhered by reacting with the irradiation of active energy rays.
  • An active energy ray-curable adhesive composition and an adhesive sheet excellent in heat resistance, film hardness and adhesion, and a laminate obtained by using the same can be provided. Therefore, it is possible to manufacture a film laminate that is lightweight, thin, and has good durability with high productivity.
  • AE curable film An example of production of an active energy ray-curable adhesive film or sheet (hereinafter referred to as “AE curable film”) using the active energy ray-curable adhesive composition of the present invention is shown.
  • An example of laminate production using the AE curable film of the present invention is shown.
  • Another example of laminate production using the AE curable film of the present invention is shown.
  • Another example of laminate production using the AE curable film of the present invention will be shown.
  • the active energy ray-curable adhesive composition is also simply referred to as “adhesive composition” or “composition”.
  • the crosslinked or cured product obtained by irradiating the composition with active energy rays is collectively referred to as “cured product”.
  • acrylate or methacrylate is represented as (meth) acrylate.
  • the description of “xx to yy” represents a numerical range including xx and yy.
  • a combination of preferred embodiments is also preferred.
  • the present invention will be described in detail.
  • the active energy ray-curable adhesive composition of the present invention includes the following component (A), component (B), component (D), component (E), and optionally component (C).
  • component (A) is 40 to 90% by weight
  • component (B) is 10 to 60% by weight
  • component (C) is contained in an amount of 0 to 20% by weight, and 0.05 to 10 parts by weight of component (D) and 0.1 part of component (E) with respect to 100 parts by weight of the total amount of components (A) to (C) below. It is characterized by containing 01 to 3 parts by weight.
  • the curable adhesive composition includes (A) component, (B) component, (D) component, and (E) component as essential components, and also includes (C) component as optional components. It is a good composition.
  • the curable component means the components (A) to (C), and is a compound having at least a maleimide group or an ethylenically unsaturated group, and a component that is crosslinked and cured by irradiation with active energy rays. means.
  • the components (A) to (E) will be described.
  • Component (A) in the present invention is a polymer having a maleimide group and a polar group, and having a glass transition temperature (hereinafter also referred to as “Tg”) of more than 0 ° C. and 40 ° C. or less. .
  • the component (A) is preferably a non-adhesive polymer.
  • the maleimide group of component (A) may have a substituent on the maleimide ring in addition to the portion linked to the polymer chain, and is preferably a group represented by the following formula (1).
  • R 1 and R 2 each independently represent a hydrogen atom, a halogen atom, an alkyl group or an aryl group, or R 1 and R 2 are combined to form a 5-membered ring or a 6-membered ring. Represents a hydrocarbon group forming a ring.
  • the alkyl group for R 1 and R 2 is preferably an alkyl group having 4 or less carbon atoms.
  • the alkenyl group for R 1 and R 2 is preferably an alkenyl group having 4 or less carbon atoms.
  • the aryl group in R 1 and R 2 is preferably an aryl group having 6 to 12 carbon atoms, and examples thereof include a phenyl group.
  • Examples of the hydrocarbon group which forms a 5-membered ring or 6-membered ring as one of R 1 and R 2 include saturated hydrocarbons such as —CH 2 CH 2 CH 2 — and —CH 2 CH 2 CH 2 CH 2 —.
  • the hydrocarbon group is preferably a saturated hydrocarbon group.
  • R 1 and R 2 one is a hydrogen atom and the other is an alkyl group having 4 or less carbon atoms, both R 1 and R 2 are alkyl groups having 4 or less carbon atoms, and each forms one to form a carbocycle
  • the saturated hydrocarbon group to be used is preferable in terms of easy molecular weight control in the production of the component (A).
  • saturated hydrocarbon groups that each form a carbocyclic ring are particularly easy to control the molecular weight in the production of component (A) and have excellent adhesion. And more preferable.
  • maleimide group in the formula (1) is shown in the following formulas (3) to (8).
  • X represents a chlorine atom or a bromine atom.
  • Ph in Formula (8) represents a phenyl group.
  • a hydroxyl group and a carboxyl group are preferable from the viewpoints of adhesion to a substrate, storage stability, solubility, and metal corrosivity.
  • the molecular weight of component (A) is preferably 10,000 to 2,000,000, more preferably 50,000 to 1,500,000 in terms of weight average molecular weight.
  • the number average molecular weight and the weight average molecular weight refer to the molecular weight measured by gel permeation chromatography (hereinafter abbreviated as “GPC”) using tetrahydrofuran as a solvent based on the molecular weight of polystyrene. It means the converted value.
  • the component (A) In order to increase the heat resistance and hardness of the cured product, the component (A) needs to have a higher Tg than that of a normal pressure-sensitive adhesive polymer. Specifically, the Tg of the component (A) alone before irradiation with active energy rays exceeds 0 ° C. and is 40 ° C. or less, preferably exceeds 5 ° C. and is less than 30 ° C. When Tg of (A) component is less than 0 degreeC, the heat resistance and hardness of the hardened
  • a transparent conductive film such as a thin film transistor layer or ITO may be formed on the obtained laminate.
  • Tg is the intersection of the tangent line between the base line and the inflection point (the point where the upward convex curve changes to the downward convex curve) of the heat flow curve obtained by the differential scanning calorimetry. means.
  • the content ratio of the component (A) in the active energy ray-curable adhesive composition of the present invention is 40 to 90 wt% in the total amount of the curable component [total amount of the components (A) to (C)]. %, Preferably 50 to 80% by weight. When the content ratio of the component (A) is less than 40% by weight, the adhesiveness is lowered. In addition, when processed into the form of an active energy ray-curable adhesive film or sheet described below, various problems such as flow and deformation occur during storage. Cannot be made high enough.
  • the component (A) various polymers can be used as long as the polymer has a maleimide group and a polar group and has a Tg of more than 0 ° C. and not more than 40 ° C. Among them, a maleimide group and a hydroxyl group can be used.
  • Polymer (A-1) [hereinafter also referred to as “component (A-1)”.
  • the component (A) is preferably a (meth) acrylic resin having a maleimide group and a polar group and having a Tg of more than 0 ° C. and 40 ° C. or less.
  • the components (A-1) and (A-2) will be described in detail.
  • A-1) Component (A-2)
  • the component (A-1) is a polymer having a maleimide group and a hydroxyl group
  • the component (A-2) is a polymer having a maleimide group and a carboxyl group.
  • the maleimide group is as described above.
  • the molecular weight of the components (A-1) and (A-2) is preferably 10,000 to 2,000,000, more preferably 50,000 to 1,500,000 in terms of weight average molecular weight.
  • components (A-1) and (A-2) include the following polymers.
  • 1-1) A copolymer comprising an ethylenically unsaturated compound containing a maleimide group and an ethylenically unsaturated compound containing a hydroxyl group (hereinafter also referred to as “hydroxyl group-containing unsaturated compound”) as essential constituent monomer units.
  • hydroxyl group-containing unsaturated compound an ethylenically unsaturated compound containing a hydroxyl group
  • Ethylenically unsaturated compound containing a hydroxyl group-containing unsaturated compound and an acid anhydride group (hereinafter also referred to as “an acid anhydride group-containing unsaturated compound”) A polymer obtained by adding a compound having a maleimide group and a hydroxyl group to an acid anhydride group-containing polymer.
  • a copolymer comprising an ethylenically unsaturated compound containing a maleimide group and an ethylenically unsaturated compound containing a carboxyl group (hereinafter also referred to as “carboxyl group-containing unsaturated compound”) as essential constituent monomer units.
