JP6172038B2 - Active energy ray-curable adhesive composition for plastic film or sheet and method for producing laminate - Google Patents

Description

The present invention relates to an active energy ray-curable adhesive composition for plastic films or sheets, an active energy ray-curable adhesive film or sheet obtained therefrom, a method for producing the same, and a cured product of the composition. It is related with the laminated body containing and its manufacturing method.
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, plastic films or sheets are collectively expressed as “plastic film”, and films or sheets are collectively expressed as “film”.

2. Description of the Related Art Liquid crystal displays (hereinafter referred to as “LCD”) and organic EL (OLED) are widely used as image display devices used in mobile devices such as mobile phones, smartphones, and portable game machines.
In recent years, in these image display devices for mobile devices, the refractive index of the voids existing between the surface protective layer or the touch panel and the display surface of the image display unit, or between the surface protective layer and the touch panel. There has been proposed a method of improving the brightness and contrast of an image display apparatus by suppressing the reflection of light by filling a transparent material close to the above, thereby improving the transparency. Examples of the transparent material include a transparent resin sheet, a reaction curable liquid resin, and an adhesive.

  Patent Document 1 discloses a viscosity that does not cause the sheet to swell and dissolve between the transparent resin sheet and one or both of the liquid crystal display panel and the transparent protective plate via a transparent resin sheet made of a plasticizer-containing acrylic polymer. A method of manufacturing an LCD is disclosed in which a viewing side of a liquid crystal display panel and a transparent protective plate are brought into close contact with each other in a state where a volatile liquid of 10 cp or less is provided, and then dried under heating and pressing.

  Patent Document 2 fixes a liquid crystal display element and a glass plate by injecting a reaction-curable silicone gel, which is a colorless and transparent elastic resin, between the liquid crystal display element and the glass plate in a liquid state and then curing the gel. An LCD manufacturing method is disclosed.

  Patent Document 3 discloses an LCD in which a transparent material is filled between a liquid crystal display element and a protective plate. As the transparent material, a material in which an unsaturated polyester is dissolved in a polymerizable monomer is used, which is solidified after being injected into a gap between the liquid crystal display element and the protective plate.

  Patent Document 4 discloses a pressure-sensitive adhesive composition for an optical member containing a (meth) acrylic polymer obtained by copolymerizing an alkyl (meth) acrylate and a hydroxyl group-containing (meth) acrylate at a specific ratio, and a peroxide. .

JP 09-197387 A Japanese Patent Laid-Open No. 06-59253 Japanese Patent Laid-Open No. 03-204616 JP 2007-31506 A

As described above, transparent resin sheets, reactive curable liquid resins, adhesives, and the like have been proposed as transparent materials for filling voids used in image display devices.
However, since the transparent resin sheet has a higher elastic modulus than the liquid resin and the pressure-sensitive adhesive, there is a problem that the gap filling property is poor.
In addition, the reaction curable liquid resin becomes a process for handling a liquid, and the manufacturing process becomes complicated. Further, the silicone gel has a low adhesive force and has a problem in reliability.

On the other hand, since the adhesive is easy to handle, has a high yield, and has high reliability, it is suitable for a structure in which the image display device and the surface protective layer are directly bonded.
However, the surface protective layer in the image display device has a concavo-convex shape such as a light-shielding layer, and when sticking an adhesive on the concavo-convex shape surface, When pasting the agent, even if the uneven shape is filled without gaps, even if it is left for a long time under high temperature and high humidity conditions, air bubbles are generated at the surface protective layer, the display surface of the image display unit, or the interface with the touch panel module. It is necessary that no peeling occurs and no whitening occurs. In recent years, the uneven film thickness tends to increase from the viewpoint of design, and the demand for gap filling properties and reliability is increasing, and there is a need for void filling resins that solve this problem.

On the other hand, for the purpose of reducing the thickness and weight of the touch panel and reducing the cost of components, plastics such as polycarbonate, polymethyl methacrylate, and polycarbonate / polymethyl methacrylate co-extruded products are used as the material constituting the touch panel. It has been studied to use it for the front plate of the machine.
In recent years, part of the so-called OGS (One Glass Solution), a cover-integrated touch panel that directly forms a touch sensor such as ITO on the cover glass, has been adopted for the purpose of reducing the thickness and weight of the touch panel, improving the transmittance, and reducing the cost of components. Has been. However, since the OGS type touch panel has insufficient impact resistance of glass, there is a problem that when the mobile device is dropped, the cover glass is easily broken and the touch panel cannot be operated.
Therefore, so-called OPS (One Plastic Solution) has been proposed in which a plastic having excellent impact resistance is used instead of glass as a cover material, and a touch sensor such as ITO is directly formed on the plastic.

However, when conventional void filling resins and adhesives are used for plastics such as polycarbonate and polymethylmethacrylate, there is a problem that bubbles are generated at the interface under conditions where heat and humidity are applied.
The inventor is excellent in void filling and reliability, and when it is attached to an article, particularly on the surface protective layer of the image display device, the display surface of the image display unit or the touch panel, bubbles do not occur at the interface, Since we conducted an intensive study to find an active energy ray-curable adhesive composition for plastic films that does not generate bubbles or peel even when left at high temperature and high humidity for a long time and has excellent peel strength. is there.

As a result of intensive studies to solve the above-mentioned problems, 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.
That is, the present invention includes the following component (A), component (B), component (D), component (E), and optionally component (C),
In the total of the following components (A) to (C) (hereinafter collectively referred to as “curable components”), the component (A) is 40 to 90% by weight, and the component (B) is 10 to 60% by weight. And (C) component 0 to 20 wt%,
For plastic film or sheet, 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 curable components The present invention relates to an active energy ray-curable adhesive composition.
(A) Component: a polymer having a maleimide group and a polar group, and having a glass transition temperature exceeding 0 ° C. and not exceeding 40 ° C. (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

  The active energy ray-curable adhesive composition of the present invention and the active energy ray-curable film obtained therefrom are excellent in void filling properties, such as bubbles, peeling and whitening even when left at high temperature and high humidity for a long time. Therefore, when the surface protective layer of the image display device, the display surface of the image display unit or the touch panel is manufactured, problems such as the above-mentioned bubbles, peeling and whitening do not occur, and the peel strength is also improved. A high-quality image display device that is excellent can be obtained.

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.

In the present specification, 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”. In the present specification, the description of “xx to yy” represents a numerical range including xx and yy. In the present invention, a combination of preferred embodiments is also preferred.
Hereinafter, 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). In the total of the components A) to (C) (hereinafter collectively referred to as “curable components”), the component (A) is 40 to 90% by weight, the component (B) is 10 to 60% by weight, and ( The component (C) is contained in an amount of 0 to 20% by weight, and the component (D) is added in an amount of 0.05 to 10 parts by weight and the component (E) is added in an amount of 0.1 to an amount of 100 parts by weight of the following components (A) to (C). It contains 0.01 to 3 parts by weight.
(A) Component: a polymer having a maleimide group and a polar group, and having a glass transition temperature exceeding 0 ° C. and not exceeding 40 ° C. (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 Active energy ray of the present invention 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.
In the present invention, 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.
Hereinafter, the components (A) to (E) will be described.

1. Component (A) 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).

（式（１）中、Ｒ¹及びＲ²は、それぞれ独立に水素原子、ハロゲン原子、アルキル基若しくはアリール基を表すか、又は、Ｒ¹及びＲ²は一つとなって５員環若しくは６員環を形成する炭化水素基を表す。）

(In 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, preferably an aryl group having 6 to 12 carbon atoms include a phenyl group.
Examples of the hydrocarbon group that forms a 5-membered 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 —. And unsaturated hydrocarbon groups such as —CH═CH—CH ₂ CH ₂ — and —CH ₂ CH═CHCH ₂ —.
In the unsaturated hydrocarbon group, in order for the maleimide group to undergo a dimerization reaction, it is necessary to select a finally obtained 5-membered or 6-membered ring having no aromaticity. The hydrocarbon group is preferably a saturated hydrocarbon group.
As 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).
Furthermore, among these, as R ¹ and R ² , 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.

  Preferred specific examples of the maleimide group in the formula (1) are shown in the following formulas (3) to (8). In the formula (7), X represents a chlorine atom or a bromine atom. Moreover, Ph in Formula (8) represents a phenyl group.