  • Polymer. 2-2) A polymer obtained by adding a compound having a maleimide group and an isocyanate group to a carboxyl group-containing polymer having a carboxyl group-containing unsaturated compound as an essential constituent monomer unit.
  • the component (A-1) is preferably the polymer 1-1), and the component (A-2) is preferably the polymer 2-1). Furthermore, as the polymer of the above 1-1) and 2-1), the compound (a) having a maleimide group represented by the formula (1) and an ethylenically unsaturated group other than the maleimide group (hereinafter referred to as “ Also referred to as “monomer (a)”. ], A compound (b) having a hydroxyl group or a carboxyl group and an ethylenically unsaturated group [hereinafter also referred to as “monomer (b)”.
  • Monomer (a) is a compound having an ethylenically unsaturated group other than the maleimide group and the maleimide group.
  • a maleimide group that is a photosensitive group can be introduced into the component (A-1), and the photocurability, adhesion, and elastic modulus after curing of the resulting composition are improved. be able to.
  • the maleimide group is preferably a group represented by the formula (1), and preferred specific examples are also the same as described above.
  • Examples of the ethylenically unsaturated group other than the maleimide group include a (meth) acryloyl group, a vinyl group and a vinyl ether group, and a (meth) acryloyl group is preferable.
  • the monomer (a) various compounds can be used as long as they have a maleimide group and an ethylenically unsaturated group other than the maleimide group, and the compound represented by the following formula (2) However, it is preferable because it is easy to produce and excellent in curability.
  • R 1 and R 2 each independently represent a hydrogen atom, a halogen atom, an alkyl group or an aryl group, or R 1 and R 2 are combined to form a 5-membered ring or a 6-membered ring. And represents a hydrocarbon group forming a ring, R 3 represents an alkylene group, R 4 represents a hydrogen atom or a methyl group, and n represents an integer of 1 to 6.
  • R 1 and R 2 one is a hydrogen atom and the other is an alkyl group having 1 to 4 carbon atoms, both R 1 and R 2 are alkyl groups having 1 to 4 carbon atoms, or R 1 and R 2 Is a saturated hydrocarbon group that forms a carbocycle by combining R 1 and R 2 together to form a carbocyclic ring, and is preferably a saturated hydrocarbon group that forms a carbocycle. It is more preferable because there is no problem such as conversion.
  • the alkylene group for R 3 may be linear or branched. An alkylene group having 1 to 6 carbon atoms is preferred.
  • the monomer (b) is a compound having a hydroxyl group or a carboxyl group and an ethylenically unsaturated group. By copolymerizing the monomer (b), a hydroxyl group or a carboxyl group can be introduced into the polymer (A11), and the adhesion of the resulting composition to the substrate can be improved.
  • various compounds can be used as long as the monomer (a) is copolymerizable with the monomer (a) and has a hydroxyl group or a carboxyl group, and one (meth) acryloyl group can be used.
  • Compound having [hereinafter also referred to as “monofunctional (meth) acrylate”. ] A vinyl compound, a vinyl ester, a conjugated diene, etc. can be mentioned. These monomers (b) can be used alone or in combination of two or more.
  • Examples of the ethylenically unsaturated compound having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, and 2-hydroxybutyl (meth).
  • Hydroxyalkyl (meth) acrylates such as acrylate, 4-hydroxybutyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate; glycerol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate And polyalkylene glycol mono (meth) acrylates such as mono (meth) acrylates of polyethylene glycol-polypropylene glycol copolymers, Ethyl (meth) acrylamide, and allyl alcohol.
  • Examples of the compound having a carboxyl group and an ethylenically unsaturated group include (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, cinnamic acid and maleic anhydride, etc .; itaconic acid Monoalkyl esters of unsaturated dicarboxylic acids such as monoethyl ester, fumaric acid monobutyl ester and maleic acid monobutyl ester; ⁇ -carboxypolycaprolactone (meth) acrylate, (meth) acrylic acid dimer, 2- (meth) acryloyl Examples thereof include carboxyl group-containing (meth) acrylates such as loxyethyl phthalic acid and 2- (meth) acryloyloxyethyl hexahydrophthalic acid.
  • a monofunctional (meth) acrylate having a hydroxyl group, an unsaturated carboxylic acid, and a carboxyl group-containing (meth) acrylate have high adhesive strength between the composition containing the copolymer and the optical film, and production It is preferable because of its ease.
  • Monomer (c) The monomer (c) can be copolymerized for the purpose of adjusting physical properties such as Tg, adhesive strength, and adhesive strength of the polymer (A11).
  • the monomer (c) is a compound that has a copolymerizability with the monomers (a) and (b) and has an ethylenically unsaturated group other than the monomers (a) and (b).
  • Various compounds can be used, and examples thereof include monofunctional (meth) acrylates, vinyl compounds, vinyl esters, conjugated dienes, and (meth) acrylamides.
  • Examples of monofunctional (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, and i-butyl.
  • Examples of the vinyl compound include styrene, vinyl toluene, acrylonitrile, methacrylonitrile, N-vinylformamide, acryloylmorpholine, N-vinyl pyrrolidone and N-vinyl caprolactam, vinyl chloride, isobutylene and the like.
  • Examples of the vinyl ester include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl laurate, and vinyl versatate.
  • Examples of the conjugated diene include butadiene, isoprene and chloroprene.
  • Examples of (meth) acrylamide include (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-methoxybutyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, 2- (meth) acrylamide-2-methylpropanesulfonic acid, N-isopropyl (meth) acrylamide and the like.
  • alkyl (meth) acrylates are preferred because of their excellent polymerizability, and among them, (meth) acrylates having an alkyl group having 1 to 20 carbon atoms are preferred.
  • the adhesive strength or adhesive strength is large, and it is more preferable because it is easily available industrially and is inexpensive.
  • Production method of polymer (A11) The production method of the polymer (A11) is not particularly limited, and may be produced according to conventional methods such as solution polymerization, emulsion polymerization and suspension polymerization.
  • Examples of the method for producing by radical polymerization by a solution polymerization method include a method in which a raw material monomer to be used is dissolved in an organic solvent and heated and stirred in the presence of a thermal polymerization initiator. Further, a chain transfer agent can be used to adjust the molecular weight of the polymer, if necessary.
  • thermal polymerization initiator used examples include peroxides that generate radical species by heat, azo compounds, and redox initiators.
  • peroxide include benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, dicumyl peroxide and the like.
  • azo compound examples include azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobis-4-methoxy-2,4-dimethylvaleronitrile, and the like.
  • redox initiators include hydrogen peroxide-iron (II) salt, peroxodisulfate-sodium hydrogen sulfite, cumene hydroperoxide-iron (II) salt, and the like.
  • Organic solvents include hydrocarbon solvents such as n-hexane, benzene, toluene, xylene, ethylbenzene and cyclohexane; Methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, 2-methoxyethanol, 2-ethoxyethanol, 2- (methoxymethoxy) ethanol, 2-isopropoxyethanol, 2-butoxy Ethanol, 2-isopentyloxyethanol, 2-hexyloxyethanol, 2-phenoxyethanol, 2-benzyloxyethanol, furfuryl alcohol, tetrahydrofurfuryl alcohol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, 1 Alcohol solvents such as methoxy-2-propanol and 1-ethoxy-2-propanol; Ether solvents such as tetrahydrofuran, di
  • chain transfer agents include cyanoacetic acid; alkyl esters having 1 to 8 carbon atoms of cyanoacetic acid; bromoacetic acid; alkyl esters having 1 to 8 carbon atoms of bromoacetic acid; anthracene, phenanthrene, fluorene, 9-phenylfluorene, etc.
  • Aromatic compounds p-nitroaniline, nitrobenzene, dinitrobenzene, p-nitrobenzoic acid, p-nitrophenol, p-nitrotoluene and other aromatic nitro compounds; benzoquinone, 2,3,5,6-tetramethyl- benzoquinone derivatives such as p-benzoquinone; borane derivatives such as tributylborane; carbon tetrabromide, 1,1,2,2-tetrabromoethane, tribromoethylene trichloroethylene, bromotrichloromethane, tribromomethane, 3-chloro- Halogenated hydrocarbons such as 1-propene; Chlora Aldehydes such as ru and furaldehyde; alkyl mercaptans having 1 to 18 carbon atoms; aromatic mercaptans such as thiophenol and toluene mercaptan; mercaptoacetic acid; alkyl esters having 1 to 10 carbon atoms
  • the preferable copolymerization ratio of each constituent monomer unit in the polymer (A11) is as follows.
  • the monomer (a) is preferably 5 to 50% by weight, more preferably 10 to 30% by weight.
  • the monomer (b) is preferably 1 to 30% by weight, and more preferably 1 to 25% by weight.
  • the monomer (c) is preferably 20 to 94% by weight, more preferably 45 to 89% by weight.
  • the adhesive force between the composition and the adherend can be increased, and by setting it to 30% by weight or less, the moisture resistance of the composition Sex can be maintained.
  • the copolymerization ratio of the monomer (c) can be 20% by weight or more, the adhesive force between the composition and the adherend can be increased. And photocurability can be maintained.
  • composition of the present invention is a compound (B) having two or more ethylenically unsaturated groups in the molecule for the purpose of imparting excellent hardness, adhesive strength and heat resistance to the cured product (B) Also simply referred to as “component (B)”.
  • component (B) also simply referred to as “component (B)”.
  • the ethylenically unsaturated group include a vinyl group, a vinyl ether group, a (meth) acryloyl group, and a (meth) acrylamide group.
  • the number of ethylenically unsaturated groups in component (B) is preferably 2 to 20, more preferably 2 to 10.
  • a compound having two or more (meth) acryloyl groups [hereinafter also referred to as “polyfunctional (meth) acrylate”.
  • polyfunctional (meth) acrylate include neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol hydroxypivalic acid di (meth) acrylate, caprolactone-modified neopentyl glycol Hydroxypivalic acid di (meth) acrylate, alkylene oxide modified neopentyl glycol di (meth) acrylate, alkylene oxide modified 1,6-hexanediol di (meth) acrylate, neopentyl glycol modified trimethylolpropane di (meth) acrylate, polyethylene Glycol di (meth) acrylate, polypropylene glycol di (meth)
  • oligomers having two or more (meth) acryloyl groups in the molecule such as urethane (meth) acrylate, epoxy (meth) acrylate, and polyester (meth) acrylate, can be mentioned.
  • Urethane (meth) acrylates include reactants of polyhydric alcohols, polyisocyanates and hydroxy (meth) acrylate compounds, and reactants of polyhydric isocyanates and hydroxy (meth) acrylate compounds without using polyhydric alcohols. It is done.
  • polyhydric alcohol examples include polyether polyols such as polypropylene glycol and polytetramethylene glycol, polyester polyols obtained by reaction of the polyhydric alcohol and the polybasic acid, the polyhydric alcohol, the polybasic acid, and ⁇ -caprolactone. And caprolactone polyol obtained by the above reaction, and polycarbonate polyol (for example, polycarbonate polyol obtained by the reaction of 1,6-hexanediol and diphenyl carbonate).
  • organic polyvalent isocyanate examples include isophorone diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane-4,4'-diisocyanate, and dicyclopentanyl diisocyanate.
  • Epoxy (meth) acrylate is a reaction product of an epoxy resin and (meth) acrylic acid.
  • the epoxy resin include bisphenol type epoxy resins such as bisphenol A type epoxy resin and bisphenol F type epoxy resin, and novolac type epoxy resins.
  • the bisphenol A type epoxy resin include Epicoat 827 (trade name, the same applies hereinafter) manufactured by Japan Epoxy Resin Co., Ltd., Epicoat 828, Epicoat 1001, Epicoat 1004, and the like. Epicoat 4004P etc. are mentioned.
  • Examples of the novolak type epoxy resin include Epicoat 152 and Epicoat 154.
  • Polyester (meth) acrylate is a reaction product of polyester polyol and (meth) acrylic acid.
  • the polyester polyol is obtained by a reaction between a polyhydric alcohol and a polybasic acid.
  • the polyhydric alcohol include neopentyl glycol, ethylene glycol, propylene glycol, 1,6-hexanediol, trimethylolpropane, pentaerythritol, tricyclodecane dimethylol and bis (hydroxymethyl) cyclohexane.
  • the polybasic acid include succinic acid, phthalic acid, hexahydrophthalic anhydride, terephthalic acid, adipic acid, azelaic acid, and tetrahydrophthalic anhydride.
  • a compound having a viscosity at 25 ° C. of 1,000 to 10,000,000 mPa ⁇ s is preferable from the viewpoint of adhesive strength before photocuring and storage stability.
  • Specific examples of the compound having a viscosity at 25 ° C. of 1,000 to 10,000,000 mPa ⁇ s include dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and caprolactone-modified dipentaerythritol hexa.
  • urethane (meth) acrylate those produced from polyether polyol, polyester polyol or polycarbonate polyol as the raw material polyol are preferable in terms of excellent weather resistance, transparency and adhesive strength.
  • raw material organic polyisocyanate what was manufactured from isophorone diisocyanate, hexamethylene diisocyanate, and xylene diisocyanate is preferable at the point which is excellent in weather resistance.
  • the content of the component (B) in the active energy ray-curable adhesive composition of the present invention is 10 to 60% by weight, preferably 20 to 50% by weight, based on the total amount of the curable components. . If the content ratio of the component (B) is less than 10% by weight, the hardness of the cured product cannot be made sufficiently high. When processed into the form of a wire curable adhesive film or sheet, various problems such as flow and deformation occur during storage. Moreover, 1 type, or 2 or more types can be used for (B) component.
  • composition of the present invention has one ethylenically unsaturated group in the molecule as a curable component, if necessary, for the purpose of obtaining a composition exhibiting superior adhesive strength and heat resistance.
  • the compound (C) having In addition, the (C) component in this invention shall not contain the silane coupling agent which has the ethylenically unsaturated group mentioned later.
  • numerator does not have a silicon atom.
  • Specific examples include the monomers (a), (b), and (c) described above, and monofunctional (meth) acrylates, vinyl compounds, vinyl esters, conjugated dienes, and (meth) acrylamides. it can.
  • the content ratio of the component (C) is 0 to 20% by weight, preferably 0 to 10% by weight, based on the total amount of the curable component. If it exceeds 20% by weight, the hardness of the cured product cannot be sufficiently increased. Moreover, 1 type, or 2 or more types can be used for (C) component.
  • Component (D) component in this invention is a photoinitiator and / or a sensitizer.
  • the cured product can be excellent in adhesive strength, heat resistance, and surface hardness.
  • the ethylenically unsaturated group of the component (A) is a vinyl group or a (meth) acryloyl group
  • the one that initiates photopolymerization of these groups is defined as a photopolymerization initiator
  • the component (A) When the ethylenically unsaturated group is a maleimide group, a substance that promotes this photodimerization is defined as a sensitizer.