As the polar group of the component (A), carboxyl group, acid anhydride group, hydroxyl group, amino group, amide group, glycidyl group, cyano group, phosphoric acid group, sulfonic acid, imide group, isocyanate group, nitrogen-containing heterocyclic residue A hydroxyl group and a carboxyl group are preferable from the viewpoints of adhesion to a substrate, storage stability, solubility, and metal corrosivity.
Furthermore, when the composition is applied to adhesive such as a transparent conductive layer formed from indium tin oxide (ITO) or silver nanowires, a hydroxyl group is preferred because of excellent corrosion resistance.

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.
In the present invention, 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.

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 | cured material obtained after active energy ray irradiation will fall. Furthermore, a transparent conductive film such as a thin film transistor layer or ITO may be formed on the obtained laminate. In this case, the laminate is rapidly heated, but if the Tg of the component (A) is less than 0 ° C., wrinkles and cracks are generated in the obtained laminate. On the other hand, if it exceeds 40 ° C., transfer to the adherend becomes difficult at room temperature.
In the present invention, Tg is the intersection of the tangent line at the base line and the inflection point (the point at which 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 weights in the total amount of the curable components [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 shape of an AE curable film described later, various problems such as flow and deformation occur during storage, and if it exceeds 90% by weight, the coating film hardness may be sufficiently increased. It becomes impossible.

As 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) having [hereinafter also referred to as “component (A-1)”. ], Polymer (A-2) having a maleimide group and a carboxyl group [hereinafter also referred to as “component (A-2)”]. ] Is preferable. 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.
Hereinafter, the components (A-1) and (A-2) will be described in detail.

1-1. (A-1) (A-2) Component The component (A-1) is a polymer having a maleimide group and a hydroxyl group, and the component (A-2) is a polymer having a maleimide group and a carboxyl group.
Here, 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.

Specific examples of the component (A-1) 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 an essential constituent monomer unit. .
1-2) A polymer obtained by adding a compound having a maleimide group and an isocyanate group to a hydroxyl group-containing polymer having a hydroxyl group-containing unsaturated compound as an essential constituent monomer unit.
1-3) Hydroxyl and carboxyl group-containing weights containing a hydroxyl group-containing unsaturated compound and a carboxyl group-containing ethylenically unsaturated compound (hereinafter also referred to as “carboxyl group-containing unsaturated compound”) as essential constituent monomer units. A polymer obtained by adding a compound having a maleimide group and an epoxy group to a coalescence.
1-4) Containing a hydroxyl group and an epoxy group containing an ethylenically unsaturated compound containing a hydroxyl group-containing unsaturated compound and an epoxy group (hereinafter also referred to as “epoxy group-containing unsaturated compound”) as an essential constituent monomer unit A polymer obtained by adding a compound having a maleimide group and a carboxyl group to a polymer.
1-5) An 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.
1-6) A polymer obtained by adding a compound having a maleimide group and a carboxyl group to a polymer containing a hydroxyl group and an epoxy group.

Specific examples of the component (A-2) include the following polymers.
2-1) Copolymers 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.
2-3) A polymer obtained by adding a compound having a maleimide group and an epoxy group to a carboxyl group-containing polymer having a carboxyl group-containing unsaturated compound as an essential constituent monomer unit.
2-4) A polymer obtained by adding a compound having a maleimide group and a hydroxyl group to an acid anhydride group-containing polymer having an ethylenically unsaturated compound containing an acid anhydride group 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 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)”. And a compound (c) having an ethylenically unsaturated group other than the monomers (a) and (b) [hereinafter also referred to as “monomer (c)”. ] To obtain a polymer [hereinafter also referred to as “polymer (A11)”]. ] Is more preferable.
Hereinafter, the monomers (a) to (c) will be described.

1-1-1. Monomer (a)
The monomer (a) is a compound having the maleimide group and an ethylenically unsaturated group other than the maleimide group. By copolymerizing the monomer (a), 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.

  As 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.

（式（２）中、Ｒ¹及びＲ²は、それぞれ独立に水素原子、ハロゲン原子、アルキル基若しくはアリール基を表すか、又は、Ｒ¹及びＲ²は一つとなって５員環若しくは６員環を形成する炭化水素基を表し、Ｒ³はアルキレン基を表し、Ｒ⁴は水素原子又はメチル基を表し、ｎは１〜６の整数を表す。）

(In Formula (2), 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. A hydrocarbon group that forms 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.)

As 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. Preferably it is a C1-C6 alkylene group.

1-1-2. Monomer (b)
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.
As the monomer (b), 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, hydroxy Chill (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; ω-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.

  Among these, 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.

1-1-3. 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 the monofunctional (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, and i-butyl. (Meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, i-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) ) Acrylate, i-nonyl (meth) acrylate, i-myristyl (meth) acrylate, n-decyl (meth) acrylate, i-decyl (meth) acrylate, n-lauryl (meth) acrylate, tridecyl (meth) acrylate and n -Stearyl (meth) acryl Alkyl of over preparative like (meth) acrylate;
Cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate and tricyclodecane (meth) ) Alicyclic alkyl (meth) acrylates such as acrylates;
Alkoxy group content such as methoxypolyethylene glycol (meth) acrylate such as 2-methoxyethyl (meth) acrylate, ethoxyethoxyethyl (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate and methoxytriethylene glycol (meth) acrylate ( (Meth) acrylate;
Such as benzyl (meth) acrylate, phenol alkylene oxide modified (meth) acrylate, alkylphenol alkylene oxide modified (meth) acrylate, p-cumylphenol alkylene oxide modified (meth) acrylate and o-phenylphenol alkylene oxide modified (meth) acrylate (Meth) acrylate having an aromatic ring (the alkylene oxide includes ethylene oxide and propylene oxide);
(Meth) acrylates having a heterocyclic ring such as pentamethylpiperidinyl (meth) acrylate, tetramethylpiperidinyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate and N- (meth) acryloyloxyethyl hexahydrophthalimide; And mono [2- (meth) acryloyloxyethyl] phosphate, mono [2- (meth) acryloyloxypropyl] phosphate, 2- (meth) acryloyloxyethyldiphenyl phosphate, mono [3-chloro-2- (meth) acryloyl Oxypropyl] phosphate, mono [(meth) acryloyloxyethyl] phosphate monoethanolamine salt, mono [(meth) acryloyloxyethyl] phosphate, [mono (diethylaminoethyl (meth) acrylate) Rate) salt, mono [(meth) acryloyloxyethyl] phosphate, and phosphoric acid (meth) acrylate such as [mono (dimethylaminoethyl (meth) acrylate) salt].

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 can be mentioned.

  Among the above-mentioned monomers (c), alkyl (meth) acrylate is preferable because of its excellent polymerizability. Among them, (meth) acrylate having an alkyl group having 1 to 20 carbon atoms is preferable. The adhesive strength or adhesive strength is large, and it is more preferable because it is easily available industrially and is inexpensive.

1-1-4. 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.

Examples of the thermal polymerization initiator used include peroxides that generate radical species by heat, azo compounds, and redox initiators.
Examples of the peroxide include benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, dicumyl peroxide and the like. Examples of the azo compound include azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobis-4-methoxy-2,4-dimethylvaleronitrile, and the like. Examples of redox initiators include hydrogen peroxide-iron (II) salt, peroxodisulfate-sodium hydrogen sulfite, cumene hydroperoxide-iron (II) salt, and the like.

As organic solvents, 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-based solvents such as methoxy-2-propanol and 1-ethoxy-2-propanol;
Ether solvents such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, bis (2-methoxyethyl) ether, bis (2-ethoxyethyl) ether and bis (2-butoxyethyl) ether;
Ketone solvents such as acetone, methyl ethyl ketone, methyl-n-propyl ketone, diethyl ketone, butyl methyl ketone, methyl isobutyl ketone, methyl pentyl ketone, di-n-propyl ketone, diisobutyl ketone, phorone, isophorone, cyclohexanone and methylcyclohexanone;
Methyl formate, ethyl formate, propyl formate, butyl formate, isobutyl formate, pentyl formate, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, pentyl acetate and isopentyl acetate Ester solvents such as;
Nitromethane, nitroethane, 1-nitropropane, 2-nitropropane, acetonitrile, propionitrile, butyronitrile, N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, 2-pyrrolidone, N-methyl And nitrogen compound solvents such as pyrrolidone and ε-caprolactam; and sulfur compound solvents such as dimethyl sulfoxide and sulfolane.

  Examples of the chain transfer agent 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; Chlorer Aldehydes such as aldehyde, fulleraldehyde, etc .; 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 of mercaptoacetic acid; Hydroxylalkyl mercaptans, and terpenes such as pinene and terpinolene.

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, and 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, and more preferably 45 to 89% by weight.
By making the copolymerization ratio of the monomer (a) 5% by weight or more, the photocurability of the resulting composition can be made sufficient, and by making it 50% by weight or less, (A- 1) In addition to facilitating the production of the components, the resulting composition has excellent adhesive strength and can be less colored.
By setting the copolymerization ratio of the monomer (b) to 1% by weight or more, 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.
By setting the copolymerization ratio of the monomer (c) to 20% by weight or more, the adhesive force between the composition and the adherend can be increased. And photocurability can be maintained.

2. Component (B) The composition of the present invention is a compound (B) having two or more ethylenically unsaturated groups (hereinafter simply referred to as “(”) for the purpose of imparting excellent hardness, adhesive strength and heat resistance to the cured product. Also referred to as “B) component”. ] Is blended.
Examples of the ethylenically unsaturated group include a vinyl group, a vinyl ether group, a (meth) acryloyl group, and a (meth) acrylamide group.
Moreover, it is preferable that the number of the ethylenically unsaturated groups in (B) component is 2-20 pieces, and it is more preferable that it is 2-10 pieces.

As an example of the component (B), a compound having two or more (meth) acryloyl groups [hereinafter also referred to as “polyfunctional (meth) acrylate”. ].
Specific examples of the 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) acrylate, tricyclodecane dimethylol di (meth) acrylate, dicyclopentanyl (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, C2-C5 aliphatic modified dipentaerythritol penta (meth) acrylate, C2-C5 aliphatic modified di Pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, pentaerythritol tetra (meth) acrylate, tris [(meth) Acryloxyethyl] isocyanurate, caprolactone-modified tris [(meth) acryloxyethyl] isocyanurate, ditrimethylolpropane tetra (meth) acrylate, etc. It is.

  Furthermore, 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.

  Examples of the polyhydric alcohol include polyether polyols such as polypropylene glycol and polytetramethylene glycol, polyester polyols obtained by the reaction of the polyhydric alcohol and the polybasic acid, the polyhydric alcohol, the polybasic acid, and ε-caprolactone. Caprolactone polyol obtained by the above reaction, polycarbonate polyol (for example, polycarbonate polyol obtained by reaction of 1,6-hexanediol and diphenyl carbonate, etc.) and the like.

  Examples of the organic polyvalent isocyanate 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.
Examples of 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. Examples of 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.
Examples of the polyhydric alcohol include neopentyl glycol, ethylene glycol, propylene glycol, 1,6-hexanediol, trimethylolpropane, pentaerythritol, tricyclodecane dimethylol and bis (hydroxymethyl) cyclohexane.
Examples of the polybasic acid include succinic acid, phthalic acid, hexahydrophthalic anhydride, terephthalic acid, adipic acid, azelaic acid, and tetrahydrophthalic anhydride.

As the component (B), among the compounds described above, 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 compounds 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. (Meth) acrylate, alkylene oxide modified isocyanuric acid di (meth) acrylate, alkylene oxide modified isocyanuric acid tri (meth) acrylate, ε-caprolactone modified isocyanuric acid di (meth) acrylate, ε-caprolactone modified isocyanuric acid tri (meth) acrylate , Urethane (meth) acrylate, epoxy (meth) acrylate, and polyester (meth) acrylate are preferable.
By setting the viscosity of the component (B) at 25 ° C. to 1,000 mPa · s or more, the adhesive strength and storage stability before irradiation with active energy rays can be improved. On the other hand, when the viscosity is 10,000,000 mPa · s or less, the workability when producing the composition and the appearance of the cured product are excellent.

  Further, as the 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. Moreover, as 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.

Content of (B) component in the active energy ray hardening-type adhesive composition of this invention is 10 to 60 weight% in the total amount of a sclerosing | hardenable component, Preferably it is 20 to 50 weight%. .
If the content ratio of the component (B) is less than 10% by weight, the hardness of the cured product cannot be sufficiently increased, and if it exceeds 60% by weight, the adhesiveness is lowered or AE curing described later. When processed into the shape of a mold film, various problems such as flow and deformation occur during storage.
Moreover, 1 type, or 2 or more types can be used for (B) component.

3. Component (C) The composition of the present invention contains 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.
Moreover, it is preferable that the compound which has one ethylenically unsaturated group in a molecule | 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.

(C) The content rate of a component is 0-20 weight% in the total amount of a sclerosing | hardenable component, Preferably it is 0-10 weight%. 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.

4). (D) Component (D) component in this invention is a photoinitiator and / or a sensitizer. By including the component (D), the cured product can be excellent in adhesive strength, heat resistance, and surface hardness.
Usually, when 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, and the component (A) When the ethylenically unsaturated group is a maleimide group, a substance that promotes this photodimerization is defined as a sensitizer. However, since there are compounds having both functions, it is difficult to distinguish them. And / or sensitizer ".

As component (D), benzyldimethyl 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, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-ylphenyl) butane Aromatic ketone compounds such as -1-one, Adekaoptomer N-1414 (manufactured by ADEKA), phenylglyoxylic acid methyl ester, ethyl anthraquinone, phenanthrenequinone;
Benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, 4- (methylphenylthio) phenylphenylmethane, methyl-2-benzophenone, 1- [4- (4-Benzoylphenylsulfanyl) phenyl] -2-methyl-2- (4-methylphenylsulfonyl) propan-1-one, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis Benzophenones such as (diethylamino) benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone, N, N′-tetraethyl-4,4′-diaminobenzophenone and 4-methoxy-4′-dimethylaminobenzophenone Compound;
Bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate and bis (2,6- Acylphosphine oxide compounds such as dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide;
Thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 1-chloro-4-propylthioxanthone, 3- [3,4-dimethyl-9-oxo-9H-thioxanthone-2-yl] oxy]- Thioxanthone compounds such as 2-hydroxypropyl-N, N, N-trimethylammonium chloride and fluorothioxanthone;
Acridone compounds such as acridone, 10-butyl-2-chloroacridone;
1,2-octanedione 1- [4- (phenylthio) -2- (O-benzoyloxime)] and ethanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] Oxime esters such as -1- (O-acetyloxime);
2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-phenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 2 2,4,5-triarylimidazole such as 2,4-di (p-methoxyphenyl) -5-phenylimidazole dimer and 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazole dimer Dimer; and acridine derivatives such as 9-phenylacridine and 1,7-bis (9,9′-acridinyl) heptane.
These compounds may be used alone or in combination of two or more.

  Among these, 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 rate of (D) component in the active energy ray hardening-type adhesive composition of this invention is 0.05-10 weight part with respect to 100 weight part of total amounts of a sclerosing | hardenable component, Preferably it is 0. .5 to 5 parts by weight.
When 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.

5. (E) component In the composition of this invention, since the storage stability and peelability which were excellent in the film before hardening can be provided, the thermosetting type crosslinking agent of (E) component is mix | blended.
As the component (E), 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.

  Examples of the polyvalent isocyanate compound include bifunctional isocyanate compounds such as isophorone diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane-4,4′-diisocyanate, dicyclopentanyl diisocyanate, and the like. 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.

Examples of the polyvalent epoxy compound 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.
The bisphenol A type epoxy resin is commercially available, and examples thereof include Epicoat 827 (trade name, the same applies hereinafter), Epicoat 828, Epicoat 1001, Epicoat 1004, etc. manufactured by Japan Epoxy Resin Co., Ltd. And Epicoat 4004P.

  In addition to these, 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 ester epoxy resins such as triglycidyl-p-aminophenol, triglycidyl-m-aminophenol, tetraglycidyl-m-xylenediamine, etc., diglycidyl phthalate, diglycidyl hexahydrophthalate, diglycidyl tetrahydrophthalate, etc. , Vinylcyclohexene dioxide, 3,4-epoxycyclohexylmethyl (3,4-epoxycyclohexane) carboxylate DOO, (3,4-epoxy-6-methylcyclohexanol methyl) cycloaliphatic type such as adipate, triglycidyl iso Woo rates, heterocyclic epoxy resins such as glycidyl glycidoxy alkyl hydantoin and the like. Furthermore, halogen compounds of these epoxy resins, polyglycidyl esters of polybasic acids or polyester polycarboxylic acids of these epoxy resins, and polyglycidyl ethers of polyester polyols.