  • a sensitizer a substance that promotes this photodimerization is defined as a sensitizer.
  • Component (D) includes benzyl dimethyl ketal, benzyl, benzoin, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, oligo [2-hydroxy-2-methyl-1- [4-1- (methyl Vinyl) phenyl] propanone, 2-hydroxy-1- ⁇ 4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl ⁇ -2-methylpropan-1-one, 2-methyl-1- [4 -(Methylthio)] phenyl] -2-morpholinopropan-1-one, 2-benzene Dil-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one
  • 1-hydroxycyclohexyl phenyl ketone, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 4-phenylbenzophenone, 4- (methylphenylthio) phenylphenylmethane, 2-chlorothioxanthone, 2,4 -Diethylthioxanthone, isopropylthioxanthone, and 1-chloro-4-propylthioxanthone are preferable from the viewpoints of photoreactivity, adhesive strength, heat resistance, and coloring.
  • the content ratio of the component (D) in the active energy ray-curable adhesive composition of the present invention is 0.05 to 10 parts by weight, preferably 0 with respect to 100 parts by weight of the total amount of the curable components. .5 to 5 parts by weight.
  • the blending ratio of the component (D) is less than 0.05 parts by weight, the composition cannot be cured with an appropriate amount of ultraviolet light, and the productivity cannot be improved. In such a case, the weather resistance and transparency of the cured product may be lowered.
  • thermosetting type crosslinking agent of (E) component is mix
  • at least one crosslinking agent selected from the group consisting of a polyvalent isocyanate compound, a polyvalent epoxy compound, an amino resin, and an organometallic crosslinking agent is preferably exemplified.
  • polyvalent isocyanate compounds include bifunctional isocyanate compounds such as isophorone diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane-4,4′-diisocyanate, dicyclopentanyl diisocyanate, and these bifunctional isocyanate compounds.
  • Terminal isocyanate urethane prepolymer obtained by reacting a bifunctional isocyanate compound and a polyol compound, trimer of bifunctional isocyanate compound, bifunctional isocyanate compound, terminal isocyanate urethane prepolymer such as phenol, oxime, etc. And a block body of a polyvalent isocyanate compound blocked with.
  • polyvalent epoxy compound examples include bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol Z type epoxy resin, and hydrogenated bisphenol type epoxy resin.
  • Bisphenol A type epoxy resins are commercially available, and examples thereof include Epicoat 827 (trade name, the same applies hereinafter), Epicoat 828, Epicoat 1001, and Epicoat 1004 manufactured by Japan Epoxy Resin Co., Ltd. And Epicoat 4004P.
  • novolac epoxy resins such as phenol novolac resins, cresol novolac epoxy resins, glycidyl ether epoxy resins such as polyalkylene polyols (neopentyl glycol, glycerol, etc.) polyglycidyl ethers, tetraglycidyl diaminodiphenylmethane, Glycidyl-epoxy resins such as triglycidyl-p-aminophenol, triglycidyl-m-aminophenol, and tetraglycidyl-m-xylenediamine, and glycidyl ester-based epoxies such as diglycidyl phthalate, diglycidyl hexahydrophthalate, and diglycidyl tetrahydrophthalate , Vinylcyclohexene dioxide, 3,4-epoxycyclohexylmethyl (3,4-epoxycyclohexane
  • amino resins examples include melamine resin, guanamine resin, urea resin, melamine-urea cocondensation resin, melamine-phenol cocondensation resin, and the like.
  • organometallic crosslinking agents include organoaluminum compounds such as aluminum trisacetylacetonate, aluminum tri-i-propionate, aluminum tri-s-butyrate, ethyl acetoacetate aluminum di-i-propylate, titanium tetra-i-propyrate, titanium Tetra-2-ethylhexylate, triethanolamine titanium di-i-propylate, ammonium salt of titanium lactate, tetraoctylene glycol titanate, polyalkyl titanate, polytitanium acylate (polymer of titanium tetrabutyrate, titanium oleate) Organic titanium compounds such as acrylate polymer), zirconium compounds such as zirconium-s-butyrate, zirconium diethoxy-t-butylate, hafni Arm -t- butyrate, other organometallic compounds antimony butyrate, and the like.
  • organoaluminum compounds such as aluminum trisacetylaceton
  • the content ratio of the component (E) in the active energy ray-curable adhesive composition of the present invention is 0.01 to 3 parts by weight, preferably 0 with respect to 100 parts by weight of the total amount of the curable components. 0.01 to 1 part by weight.
  • the content ratio of the component (E) is out of the range of 0.01 to 3 parts by weight, the initial adhesive strength of the layer obtained by curing the composition becomes too low or the storage stability is lowered.
  • composition of the present invention comprises the above-described component (A), component (B), component (D) and component (E), but in addition to these, It may contain C) component and other various components.
  • component (A) component (B), component (D) and component (E), but in addition to these, It may contain C) component and other various components.
  • C component and other various components.
  • Organic Solvent The composition of the present invention preferably contains an organic solvent for the purpose of improving the coating property to the substrate.
  • an organic solvent the organic solvent used by manufacture of (A) component may be used as it is, and you may add separately.
  • Specific examples of the organic solvent include organic solvents used in the production of the component (A).
  • the blending ratio of the organic solvent may be appropriately set, but is preferably 10 to 90% by weight, more preferably 30 to 80% by weight in the composition.
  • a deterioration preventive agent in the composition of the present invention, it is preferable to blend a deterioration preventive agent in order to prevent deterioration of the cured product over time.
  • the deterioration preventing agent include an antioxidant, an ultraviolet absorber, and a light stabilizer.
  • -Antioxidant- Antioxidants include various phenolic antioxidants such as phenolic compounds such as hydroquinone and hydroquinone monomethyl ether, hindered phenolic compounds such as 2,6-di-tert-butyl-4-methylphenol, and polymeric phenolic compounds. And hindered amine-based, sulfur-based secondary antioxidants, phosphorus-based secondary antioxidants, and cuperone-based antioxidants.
  • UV absorber examples include triazine ultraviolet absorbers such as TINUVIN 400, TINUVIN 405, TINUVIN 460, and TINUVIN 479 manufactured by BASF, and benzotriazole ultraviolet absorbers such as TINUVIN 900, TINUVIN 928, and TINUVIN 1130.
  • the light stabilizer examples include hindered amine light stabilizers such as TINUVIN 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 292, and TINUVIN 5100 manufactured by BASF.
  • hindered amine light stabilizers such as TINUVIN 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 292, and TINUVIN 5100 manufactured by BASF.
  • the blending ratio of these deterioration inhibitors is preferably from 0.1 to 5% by weight, more preferably from 0.5 to 2% by weight, based on 100 parts by weight of the solid content of the composition.
  • a silane coupling agent is a compound having one or more alkoxysilyl groups and one or more organic functional groups in one molecule.
  • the organic functional groups include (meth) acryloyl groups, epoxy groups, amino groups, and thiols. Group is preferred, more preferably a (meth) acryloyl group.
  • the silane coupling agent having a (meth) acryloyl group is not included in the component (C).
  • the number of alkoxysilyl groups in the silane coupling agent is preferably 1-20, more preferably 1-10, and the number of organic functional groups in the silane coupling agent is 1-20. It is preferably 1-10.
  • the blending ratio of the silane coupling agent is preferably 0.5 parts by weight or more and 5% by weight or less with respect to 100 parts by weight of the solid content of the composition from the viewpoint of improving heat and moisture resistance and reducing outgas.
  • composition of the present invention can be blended with other components as described later, if necessary.
  • specific examples include photopolymerization initiation assistants, inorganic materials, leveling agents, polymer polymers other than the component (A), plasticizers, polymerization inhibitors, surface lubricants, antifoaming agents, antistatic agents, and the like. it can.
  • these components will be described.
  • a photopolymerization initiation auxiliary agent can be added to the composition of the present invention.
  • the photopolymerization initiation assistant include aliphatic amines and aromatic amines such as diethylaminophenone, dimethylaminobenzoic acid ethyl, and dimethylaminobenzoic acid isoacyl.
  • the blending ratio of the photopolymerization initiation assistant is preferably 0 to 10% by weight, more preferably 0 to 5% by weight, based on 100 parts by weight of the solid content of the composition.
  • the inorganic material can also be blended for the purpose of relaxing the strain at the time of curing of the composition or improving the adhesive force.
  • the inorganic material include colloidal silica, silica, alumina, talc, and clay.
  • the blending ratio of the inorganic material is preferably 0 to 50% by weight, more preferably 0 to 30% by weight, and more preferably 0 to 10% by weight with respect to 100 parts by weight of the solid content of the composition. Is more preferable.
  • the leveling agent include silicone compounds and fluorine compounds.
  • the blending ratio of the leveling agent is preferably 0.5% by weight or less with respect to 100 parts by weight of the solid content of the composition because the adverse effect on the adhesive performance is small.
  • Examples of the polymer other than the component (A) include polyester-based, polycarbonate-based, polyacryl-based, polyurethane-based, and polyvinyl-based resins.
  • Examples of the plasticizer include dioctyl phthalate, diisononyl phthalate, dioctyl adipate, tricresyl phosphate, epoxidized soybean oil, trioctyl trimellitic acid, chlorinated paraffin, and the like.
  • Examples of the polymerization inhibitor include methoquinone, methylhydroquinone, phenothiazine and the like.
  • Examples of the surface lubricant and antifoaming agent include organic polymer, silicone, and fluorine.
  • Examples of the antistatic agent include quaternary ammonium type, polyether type, and conductive powder. The amount of these additives used is appropriately determined within the above range according to the purpose.
  • composition of the present invention essentially comprises the component (A), the component (B), the component (D), and the component (E).
  • the method for producing the composition of the present invention may be in accordance with a conventional method, and the component (A), component (B), component (D) and component (E), and optionally component (C) and other components. Can be obtained by stirring and mixing. If necessary, the mixing time can be shortened by heating.
  • Active energy ray-curable adhesive film or sheet The composition of the present invention is used for production of an active energy ray-curable adhesive film or sheet (AE-curable film).
  • the AE curable film has an adhesive layer of the composition on a substrate.
  • the base material may be a material for adhesion (hereinafter referred to as “adhered body”), and a peelable base material (hereinafter referred to as “release material”) that is independent of the adherend. It may be.
  • adherend body a material for adhesion
  • release material a peelable base material
  • Specific examples of the material of the base material include metals such as glass and aluminum, vapor deposition films of metals and metal oxides, silicon, and polymers.
  • Polymers include polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyamide, polyimide, polycarbonate, epoxy resin, polyurethane, polylactic acid, polyethylene, polypropylene, cycloolefin polymer, acrylic resin, methacrylic resin, polystyrene, polymethacrylstyrene, polyvinyl acetate , Polyvinyl alcohol, triacetyl cellulose, cellulose acetate butyrate, hydroxypropyl cellulose, polyether sulfone, copolymers of the above polymers, liquid crystal polymers and fluororesins.
  • the polymer is preferably a sheet or film.
  • examples include members composed of the materials described above, and preferably include members used in image display devices.
  • release-treated film a film-like or sheet-like substrate subjected to release treatment
  • surface untreated film or sheet-like substrate having releasability hereinafter referred to as “surface untreated”.
  • release treatment in the release treatment film include silicone treatment, long-chain alkyl treatment, and fluorine treatment.
  • Specific examples include a polyethylene terephthalate (hereinafter also referred to as “PET”) film, a polyolefin film, a cycloolefin polymer and the like that have been subjected to a release treatment.
  • PET polyethylene terephthalate
  • Preferable specific examples include silicone-treated PET films.
  • Examples of the surface untreated film having peelability include a surface untreated polyolefin film such as a surface untreated PET film and a surface untreated OPP (stretched polypropylene) film, and a surface untreated cycloolefin polymer.
  • a surface untreated polyolefin film such as a surface untreated PET film and a surface untreated OPP (stretched polypropylene) film
  • a surface untreated cycloolefin polymer As the release material, a silicone-treated PET film, a surface untreated PET film, and a surface untreated cycloolefin polymer are preferable.
  • AE curable film B2 base material / adhesive layer / release material
  • AE curable film B3 release material / adhesive layer / release material
  • the film of B3 is preferable, In the film of B3, a film having the following embodiment is more preferable, in which the release material is a PET film subjected to silicone treatment and an untreated surface PET film.
  • silicone treatment Silicone-treated PET-treated film / Adhesive layer / Silicone-treated PET-treated film Silicone-treated PET-treated film / Adhesive layer / Untreated surface PET film
  • the mold release material a film having a small surface roughness is preferable.
  • the arithmetic average roughness Ra specified in JIS B0601: 2000 is preferably 30 nm or less, and more preferably 20 nm or less.
  • the lower limit of Ra is 0, and Ra of the release material is preferably 0 to 30 nm, more preferably 1 to 30 nm, and further preferably 2 to 20 nm.
  • the thickness of the adhesive layer is preferably 0.5 to 500 ⁇ m, more preferably 10 to 100 ⁇ m.
  • the peel strength can be increased, and even when unevenness is present on the adherend, it can be filled without gaps.
  • the film thickness of a laminated body can be made small and a weight reduction is attained, and the solvent contained in the coating film after drying can be decreased.
  • the adhesive layer is deformed when the release material is peeled off at the time of use, and the force required for peeling increases. Or peeling may not be possible.
  • the adhesive layer is peeling the release material, it is called the slip stick phenomenon, and the substrate is caught during the peeling or is peeled off rapidly. When a phenomenon that vibrates between low peeling forces occurs, the adhesive layer is likely to be deformed to leave a mark.
  • a release-treated film is used as a release material, and the peel strength (pulling speed 300 mm / min) before irradiation with active energy rays between the release-treated film and the adhesive layer is 0.01 N. It is preferable to use one that is less than / mm. By setting this value to less than 0.01 N / mm, it is possible to prevent problems such as the release-processed film not being peeled off smoothly and leaving a mark, or the AE curable film being misaligned.
  • the lower limit of the peel strength is 0 N / mm.
  • Examples of the release treatment film satisfying the peel strength include film binders HTA, KF, BD, DG-2 manufactured by Fujimori Kogyo Co., Ltd.
  • the relationship between the thickness of the adhesive layer and the thickness of the two release processing films is also important.
  • an AE curable film in which the film thickness of the adhesive layer and the film thickness of the two release treatment films is 1 or less in the value of the following formula (T) is preferable.
  • a value of 0.1 to 1 is more preferable, and a value of the following formula (T) is further preferably 0.4 to 0.9.
  • the AE curable film having a value of 1 or less in the above formula (T) can prevent the occurrence of wrinkles and tunnel defects during storage of the AE curable film.