  Examples of the amino resin include melamine resin, guanamine resin, urea resin, melamine-urea cocondensation resin, and melamine-phenol cocondensation resin.

  Examples of organometallic crosslinking agents include organoaluminum compounds such as aluminum trisacetylacetonate, aluminum tri-i-propionate, aluminum tri-s-butyrate, ethylacetoacetate aluminum di-i-propylate, titanium tetra-i-propylate, and 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, -t- butyrate, other organometallic compounds such as antimony butyrate, and the like.

The content rate of (E) component in the active energy ray hardening-type adhesive composition of this invention is 0.01-3 weight part with respect to 100 weight part of total amounts of a sclerosing | hardenable component, Preferably it is 0. 0.01 to 1 part by weight.
When the content rate of (E) component remove | deviates from the range of 0.01-3 weight part, the initial stage adhesive force of the layer which hardened | cured the said composition will become low too much, or storage stability will fall.

6). Other components The composition of the present invention comprises the above-described component (A), component (B), component (D) and component (E), but in addition to these, C) A component and other various components may be included. Hereinafter, other components will be described.

6-1. Organic Solvent The composition of the present invention preferably contains an organic solvent for the purpose of improving the coating property to the substrate. As 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.

6-2. 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.
Examples of 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, cuperone-based antioxidants, and the like.

<Ultraviolet absorber>
Examples of the UV absorber include triazine UV absorbers such as TINUVIN 400, TINUVIN 405, TINUVIN 460, and TINUVIN 479 manufactured by BASF, and benzotriazole UV absorbers such as TINUVIN 900, TINUVIN 928, and TINUVIN 1130.

<Light stabilizer>
Examples of the light stabilizer include 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 0.1 to 5% by weight and more preferably 0.5 to 2% by weight with respect to 100 parts by weight of the solid content of the composition.

6-3. Silane coupling agent It is preferable to mix | blend a silane coupling agent with the composition of this invention for the purpose of improving adhesiveness with a base material and improving wet heat resistance.
A silane coupling agent is a compound having one or more alkoxysilyl groups and one or more organic functional groups in one molecule. Examples of the organic functional groups include (meth) acryloyl groups, epoxy groups, amino groups, and thiols. Group is preferred, more preferably a (meth) acryloyl group.
As described above, 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. Preferably, it is 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.

6-4. In addition to the above, the composition of the present invention can be blended with other components described later as required. 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.
Hereinafter, these components will be described.

In order to further increase the reactivity, a photopolymerization initiation assistant can be added to the composition of the present invention.
Examples of 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 and more preferably 0 to 5% by weight with respect to 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.
Examples of 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 0 to 10% by weight with respect to 100 parts by weight of the solid content of the composition. Is more preferable.
Examples of 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.

7). Active energy ray curable adhesive composition for plastic film or sheet The composition of the present invention essentially comprises the component (A), component (B), component (D) and component (E). is there.
The production method of the composition of the present invention may be in accordance with a conventional method, the component (A), the component (B), the component (D) and the component (E), and optionally the component (C) and other components. Can be obtained by stirring and mixing. If necessary, the mixing time can be shortened by heating.

As the composition of the present invention,
The 25 ° C. storage elastic modulus G ′ (frequency 1 Hz) (hereinafter simply referred to as “G ′ (25 ° C.)”) of the coating layer (coating coating or dry coating) of the composition is 0.001 to 1.0 MPa,
The composition has a 85 ° C. storage elastic modulus G ′ (frequency: 1 Hz) (hereinafter simply referred to as “G ′ (85 ° C.)”) of 0.001 to 0.05 MPa and a composition after irradiation with active energy rays. It is preferable that the cured product has a storage elastic modulus E ′ (frequency: 1 Hz) (hereinafter simply referred to as “E ′”) of 5.0 to 5000 MPa.
In addition, a coating film means the film obtained by coating the solventless composition which does not contain (D) component (organic solvent), and a dry film contains (D) component (organic solvent). It means a film obtained by heating and drying after applying the composition.

G ′ (25 ° C.) of the coating layer of the composition is an especially important factor for void filling.
By setting G ′ (25 ° C.) of the coating layer before irradiation with active energy rays to 0.001 MPa or more, the coating layer (filled resin layer) does not leak out when being applied to the adherend, and the laminate. Can be made favorable. In addition, when G ′ (25 ° C.) is set to 1.0 MPa or less, a display defect of an image display device is caused when a film including a coating layer is bonded to an adherend having an uneven surface of about 10 to 20 μm. And display unevenness can be prevented.
In addition, as G '(25 degreeC), 0.002-0.7 Mpa is more preferable.

By setting G ′ (85 ° C.) of the coating layer before irradiation with the active energy ray to 0.001 MPa or more, the coating layer (filled resin layer) does not leak out when being applied to the adherend, and the laminate. Can be made favorable. Further, by setting G ′ (85 ° C.) to 0.05 MPa or less, even when a film including a composition layer is bonded to an adherend having an uneven surface of about 10 to 20 μm, the display of the image display device The occurrence of defects and display unevenness can be prevented.
As G ′ (85 ° C.), 0.001 to 0.01 MPa is more preferable.

  In addition, G '(25 degreeC) and G' (85 degreeC) of the coating layer before hardening can be adjusted by changing suitably the kind of each component, molecular weight, and composition ratio in a composition.

G ′ (25 ° C.) and G ′ (85 ° C.) before active energy ray irradiation are obtained by laminating a coating layer and preparing a sample with a predetermined thickness, and then moving in shear mode according to JIS K7244-6. It is obtained by measuring the dynamic viscoelasticity. The thickness of the sample is appropriately selected depending on the elastic modulus of the sample, the amount of strain applied, and the like.
In the present invention, G ′ (25 ° C.) means a value measured at 25 ° C. by measuring at a thickness of 100 μm, a strain of 0.2%, a measurement frequency of 1 Hz, and a heating rate of 2 ° C./min. 85 ° C.) means a value measured at 85 ° C. under the same conditions.

Moreover, by setting E ′ of the cured product of the composition after irradiation with active energy rays to 5.0 MPa or more, the water resistance and heat resistance of the cured product can be improved. As a result, an image display device excellent in reliability can be obtained. E ′ is preferably 5.0 to 5000 MPa, more preferably 5.0 to 100 MPa.
E ′ of the cured product of the composition can be adjusted by appropriately changing the type, molecular weight, and composition ratio of each component in the composition.

E ′ of the cured product of the composition after irradiation with active energy rays was obtained by laminating a filling resin layer and preparing a sample with a predetermined thickness, and then curing the sample by irradiating with active energy rays. The cured product was determined by measuring dynamic viscoelasticity in the tensile mode according to JIS K7244-4. The thickness of the sample is appropriately selected depending on the elastic modulus of the sample, the width of the sample, the amount of strain applied, and the like.
In the present invention, E ′ is a sample cured with a thickness of 100 μm and a UV integrated light quantity of ² J / cm ² (365 nm light), and measured at a strain of 0.5%, a frequency of 1 Hz, and a temperature rising rate of 2 ° C./min. The value measured at 85 ° C.

8). 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.
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 polycarbonate, (meth) acrylic resin, polyethylene terephthalate, polyethylene naphthalate and other polyester, polyamide, polyimide, epoxy resin, polyurethane, polylactic acid, polyethylene, polypropylene, cycloolefin polymer, 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.
As described above, the composition of the present invention has excellent foam resistance even when applied to polycarbonate and (meth) acrylic resin as an adherend.
In the case where the substrate is an adherend, examples include members composed of the materials described above, and preferably include members used in image display devices.

As the release material, a film-like or sheet-like substrate subjected to a release treatment (hereinafter referred to as “release-treated film”) and a surface untreated film or sheet-like substrate having peelability (hereinafter referred to as “surface untreated”). And so on).
Examples of the 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. 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.
As the release material, a silicone-treated PET film, a surface untreated PET film, and a surface untreated cycloolefin polymer are preferable.

Examples of the AE curable film include films having the following forms.
AE curable film B2: base material / adhesive layer / release material AE curable film B3: release material / adhesive layer / release material As the AE curable film, 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-treated PET-treated film / Adhesive layer / Silicone-treated PET-treated film Silicone-treated PET-treated film / Adhesive layer / Untreated surface PET film

As the mold release material, a film having a small surface roughness is preferable. Specifically, the arithmetic average roughness Ra specified in JIS B0601: 2000 is preferably 30 nm or less, and more preferably 20 nm or less. By using a release material having an Ra of 30 nm or less, the transparency of the cured coating film can be increased.
Moreover, the lower limit value 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.

As a film thickness of an adhesive agent layer, 0.5-500 micrometers is preferable, More preferably, it is 10-500 micrometers, Especially preferably, it is 50-500 micrometers.
By setting the film thickness of the adhesive layer to 0.5 μm or more, the peel strength can be increased, and even when unevenness is present on the adherend, it can be filled without a gap. Moreover, by setting the film thickness to 500 μm or less, it is possible to reduce the film thickness of the laminate to reduce the weight, and to reduce the solvent contained in the coating film after drying.

In the AE curable film B3, 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.
In addition, when 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.

In order to prevent this, 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 displaced.
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, and DG-2 manufactured by Fujimori Kogyo Co., Ltd.

Furthermore, in this case, the relationship between the thickness of the adhesive layer and the thickness of the two release processing films is also important.
In this case, 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 more preferably 0.4 to 0.9.
(Film thickness of adhesive layer) / (Total film thickness of two release treatment films) (T)
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). The gaps can be absorbed and the gaps can be filled, and as a result, display defects in the image display device can be prevented. 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. .

9. Manufacturing method of 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.

A more specific manufacturing method will be described with reference to FIG.
FIG. 1 shows an example of a preferred method for producing an AE curable film B2 composed of a substrate / adhesive layer / release material.
In FIG. 1, (1) means a base material, and (3) means a release material.
When the composition is a solventless type (FIG. 1: A1), the composition is applied to a substrate [FIG. 1: (1)]. When 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 or the like (FIG. 1: 1). -1).
By these methods, an adhesive layer is formed on the substrate [FIG. 1: (2)], and an AE curable film is produced (FIG. 1: B1).
In this AE curable film B1, it is preferable to laminate a release material (3) as a protective film on the adhesive layer as required (FIG. 1: B2).
In the above, if 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.
As 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.

When the composition contains an organic solvent or the like, it is dried after coating to evaporate the organic solvent or the like.
What is necessary is just to set drying conditions suitably according to the organic solvent etc. to be used, and the method etc. which heat to the temperature of 40-140 degreeC are mentioned.

  After the production of the AE curable film, as described above, it is preferable to laminate 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.

10. Method of using AE curable film The AE curable film of the present invention can be preferably used for production of a laminate.
As a method for producing a laminate, a method is used in which at least one of the substrate or adherend of an AE curable film is made of a transparent material, these are bonded together, and are cured by irradiating active energy rays from the transparent material side. Is mentioned. Moreover, after bonding an AE curable film and a to-be-adhered body, it can harden | cure with an active energy ray, or it can also irradiate an active energy ray after adhering to-be-adhered bodies.
Further, the AE curable film of the present invention can be used for filling voids of articles having various voids (hereinafter simply referred to as “articles”), and manufacturing image recording devices, recording media such as Blu-ray, and nanoimprint materials. Can be preferably used, and can be preferably used by manufacturing an image display device.
As a method for filling a gap in an article, a method in which at least one of a base material or an adherend of an AE curable film is made of a transparent material, these are bonded, and cured by irradiating active energy rays from the transparent material side. Etc.

Examples of the active energy rays include ultraviolet rays, visible rays, X-rays, and electron beams. Since an inexpensive apparatus can be used, it is preferable to use ultraviolet rays or / and 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 | strength in active energy ray irradiation, according to the composition to be used, a base material, the objective, etc.

A more specific method for manufacturing a laminate will be described with reference to FIGS.
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. In the AE curable film B2 of FIG. 2, (1) means a base material, (2) means an adhesive layer (or void resin layer), and (3) means a release material.
In FIG. 2, 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) An active energy ray is irradiated from the base material side (FIG. 2: 2-3), and the article | item (FIG. 2: 2-4) which is a laminated body 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. In the AE curable film B3 of FIG. 3, (2) means an adhesive layer (or void resin layer), and (3) means a release material.
In FIG. 3, 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), after releasing the other release material (FIG .: 3-3) and bringing the adhesive layer and another adherend [FIG. 2: (4)] into close contact (FIG. 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. In the AE curable film B3 of FIG. 4, (2) means an adhesive layer (or a void resin layer), and (3) means a release material.
In FIG. 4, the release material is released from the AE curable film immediately before use (FIG .: 4-1), and the adhesive layer (or the void resin layer) and the adherend [FIG. 4: (5)]. (FIG. 4: 4-2), and then, the active energy ray is irradiated from the release material (3) side (FIG. 4: 4-3), and the other release material is released (FIG. 4: 4-4) An article (FIG. 4: 4-5) which is a laminate is manufactured.

11. Image Display Device Including Touch Panel As described above, 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. (Hereinafter, referred to as “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 examples thereof include acrylic resins such as polycarbonate and polymethyl methacrylate (PMMA), glass, and the like. Since the curable film is excellent in the foam resistance of the plastic film as described above, it can be preferably applied when polycarbonate and (meth) acrylic resin are used as the surface protective layer.
The thickness of the surface protective layer is preferably 0.1 to 5 mm.

When the surface protective layer is a laminate composed of a plurality of layers, 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.
For example, abrasion resistance and scratch resistance can be obtained by forming a hard coat layer. Furthermore, it is possible to impart antistatic properties, antifouling properties and the like to the hard coat layer.

When 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.
When such an additional layer is formed in a partial region of the surface protective layer, the surface protective layer becomes a surface having an uneven shape. The thickness of the surface protective layer in this case is preferably 0.1 to 6 mm as a whole.

  When sticking the adhesive to the surface protective layer having an uneven shape at the end, or when attaching the adhesive to the display surface of the image display unit provided with a layer having an uneven shape at the end, Even if those uneven shapes are filled without any gaps, and bubbles and peeling do not occur at the interface with the surface protective layer, the display surface of the image display unit, or the touch panel module even when left under high temperature and high humidity conditions for a long time, Further, it is necessary that no whitening occurs. By laminating using the composition of the present invention, no bubbles are generated at the interface, no bubbles or peeling occurs even if left for a long time under high temperature and high humidity, and further no whitening occurs. A high-quality image display device can be obtained.

  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 image display units such as electronic paper.
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.
Specific examples of the electronic device include a mobile phone, a smartphone, 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).

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. In the following description, “part” means part by weight, and “%” means weight%. Further, “room temperature” represents 23 ° C. unless otherwise specified.

ＨＥＡ ：２−ヒドロキシエチルアクリレート
ＭＭＡ ：メチルメタクリレート
ＨＡ ：２−エチルヘキシルアクリレート
ＢＡ ：ブチルアクリレート
ＥＨＭＡ ：２−エチルヘキシルメタクリレート
ＣＨＡ ：シクロヘキシルアクリレート
ＣＨＭＡ ：シクロヘキシルメタクリレート
ＥｔＡｃ ：酢酸エチル
ＢｕＡｃ ：酢酸ブチル
Ｖ−６５ ：２，２’−アゾビス（２，４−ジメチルバレロニトリル）
ＡＭＢＮ ：２，２’−アゾビス（２−メチルブチロニトリル）
ＤＭ ：ドデシルメルカプタン 1. Production Examples The meanings of the abbreviations used in the production examples are as follows.
THPI: Compound represented by the following formula (11)

HEA: 2-hydroxyethyl acrylate MMA: methyl methacrylate HA: 2-ethylhexyl acrylate BA: butyl acrylate EHMA: 2-ethylhexyl methacrylate CHA: cyclohexyl acrylate CHMA: cyclohexyl methacrylate EtAc: ethyl acetate BuAc: butyl acetate V-65: 2, 2 '-Azobis (2,4-dimethylvaleronitrile)
AMBN: 2,2′-azobis (2-methylbutyronitrile)
DM: Dodecyl mercaptan

1) Production Example 1 [ Production of Component (A) A-1]
The following compounds were charged in a flask equipped with a stirrer, a thermometer, and a cooler at 25 ° C. in the following amounts, and uniformly dissolved while blowing nitrogen at a flow rate of 50 mL / min.
THPI: 15.0 g, MMA: 14.5 g, BA: 10.5 g, HEA: 10.0 g, EtAc: 73 g, V-65: 0.10 g, DM: 0.01 g
While continuing nitrogen blowing, the temperature was raised and the mixture was stirred at 85 ° C. for 30 minutes, then heated to 90 ° C., and the following mixture was added dropwise over 3 hours, and then stirred for 5 hours.
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-1 had a non-volatile content of 49.8%, the Mn of A-1 was 15,300, the Mw was 223,000, and the Tg was 10 ° C.