  • the AE curable film of the present invention has sufficient peel strength and gap filling property when applied before curing, and sufficient optical properties, adhesion, surface hardness, heat resistance, low colorability, reliability after curing. Have sex. Even when such an AE curable film is used, even when applied to an image display unit display surface provided with a surface protective layer having an uneven shape or a layer having an uneven shape (for example, a polarizing plate). As a result, it is possible to absorb the irregularities and fill the gaps, and as a result, it is possible to prevent the occurrence of display defects in the image display device. In addition, even when there are variations in the thickness of the film itself, it has sufficient flexibility so that it can be bonded to the surface of the adherend without any gaps, and display unevenness in the image display device can be prevented. .
  • AE curable film As a manufacturing method of AE curable film, various usage methods can be adopted according to the purpose. Specifically, the composition of the present invention is applied to a substrate to form a coating film, or if necessary, after heating and drying to form a dry film, another substrate is pasted. The method etc. which manufacture together are mentioned.
  • FIG. 1 shows an example of a preferred method for producing an AE curable film B2 composed of a substrate / adhesive layer / release material.
  • (1) means a base material
  • (3) means a release material.
  • the composition is a solventless type (FIG. 1: A1)
  • the composition is applied to a substrate [FIG. 1: (1)].
  • the composition contains an organic solvent or the like (FIG. 1: A2)
  • the composition is applied to a substrate [FIG. 1: (1)] and then dried to evaporate the organic solvent (FIG. 1: 1).
  • an adhesive layer is formed on the substrate [FIG. 1: (2)], and an AE curable film is produced (FIG. 1: B1).
  • a release material (3) as a protective film on the adhesive layer as necessary (FIG. 1: B2).
  • a release material is used as the substrate (1), an AE curable film B3 composed of a release material / adhesive layer / release material can be produced.
  • the coating amount of the composition of the present invention may be appropriately selected according to the application to be used, but it is preferable that the coating is performed so that the adhesive layer has the above-described preferable film thickness.
  • a coating method it may be appropriately set depending on the purpose, and a method of coating with a conventionally known bar coat, doctor blade, knife coater, comma coater, reverse roll coater, die coater, gravure coater, micro gravure coater, etc. Is mentioned.
  • the composition When the composition contains an organic solvent or the like, the composition is dried after application to evaporate the organic solvent or the like.
  • the drying conditions may be appropriately set according to the organic solvent to be used, and examples thereof include a method of heating to a temperature of 40 to 140 ° C.
  • a release material [FIG. 1: (3)] as a protective film on the adhesive layer (FIG. 1: B2), and release as a substrate.
  • a mold material can be used, and the adhesive layer can also be laminated with a release material.
  • the AE curable film of the present invention can be preferably used for production of a laminate.
  • a manufacturing method of a laminated body at least any one of the base material or adherend of an AE hardening type adhesive sheet is made into a transparent material, these are bonded together, and an active energy ray is irradiated from the transparent material side.
  • the method of hardening is mentioned.
  • the AE curable film and the adherend after they can be cured with active energy rays, or the active energy rays can be irradiated after the adherends are bonded together.
  • the active energy rays include ultraviolet rays, visible rays, X-rays, and electron beams. Since inexpensive devices can be used, it is preferable to use ultraviolet rays and / or visible rays.
  • Various light sources can be used as the light source in the case of curing with ultraviolet rays and / or visible light. Suitable light sources include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultrahigh-pressure mercury lamps, metal halide lamps, UV electrodeless lamps, and LEDs that emit ultraviolet light and / or visible light. What is necessary is just to set suitably irradiation conditions, such as irradiation intensity
  • FIG. 2 shows an example in which an AE curable film laminated with a release material is used and cured by irradiation with active energy rays from the sheet-like substrate side.
  • (1) means a base material
  • (2) means an adhesive layer
  • (3) means a release material.
  • the release material is released from the AE curable film immediately before use (FIG. 2: 2-1), and the adhesive layer and the adherend (4) are brought into close contact (FIG. 2: 2- 2)
  • Active energy rays are irradiated from the substrate side (FIG. 2: 2-3), and an article (FIG. 2: 2-4) as a laminate is manufactured.
  • FIG. 3 shows an example in which a laminate is manufactured by using an AE curable film B3 laminated with two release materials and bonding two adherends together.
  • (2) means an adhesive layer
  • (3) means a release material.
  • the release material is released from the AE curable film immediately before use (FIG .: 3-1), and the adhesive layer and the adherend [FIG. 2: (5)] are brought into close contact (FIG. 3).
  • 3: 3-2) the other release material is released (FIG .: 3-3), and the adhesive layer and another adherend [FIG. 2: (4)] are brought into close contact (FIG. 2).
  • 3: 3-4) active energy rays are irradiated from the adherend (1) side (FIG. 3: 3-5), and an article (FIG. 3: 3-6) as a laminate is manufactured.
  • FIG. 4 uses an AE curable film B3 laminated with two release materials, and is bonded to an adherend and cured by irradiating active energy rays, and then the release material is removed.
  • An example of manufacturing is shown.
  • (2) means an adhesive layer
  • (3) means a release material.
  • the release material is released from the AE curable film immediately before use (FIG .: 4-1), and the adhesive layer and the adherend [FIG. 4: (5)] are brought into close contact (FIG. 4). 4: 4-2), active energy rays were irradiated from the release material (3) side (FIG. 4: 4-3), the other release material was released (FIG. 4: 4-4), and the laminate Are produced (FIG. 4: 4-5).
  • the article manufactured from the AE curable film of the present invention includes an image display device, a recording medium, a nanoimprint material, and the like.
  • An image display device is preferable, and a touch panel is more preferable.
  • touch panel type image display device hereinafter, the touch panel type image display device will be described.
  • the touch panel type image display device is mainly composed of a surface protective layer, a touch panel, and an image display unit.
  • the AE curable film of the present invention can be mainly used to fill a gap between the surface protective layer or the touch panel and the image display unit and a gap between the surface protective layer and the touch panel.
  • the image forming apparatus of the present invention is at least one selected from the group consisting of a touch panel module, a surface protective layer, and an image display unit by a cured product of the resin composition for an active energy ray-curable adhesive according to the present invention. One is preferably fixed.
  • the surface protective layer is a layer disposed on the outermost surface when disposed on the image display device.
  • the surface protective layer may be composed of only a polymer film, glass, or the like, or may be composed of a plurality of layers together with other layers.
  • the surface protective layer only needs to be conventionally used as a protective film for an image display device, and can be, for example, an acrylic resin such as polymethyl methacrylate (PMMA), a polycarbonate resin, or glass.
  • the thickness of the surface protective layer is preferably 0.1 to 5 mm.
  • the observer side of the image display device has functions such as wear resistance, scratch resistance, antifouling properties, antireflection properties, and antistatic properties.
  • a layer for imparting characteristics can be provided.
  • abrasion resistance and scratch resistance can be obtained by forming a hard coat layer.
  • antistatic properties, antifouling properties and the like can be impart to the hard coat layer.
  • the surface protective layer is a laminate composed of a plurality of layers
  • an additional layer such as a printed layer, a hard coat layer, or a vapor deposition layer is formed on the entire surface or a part of the surface protective layer on the opposite side of the observer side. It may be included in the area.
  • the surface protective layer becomes a surface having an uneven shape.
  • the thickness of the surface protective layer is preferably 0.1 to 6 mm as a whole.
  • Examples of the touch panel include various methods such as a resistance film method, a surface capacitance method, and a capacitance method such as a projection capacitance method.
  • Examples of the image display unit include transmissive or reflective liquid crystal display units, plasma display units, organic EL (OLED) units, and electronic paper image display units.