2) Production Example 2 [ Production of Component (A) A-2]
The following compounds were charged in the same manner as in Production Example 1 and dissolved uniformly.
THPI: 15.0 g, CHA: 25.0 g, HA: 2.5 g, BA: 2.5 g, HEA: 5.0 g, EtAc: 94.9 g, V-65: 0.1 g
Thereafter, the temperature was raised and the mixture was stirred in the same manner and under the same conditions as in Production Example 1, and then the following mixed solution was added dropwise, followed by stirring.
THPI: 15.0 g, CHA: 25.0 g, HA: 2.5 g, BA: 2.5 g, HEA: 5.0 g, EtAc: 58.5 g, V-65: 0.4 g
The non-volatile content of the solution containing the obtained copolymer A-2 was 39.4%, Mn of A-2 was 18,300, Mw was 139,000, and Tg was 14 ° C.

3) Production Example 3 [ Production of Component (A) A-3]
The following compounds were charged in the same manner as in Production Example 1 and dissolved uniformly.
THPI: 0.5 g, MMA: 28.5 g, BA: 16.0 g, HEA: 5.0 g, EtAc: 91.3 g, V-65: 0.10 g, DM: 0.01 g
Thereafter, the temperature was raised and the mixture was stirred in the same manner and under the same conditions as in Production Example 1, and then the following mixed solution was added dropwise, followed by stirring.
THPI: 0.5 g, MMA: 28.5 g, BA: 16.0 g, HEA: 5.0 g, EtAc: 56.3 g, V-65: 0.40 g, DM: 0.05 g
The solution containing the obtained copolymer A-3 had a non-volatile content of 40.0%, Mn of A-3 was 24,500, Mw was 156,000, and Tg was 12 ° C.

4) Production Example 4 [ Production of Component (A) A-4]
The following compounds were charged in the same manner as in Production Example 1 and dissolved uniformly.
THPI: 2.5 g, MMA: 26.5 g, BA: 16.0 g, HEA: 5.0 g, EtAc: 62.8 g, V-65: 0.10 g, DM: 0.01 g
Thereafter, the temperature was raised and the mixture was stirred in the same manner and under the same conditions as in Production Example 1, and then the following mixed solution was added dropwise, followed by stirring.
THPI: 2.5 g, MMA: 26.5 g, BA: 16.0 g, HEA: 5.0 g, EtAc: 38.7 g, V-65: 0.40 g, DM: 0.05 g
The solution containing the obtained copolymer A-4 had a non-volatile content of 49.7%, M-4 of A-4 was 28,200, Mw was 139,000, and Tg was 33 ° C.

5) Production Example 5 [ Production of Component (A) A-5]
The following compounds were charged in the same manner as in Production Example 1 and dissolved uniformly.
THPI: 5.0 g, MMA: 24.5 g, BA: 15.5 g, HEA: 5.0 g, EtAc: 62.1 g, V-65: 0.10 g, DM: 0.01 g
Thereafter, the temperature was raised and the mixture was stirred in the same manner and under the same conditions as in Production Example 1, and then the following mixed solution was added dropwise, followed by stirring.
THPI: 5.0 g, MMA: 24.5 g, BA: 15.5 g, HEA: 5.0 g, EtAc: 38.3 g, V-65: 0.40 g, DM: 0.05 g
The non-volatile content of the solution containing the obtained copolymer A-5 was 49.8%, Mn of A-5 was 26,300, Mw was 175,000, and Tg was 30 ° C.

6) Production Example 6 [ Production of Component (A) A-6]
The following compounds were charged in the same manner as in Production Example 1 and dissolved uniformly.
THPI: 15.0 g, CHA: 20.0 g, HA: 2.5 g, BA: 2.5 g, HEA: 10.0 g, EtAc: 73.0 g, V-65: 0.1 g
Thereafter, the temperature was raised and the mixture was stirred in the same manner and under the same conditions as in Production Example 1, and then the following mixed solution was added dropwise, followed by stirring.
THPI: 15.0 g, CHA: 20.0 g, HA: 2.5 g, BA: 2.5 g, HEA: 10.0 g, EtAc: 45.0 g, V-65: 0.40 g
The non-volatile content of the solution containing the obtained copolymer A-6 was 37.2%, Mn of A-6 was 19,300, Mw was 231,000, and Tg13 ° C.

7) Production Example 7 [ Production of Component (A) A-7]
The following compounds were charged in the same manner as in Production Example 1 and dissolved uniformly.
THPI: 5.0 g, MMA: 20.0 g, BA: 15.0 g, HEA: 10.0 g, EtAc: 89.8 g, V-65: 0.10 g, DM: 0.01 g
Thereafter, the temperature was raised and the mixture was stirred in the same manner and under the same conditions as in Production Example 1, and then the following mixed solution was added dropwise, followed by stirring.
THPI: 5.0 g, MMA: 20.0 g, BA: 15.0 g, HEA: 10.0 g, EtAc: 55.4 g, V-65: 0.40 g, DM: 0.05 g
The solution containing the obtained copolymer A-7 had a non-volatile content of 40.8%, and M-7 of A-7 was 23,500, Mw was 242,000, and Tg was 1 ° C.

8) Comparative Production Example 1 [ Production of Polymer A′-1 Other than Component (A)]
The following compounds were charged in the same manner as in Production Example 1 and dissolved uniformly.
THPI: 2.5 g, CHA: 20.0 g, HA: 10.0 g, BA: 15.0 g, HEA: 2.5 g, EtAc: 86.1 g, V-65: 0.10 g
Thereafter, the temperature was raised and the mixture was stirred in the same manner and under the same conditions as in Production Example 1, and then the following mixed solution was added dropwise, followed by stirring.
THPI: 2.5 g, CHA: 20.0 g, HA: 10.0 g, BA: 15.0 g, HEA: 2.5 g, EtAc: 53.1 g, V-65: 0.40 g
The solution containing the copolymer A′-1 had a non-volatile content of 40.6%, and M ′ of A′-1 was 24,400, Mw was 319,000, and Tg−18 ° C.

9) Comparative Production Example 2 [ Production of Polymer A′-2 Other than Component (A)]
The following compounds were charged in the same manner as in Production Example 1 and dissolved uniformly.
THPI: 6.0 g, EHMA: 18.0 g, BA: 24.0 g, HEA: 12.0 g, BuAc: 76.0 g, AMBN: 0.12 g
Thereafter, the temperature was raised and the mixture was stirred under the same method and conditions as in Production Example 1, and then the following mixed solution was added dropwise, followed by stirring.
THPI: 6.0 g, EHMA: 18.0 g, BA: 24.0 g, HEA: 12.0 g, BuAc: 76.0 g, AMBN: 0.12 g
The resulting copolymer solution had a non-volatile content of 42.0%, Mn 20,000, Mw 294,000, and Tg-26 ° C.

10) Comparative Production Example 3 [ Production of Polymer A′-3 Other than Component (A)]
The following compounds were charged in the same manner as in Production Example 1 and dissolved uniformly.
THPI: 18.0 g, EHMA: 12.0 g, BA: 18.0 g, HEA: 12.0 g
BuAc: 76.0 g, AMBN: 0.12 g, DM: 0.24 g
Thereafter, the temperature was raised and the mixture was stirred under the same method and conditions as in Production Example 1, and then the following mixed solution was added dropwise, followed by stirring.
THPI: 18.0 g, EHMA: 12.0 g, BA: 18.0 g, HEA: 12.0 g
BuAc: 76.0 g, AMBN: 0.48 g, DM: 0.24 g
The resulting copolymer solution had non-volatile content of 41.1%, Mn 13,900, Mw 200,600, and Tg-11 ° C.