  • An additional functional layer (single layer or multiple layers), for example, a polarizing plate or the like can be provided on the display surface of the image display unit.
  • a touch panel may be present on the display surface of the image display unit.
  • the touch panel image display device can be used for various electronic devices.
  • the electronic device include a mobile phone, a smart phone, a portable information terminal, a portable game machine, an electronic book, a car navigation system, a portable music player, a clock, a tablet computer, a video camera, a video player, a digital camera, Examples include a positioning system (GPS) device and a personal computer (PC).
  • GPS positioning system
  • PC personal computer
  • part means part by weight
  • % means weight%
  • room temperature represents 23 ° C. unless otherwise specified.
  • MMA methyl methacrylate
  • EHMA 2-ethylhexyl methacrylate
  • BA butyl acrylate
  • HEA 2-hydroxyethyl acrylate
  • AA acrylic acid
  • V-65 2,2′-azobis (2,4-dimethylvaleronitrile)
  • DM dodecyl mercaptan
  • EtAc ethyl acetate
  • the solution containing the copolymer A-1 had a nonvolatile content of 46.1%, the number average molecular weight of A-1 (hereinafter also referred to as Mn) was 15,700, and the weight average molecular weight (hereinafter also referred to as Mw). It was 173,000.
  • THPI 15.0 g
  • MMA 17.5 g
  • BA 7.5 g
  • HEA 10.0 g
  • EtAc 45 g
  • V-65 0.40 g
  • DM 0.05 g
  • the solution containing the obtained copolymer A-6 had a non-volatile content of 50.1%, Mn of A-6 was 16,500, and Mw was 216,000.
  • THPI 15.0 g
  • MMA 14.5 g
  • BA 10.5 g
  • HEA 10.0 g
  • EtAc 45 g
  • V-65 0.40 g
  • DM 0.05 g
  • the solution containing the copolymer A-7 had a non-volatile content of 49.8%, the Mn of A-7 was 15,300, and the Mw was 223,000.
  • MMA 24.5 g
  • BA 15.5 g
  • HEA 10.0 g
  • EtAc 45 g
  • V-65 0.55 g
  • DM 0.09 g
  • BHT 0.05 g
  • DBTDL 0.05 g
  • Table 1 summarizes the monomers and other components used for the polymers (A) and the polymers other than the component (A) obtained in Production Examples 1 to 7 and Comparative Production Examples 1 to 4.
  • the total amount of monomers used is shown in parts so that the total amount is 100 parts.
  • the non volatile matter, molecular weight, and Tg were measured in accordance with the following method. The results are shown in Table 1.
  • Nonvolatile content The obtained copolymer solution was dried at 150 ° C for 1 hour, and the nonvolatile content (% by weight) was calculated from the weight before and after the drying of the sample.
  • Tg glass transition temperature
  • Example 1 to 12 The compounds shown in Table 2 below were charged into a stainless steel container at the ratio shown in Table 2 and stirred at room temperature until uniform with a magnetic stirrer to obtain an active energy ray-curable adhesive composition.
  • the unit of the amount used of each component in Table 2 is “part”.
  • the component (A) and the organic solvent were blended using the copolymer solutions obtained in Production Examples 1 to 7.
  • the components (A) and The organic solvents are listed separately. Comparative examples S1 to S4 are also described in the same manner.
  • a release film “Film Vina HTA” (silicone-treated polyethylene terephthalate film, thickness 75 ⁇ m) manufactured by Fujimori Kogyo Co., Ltd. having a width of 300 mm and a length of 300 mm so that the film thickness after drying the obtained composition is 25 ⁇ m. It was coated with a bar coater and dried with a hot air dryer at 90 ° C. for 5 minutes. Thereafter, a release film “Film Vina KF” (silicone-treated PET film, thickness 50 ⁇ m) manufactured by Fujimori Kogyo Co., Ltd.
  • adheresive sheet AE-curing adhesive A sheet having a width of 300 mm ⁇ a length of 300 mm is laminated on the adhesive layer, and AE-curing adhesive A sheet (hereinafter simply referred to as “adhesive sheet”) was obtained. About the obtained adhesive sheet, it evaluated by the following method. The results are shown in Table 3.
  • the release film “Film Binder KF” of the adhesive sheet is peeled off, and in accordance with JIS K6854-3 under the conditions of a peel width of 25 mm, 23 ° C., 50% RH, and a tensile speed of 300 mm / min. Accordingly, a T-shaped peel test was performed to obtain a release treatment film peelability (1). Next, a 50 ⁇ m thick PET film (trade name “Cosmo Shine A-4300” manufactured by Toyobo Co., Ltd.) was applied to the adhesive film from which the release film “Film Vina KF” was peeled off.
  • the other release treatment film “Film Bina HTA” was peeled off, and a T-type peel test was performed under the above measurement conditions to obtain a release treatment film peelability (2).
  • peelability an AE curable film or an adhesive film was cut into a 15 cm square size, a release treatment film on one side was peeled off with a finger, and an easy adhesion treated polyethylene terephthalate film (product) The film was bonded to a name “Cosmo Shine A-4300” manufactured by Toyobo Co., Ltd. using a bonding roller.
  • the other release treatment film was peeled off with the finger in the same manner, and bonded to a 20 cm square slide glass.
  • Adhesion peel off the release film “Film Binder KF” of the adhesive sheet, and paste the easy-adhesion-treated PET film “Cosmo Shine A-4300” (manufactured by Toyobo Co., Ltd., film thickness 50 ⁇ m).
  • the film “Film Bina HTA” was peeled off and bonded to a white slide glass (S-1112 manufactured by Matsunami Glass Industrial Co., Ltd.).
  • Ultraviolet rays were irradiated through the “Cosmo Shine A-4300” by passing four passes under a condensing high-pressure mercury lamp (120 W / cm, one lamp, lamp height 30 cm) at a conveyor speed of 7 m / min (365 nm light). Illuminance of 200 mW / cm 2 , integrated light quantity per pass 0.5 J / cm 2 ).
  • a cross-cut test was conducted in accordance with JIS K5400 under the conditions of 23 ° C. and 50% RH, and used as an index of adhesion.
  • the numerical value of the adhesiveness described in Table 3 represents the number of squares in which the film was not peeled and the adhesiveness was good in the 100 square cross cut test according to JIS K5400.
  • the release film “Film Bina KF” of the adhesive sheet was peeled off and bonded to a white slide glass (S-1112 manufactured by Matsunami Glass Industrial Co., Ltd.).
  • the other release film “Film Bina HTA” was irradiated with ultraviolet rays using the same apparatus and conditions as in the adhesion test. After the ultraviolet irradiation, the release film was peeled off, and the Martens hardness was measured using an ultra-fine film hardness meter (Fischer Scope H100C manufactured by Fischer Instruments) under the conditions of 23 ° C. and 50% RH.
  • the Martens hardness here is a value calculated according to ISO 14577 from the load-penetration depth curve using a Vickers indenter, applying a load of 10 mN in 5 seconds, removing the load after holding for 5 seconds. is there.
  • the release film “Film Vina KF” of the adhesive sheet is peeled off, and an easy adhesion treated PET film “Cosmo Shine A-4300” (manufactured by Toyobo Co., Ltd., film thickness 50 ⁇ m) is further bonded.
  • the other release film “Film Bina HTA” was peeled off and bonded to a white slide glass (S-1112 manufactured by Matsunami Glass Industry Co., Ltd.).