11) Comparative Production Example 4 [ Production of Polymer A′-4 Other than Component (A)]
The following compounds were charged in the same manner as in Production Example 1 and dissolved uniformly.
EHMA: 21.0 g, BA: 27.0 g, HEA: 12.0 g, BuAc: 76.0 g, AMBN: 0.12 g
Thereafter, the temperature was raised and the mixture was stirred under the same method and conditions as in Production Example 1, and then the following mixed solution was added dropwise, followed by stirring.
EHMA: 21.0 g, BA: 27.0 g, HEA: 12.0 g, BuAc: 76.0 g, AMBN: 0.48 g
The obtained copolymer solution had a non-volatile content of 41.5%, Mn 18,000, Mw 63,000, and Tg 21 ° C.

12) Comparative Production Example 5 [ Production of Polymer A′-5 Other than Component (A)]
The following compounds were charged in the same manner as in Production Example 1 and dissolved uniformly.
THPI: 2.5 g, CHMA: 20.0 g, HA: 4.0 g, BA: 21.0 g, HEA: 2.5 g, EtAc: 102.2 g, V-65: 0.10 g
Thereafter, the temperature was raised and the mixture was stirred in the same manner and under the same conditions as in Production Example 1, and then the following mixed solution was added dropwise, followed by stirring.
THPI: 2.5 g, CHMA: 20.0 g, HA: 4.0 g, BA: 21.0 g, HEA: 2.5 g, EtAc: 63.0 g, V-65: 0.40 g
The non-volatile content of the solution containing the obtained copolymer A-6 was 37.7%, Mn 21,300, and Mw were 162,000 and Tg-3 ° C.

For the polymers other than the (A) component and the (A) component obtained in Production Examples 1 to 7 and Comparative Production Examples 1 to 5, used monomers and other components are summarized in Table 1. In Table 1, the number of parts used is shown so that the total amount of monomers used is 100 parts.
Moreover, about these polymers, the non volatile matter, molecular weight, and Tg were measured in accordance with the following method. The results are shown in Table 1.

(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 sample was dried.

(2) Molecular weight GPC (manufactured by Tosoh Corporation: HLC-8120, column: TSKgel-GMHxl × 2, eluent: tetrahydrofuran (THF) 1 mL / min, detector: differential refractometer (RI)) The molecular weight in terms of polystyrene was measured.

(3) Tg (glass transition temperature)
Using a differential scanning calorimeter DSC 6220 manufactured by SII NanoTechnology, Inc., differential scanning calorimetry was performed at a heating rate of 10 ° C./min. The point of intersection of the tangent line at the point where the curve of (1) changes to a downwardly convex curve was defined as Tg.

2. Examples 1 to 13 and Comparative Examples 1 to 9 (Production of Composition)
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 of each component used in Table 2 is “parts”. In Examples 1 to 13, the component (A) and the organic solvent are blended using the copolymer solution obtained in Production Examples 1 to 7. In Table 2, the components (A) and The organic solvents are listed separately. Comparative examples 1 to 9 are also described in the same manner.

The abbreviations in Table 2 mean the following.
M-313: Isocyanuric acid ethylene oxide-modified di- and triacrylate, Aronix M-313 manufactured by Toagosei Co., Ltd., viscosity at 25 ° C. = 27,000 mPa · s
SP-1509: Epoxy acrylate, “Lipoxy SP-1509” manufactured by Showa Denko KK, 25 ° C. viscosity = 30,000 mPa · s

M-1200: Polyester urethane acrylate, Aronix M-1200 manufactured by Toagosei Co., Ltd., viscosity at 25 ° C. = 2,000,000 mPa · s
M-140: N-acryloyloxyethyl hexahydrophthalimide, Aronix M-140 manufactured by Toagosei Co., Ltd.
ACMO: acryloylmorpholine, manufactured by Kojin Film & Chemicals Co., Ltd. TPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide PBZ: 4-phenylbenzophenone P301-75E: trifunctional isocyanate compound, Asahi Kasei Chemicals Co., Ltd. ) “Duranate P301-75E”
CO-L: Trifunctional isocyanate compound, Nippon Polyurethane Co., Ltd. Coronate L
FTR8120: Petroleum-based resin, manufactured by Mitsui Chemicals Co., Ltd. S-1511: Acrylic adhesive, Aron Tack S-1511 (X) manufactured by Toagosei Co., Ltd. Solid content 40 wt% (ethyl acetate, toluene solution)

3. Examples F1 to F13 and Comparative Examples F1 to F9 (Production of AE curable film)
Release film “Film Vina HTA” (silicone-treated polyethylene terephthalate film, thickness 75 μm) 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 is 100 μm. It was coated with a bar coater and dried with a hot air dryer at 60 ° C. for 5 minutes and further at 90 ° C. for 10 minutes.
Thereafter, a release film “Film Vina KF” (silicone-treated PET film, thickness 50 μm) manufactured by Fujimori Kogyo Co., Ltd. having a width of 300 mm × a length of 300 mm is laminated on the adhesive layer to obtain an AE curable film. It was.
The obtained AE curable film was evaluated by the following method. The results are shown in Table 3.

(1) G ′ before curing (25 ° C.) and G ′ (85 ° C.)
The AE curable films obtained in Examples F1 to F13 and Comparative Examples F1 to F9 were laminated to prepare a sample having a thickness of 500 μm.
The dynamic viscoelasticity of this AE curable film was measured according to JIS K7244-4 (frequency 1 Hz, heating rate 2 ° C./min), and the storage elastic modulus G ′ (25 ° C.) at 25 ° C. in shear mode. The storage elastic modulus G ′ at 85 ° C. (85 ° C.) was calculated by the same method.

(2) E ′ after curing (85 ° C.)
The AE curable films obtained in Examples F1 to F13 and Comparative Examples F1 to F9 were laminated to produce a strip-shaped sample having a width of 5 mm, a length of 50 mm, and a thickness of 100 μm.
Thereafter, a cured product was produced by ultraviolet irradiation with a high-pressure mercury lamp (illuminance of 365 nm light: 100 mW / cm ² , integrated light amount: ² J / cm ² ). The mechanical properties of this cured adhesive product were measured according to JIS K7244-4 (frequency 1 Hz, temperature rising rate 2 ° C./min), and storage elastic modulus E ′ at 85 ° C. in the tensile mode was calculated.

(3) High temperature peel strength after curing The release film on one side of the AE curable film is peeled off and bonded to a 125 μm thick polyethylene terephthalate film (trade name “Cosmo Shine A-4300” manufactured by Toyobo Co., Ltd.). It was. The other release film is peeled off and bonded to a polycarbonate (PC) sheet “Polyca Ace EC105” (Sumitomo Bakelite Co., Ltd., film thickness: 1 mm). Ultraviolet rays were irradiated by passing through 4 passes at a conveyor speed of 7 m / min (30 nm), with an illumination intensity of 365 nm light of 200 mW / cm ² and an integrated light amount of 0.5 J / cm ² per pass.
The laminate was subjected to a 90-degree peel test in accordance with JIS K-6854-1 under the conditions of a peel width of 25 mm, 85 ° C., and 23% RH to obtain peel strength.
The high temperature peel strength after UV curing (85 ° C.) is preferably 3.0 N / 25 mm or more, more preferably 5.0 N / 25 mm or more, and particularly 10.0 N / 25 mm or more. preferable.

(4) Foam resistance test (base material composition: PET / PC / PET)
The release film “Film Binder KF” of AE curable film is peeled off and bonded to easy-adhesion-treated PET film “Cosmo Shine A-4300” (manufactured by Toyobo Co., Ltd., film thickness 125 μm), and the other release The film “Film Bina HTA” was peeled off and bonded to a polycarbonate (PC) sheet “Polyca Ace EC105” (Sumitomo Bakelite Co., Ltd., film thickness: 1 mm).
Through “Polyca Ace EC105”, ultraviolet rays were irradiated by passing four passes under a condensing type high-pressure mercury lamp (120 W / cm, one lamp, lamp height 30 cm) at a conveyor speed of 7 m / min (illuminance of 365 nm light: 200 mW) / Cm ² , integrated light quantity per pass 0.5 J / cm ² ). In the same manner as described above, “Cosmo Shine A-4300” was bonded to the back surface of “Polyca Ace EC105” with an AE curable film to produce a laminate sample.
The laminate sample was conditioned at room temperature for 12 hours and then subjected to an environmental test of 85 ° C./85% RH × 100 hours to visually check the appearance change of the laminate, and evaluated at the following levels.
○: Pass; there is no appearance defect such as foaming and peeling.
X: Fail: Foaming, interface peeling, wrinkles of the adhesive layer, and one or more occurrences of cracks

(5) Void filling test Using a solder resist film (“SRF-8000”, 20 μm) on a smooth glass plate (100 mm × 100 mm), a length of 50 mm, a width of 5 mm, and a thickness by photolithography. A rectangular uneven shape having a thickness of 15 μm was produced. An AE curable film or an adhesive film was pasted on the entire uneven surface. At that time, the presence or absence of air pockets (air) at the edges of the concavo-convex shape was confirmed with an optical microscope (magnification 100 times). If there was no air and it could be pasted, ○: passed, otherwise X: rejected.