  • Ultraviolet rays were irradiated through the “Cosmo Shine A-4300” by passing four passes under a condensing high-pressure mercury lamp (120 W / cm, one lamp, lamp height 30 cm) at a conveyor speed of 7 m / min (365 nm light). Illuminance of 200 mW / cm 2 , integrated light quantity per pass 0.5 J / cm 2 ). Then, it heated at 200 degreeC * 30 minutes supposing forming transparent conductive films, such as a thin-film transistor layer and ITO, in the obtained laminated body. Then, it cooled to room temperature and external appearance observation was carried out, and it was set as heat resistance evaluation.
  • TPO 2,4,6-trimethylbenzoyldiphenylphosphine oxide
  • PBZ 4-phenylbenzophenone
  • BMS 4-benzoyl-4′-methyldiphenyl sulfide
  • Irg-184 1-hydroxycyclohexyl phenyl ketone, BASF Japan
  • Irgacure 184 P301-75E: Trifunctional isocyanate compound, “Duranate P301-75E” manufactured by Asahi Kasei Chemicals Corporation
  • M-313 Isocyanuric acid ethylene oxide-modified di- and triacrylate, Aronix M-313 manufactured by Toagosei Co., Ltd., viscosity at 25 ° C.
  • Examples 1 to 12 which are the adhesive compositions of the present invention, are excellent in releasability from a release material and transferability at room temperature, and further, adhesion after irradiation with active energy rays, hardness of a cured product, low It was excellent in coloring and wet heat resistance.
  • Comparative Examples 1 and 4 are adhesive compositions containing A′-1 and A′-4, which are copolymers having a Tg of 0 ° C. or less, respectively, but after irradiation with active energy rays. The hardness of the cured product was insufficient.
  • Comparative Example 2 is a composition containing a polymer A′-2 having a Tg of more than 40 ° C., and the cured product after UV irradiation was not tacky, so that the cured product can be evaluated. In addition, transferability at room temperature was poor.
  • Comparative Example 3 is a composition containing the copolymer A′-3 containing an acryloyl group, but the cured product has very low adhesion and is also inferior in heat and humidity resistance, so it cannot be put into practical use. It was.
  • Example S1 to S12 and Comparative Examples S1 to S4 Compositions excellent in coloration resistance and wet heat resistance
  • the following AO-80 and 0. 10 parts and 1 part of the following KBM-5103 as a silane coupling agent.
  • compositions corresponding to the compositions of Examples 1 to 12 and Comparative Examples 1 to 4 and further containing a deterioration inhibitor and a coupling agent were used as Examples S1 to S12 and Comparative Examples S1 to S1, respectively. It is called S4.
  • AO-80 Phenol antioxidant, “ADEKA STAB AO-80” manufactured by ADEKA Corporation AS3010: Phosphite antioxidant, “ADEKA STAB 3010” manufactured by ADEKA Corporation KBM-5103: 3-acryloxypropyltrimethoxysilane, “KBM-5103” manufactured by Shin-Etsu Chemical Co., Ltd.
  • compositions of Examples S1 to S12 and the compositions of Comparative Examples S1 to S4 were evaluated for the release treatment film peelability, room temperature transferability, adhesion, Martens hardness and heat resistance. The same results as those of the corresponding compositions of Examples 1 to 12 and Comparative Examples 1 to 4 were obtained.
  • the compositions of Examples S1 to S12 and the compositions of Comparative Examples S1 to S4 were further evaluated for color resistance using a yellow index according to the following method, and wet heat resistance was evaluated. The results are shown in Table 4.
  • compositions of Examples 1 to 12 have a yellow index after the heat resistance test of about 1.2 to 1.5, whereas the compositions of Examples S1 to S12 are yellow after the heat resistance test. The index was 0.32 to 0.87 with little coloring.
  • the compositions of Examples 1 to 12 hardly show any cured product after the cross cut test, whereas all the compositions of Examples S1 to S12 have the cross cut test. The number of remaining masses was 100, which was excellent in heat and humidity resistance.
  • the adhesive compositions of Comparative Examples S1 and S4 had no problem with respect to coloring resistance and moist heat resistance. However, as described above, the hardness and wet heat resistance of the cured product after irradiation with active energy rays were insufficient.
  • Examples F1 to F3, Comparative Examples F1 and F2 The composition obtained in Example 11 was applied to various films having a width of 300 mm and a length of 300 mm with a bar coater so that the film thickness after drying was 25 ⁇ m, and dried with a hot air dryer at 90 ° C. for 5 minutes. Thereafter, a release film “Film Vina KF” (silicone-treated PET film, thickness 50 ⁇ m) manufactured by Fujimori Kogyo Co., Ltd. having a width of 300 mm ⁇ a length of 300 mm is laminated on the adhesive layer, and AE-curing adhesive A sheet (hereinafter also simply referred to as “adhesive sheet”) was obtained. About the obtained adhesive sheet, it evaluated by the following method. The results are shown in Table 5.
  • Coating-side film surface roughness was measured in accordance with JIS B0601: 2000 using a Keyence laser microscope "VK-9710".
  • the adhesive side film of the adhesive film is peeled off, and using a haze meter NDH2000 manufactured by Nippon Denshoku Industries Co., Ltd. under the conditions of 23 ° C. and 50% RH, according to JIS K7165: 1981, D65
  • the haze of the coating film was measured using a light source and used as an index for the transparency of the coating film.
  • ZF14 cycloolefin polymer film, “ZEONOR ZF-14” manufactured by Zeon Corporation (film thickness 100 ⁇ m)
  • A4100 Easy adhesion treated PET film, “COSMO SHINE A-4100” manufactured by Toyobo Co., Ltd.
  • U49G Easy adhesion treated PET film, “Lumirror U-49G” manufactured by Toray Industries, Inc.
  • BX8 Silicone-treated PET film, “Therapel BX-8” (film thickness: 38 ⁇ m) manufactured by Toray Film Processing Co., Ltd.
  • ⁇ HTA Silicone-treated PET film, “Film Bina HTA” (film thickness 50 ⁇ m) manufactured by Fujimori Industry Co., Ltd.
  • Examples F1 to F3 are the compositions of Example 11 and are examples in which a film having a small surface roughness was used as a release material on the coating side, and the cured product was excellent in transparency.
  • Comparative Examples F1 and F2 used a film having a large surface roughness, and thus the transparency of the cured coating film was low.
  • the composition of the present invention when bonded to the adherend, it can be tacky and temporarily bonded, and can be firmly bonded to the adherend by reacting with irradiation of active energy rays.
  • An AE curable adhesive sheet excellent in film hardness can be produced.
  • an optical film laminate that is particularly lightweight, thin, and durable can be produced with high productivity.
  • the active energy ray-curable adhesive sheet of the present invention is useful as an adhesive between the same or different materials such as fibers, composite materials, ceramics, glass, rubber, concrete, paper, metal, and plastics.
  • Adhesion of display materials, touch panel and liquid crystal panel, and touch panel and touch panel such as front window Various optical films used for flat panel displays (brightness enhancement film, prism sheet, light diffusion sheet, Fresnel lens, lenticular lens, polarizing film, retardation film, color filter, light guide plate, antiglare film, antireflection film, Adhesion of reflective sheets, conductive films, near-infrared cut filters, electromagnetic wave shielding films, viewing angle control films, viewing angle compensation films, heat ray reflective films, gas barrier films, thin film transistors, etc., and adhesion of laminates used in electrical circuits Various materials and members such as and the like can be suitably used for bonding and manufacturing a laminate.

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