Examples F1 to F13, which are the compositions of the present invention, were also excellent in peeling strength, foam resistance and void filling.
In contrast, a composition containing a polymer A′-1 having a maleimide group and a polar group but having a Tg of less than 0 ° C. (Comparative Example F1), a composition containing the polymer A′-2 (Comparative Example F2) F3), a composition containing a polymer A′-3 (Comparative Example F4) and a composition containing a polymer A′-5 (Comparative Examples F7 and F8) have excellent peel strength, The foamability was poor. Furthermore, in the composition containing the polymer A′-3 (Comparative Example F5), the peel strength was also lowered.
In addition, a composition (Comparative Example F6) containing a polymer A′-4 having a polar group and Tg exceeding 0 ° C. but not having a maleimide group, although the peel strength is excellent, the foam resistance is poor. It was.
In addition, Comparative Example F9 using a commercially available acrylic pressure-sensitive adhesive had poor foam resistance and void filling properties.

4). Examples S1 to S13 and Comparative Examples S1 to S9
One part of the following KBM-5103 was blended as a silane coupling agent with respect to 100 parts of the curable component contained in the compositions of Examples F1 to F13 and Comparative Examples F1 to F9.
Hereinafter, the compositions further containing a coupling agent corresponding to the compositions of Examples F1 to F13 and Comparative Examples F1 to F9 are referred to as Examples S1 to S13 and Comparative Examples 1 to S9, respectively.
KBM-5103: 3-acryloxypropyltrimethoxysilane, “KBM-5103” manufactured by Shin-Etsu Chemical Co., Ltd.

About the composition of Example S1-S13 and the composition of comparative example S1-S9, it evaluated by the following base-material structure as a foaming resistance test.
(Base material composition: PC / glass)
The film binder KF of the AE curable film is peeled off and bonded to a polycarbonate (PC) sheet “Polyca Ace EC105” (manufactured by Sumitomo Bakelite Co., Ltd., film thickness 1 mm), and the other release film “film binder HTA” Was peeled off and bonded to a white slide glass (S-1112 manufactured by Matsunami Glass Industry Co., Ltd.).
Through “Polyca Ace EC105”, ultraviolet rays were irradiated by passing four passes under a condensing type high-pressure mercury lamp (120 W / cm, one lamp, lamp height 30 cm) at a conveyor speed of 7 m / min (illuminance of 365 nm light: 200 mW) / Cm ² , integrated light quantity per pass 0.5 J / cm ² ), a laminate sample was manufactured.
The laminate sample was conditioned at room temperature for 12 hours and then subjected to an environmental test of 85 ° C./85% RH × 100 hours to visually check the appearance change of the laminate, and evaluated at the following levels.
○: Pass; there is no appearance defect such as foaming and peeling.
X: Fail: Foaming, interface peeling, wrinkles of the adhesive layer, and one or more occurrences of cracks

As a result, the compositions of Examples S1 to S13 were all evaluated as ◯.
In contrast, the compositions of Comparative Examples S1 to S9 were all evaluated as x.
The compositions of Examples S1 to S13 were also evaluated for peel strength and void filling properties, and had the same effects as in Table 3 above.

5. Examples P1 to P13
About the composition of Example F1-F13, 0.50 part of following AO-80 and 0.10 part of following AS3010 were further mix | blended with 100 parts of sclerosing | hardenable components to contain as a deterioration inhibiting agent, respectively.
Hereinafter, corresponding to the compositions of Examples F1 to F13, compositions further containing a deterioration inhibitor are referred to as Examples P1 to P13, respectively.
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.

About the composition of Example P1-P13, according to the following method, coloring resistance was evaluated by the yellow index and wet heat resistance was evaluated.
The compositions of Examples F1 to F13 have a yellow index after the heat resistance test of about 1.2 to 1.5, whereas the compositions of Examples P1 to P13 are yellow even after the heat resistance test. The index was 0.32 to 0.87 with little coloring.

(6) Using a yellow index AE curable film, polyethylene terephthalate films (trade name “COSMO SHINE A-4300” manufactured by Toyobo Co., Ltd.) having a film thickness of 50 μm subjected to easy adhesion treatment were bonded to each other. Thereafter, ultraviolet rays were irradiated using the same apparatus and conditions as in the adhesion test.
After 1 day, the yellow index was measured with a color difference meter. Thereafter, the yellow index after 100 ° C. × 100 hours was also measured and used as an index of coloring.

The composition of the present invention can be preferably used for the production of an AE curable film, particularly suitable for the production of an active energy ray-curable void filling film, and further suitable for the production of a laminate. Can be used for
As a laminated body, it can use suitably for manufacture of the surface protective layer of the image display apparatus with a touchscreen comprised from plastic base materials, such as a polycarbonate and a polymethylmethacrylate, the display surface of an image display unit, or a touch panel.

Claims (18)

Including the following (A) component, (B) component, (D) component, (E) component, and optionally (C) component, the following (A) to (C) components (hereinafter referred to as “curing” In the total of the "component"), 40 to 90% by weight of component (A), 10 to 60% by weight of component (B) and 0 to 20% by weight of component (C),
For plastic film or sheet, 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 curable components An active energy ray-curable adhesive composition.
(A) Component: a polymer having a maleimide group and a polar group, and having a glass transition temperature exceeding 0 ° C. and not exceeding 40 ° C. (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 The active energy ray-curable adhesive composition for plastic film or sheet according to claim 1, wherein the maleimide group of component (A) is a group represented by the following formula (1).

(In 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.)   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). ] The active energy ray hardening-type adhesive composition for plastic films or sheets of Claim 1 or Claim 2 which is a copolymer which at least was copolymerized. The active energy ray hardening-type adhesive composition for plastic films or sheets of Claim 3 whose said monomer (a) is a compound represented by following formula (2).

(In Formula (2), 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. A hydrocarbon group that forms 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 component (A) is a monomer (a), the monomer (b), and a compound (c) having an ethylenically unsaturated group other than the monomers (a) and (b) [hereinafter, simply Also referred to as a monomer (c). The active energy ray-curable adhesive composition for plastic film or sheet according to claim 3 or 4, which is a copolymer having a monomer unit derived therefrom. The plastic film according to any one of claims 3 to 5, wherein the component (A) has a monomer unit derived from the following monomer and is a copolymer having the following copolymerization ratio. Or the active energy ray hardening-type adhesive composition for sheets.
-Monomer (a): 5 to 50% by weight
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   The active energy ray curing for plastic film or sheet according to any one of claims 1 to 6, wherein the viscosity of component (B) at 25 ° C is 1,000 to 10,000,000 mPa · s. Type adhesive composition.   The active energy ray hardening-type adhesive composition for plastic films or sheets as described in any one of Claims 1-7 which further contains an organic solvent.   The active energy ray-curable adhesive composition for plastic film or sheet according to any one of claims 1 to 8, further comprising a silane coupling agent.   The active energy ray hardening-type adhesive composition for plastic films or sheets as described in any one of Claims 1-9 which further contains a degradation inhibitor.   The plastic film or sheet is a polycarbonate or a (meth) acrylic resin, The active energy ray-curable adhesive composition for a plastic film or sheet according to any one of claims 1 to 10.   The adhesive film obtained by applying the active energy ray-curable adhesive composition for plastic film or sheet according to any one of claims 1 to 11 to a substrate and drying it to form a film. An active energy ray-curable adhesive film or sheet obtained by bonding another base material to the wearing surface.   The active energy ray hardening-type adhesive film or sheet | seat of Claim 12 whose arithmetic mean roughness Ra of at least one base material is 30 nm or less.   The active energy ray-curable adhesive film or sheet according to claim 12 or 13, wherein one of the substrates is subjected to a release treatment.   The active energy ray-curable adhesive film or sheet according to claim 12 or 13, wherein both of the base materials are subjected to a release treatment. The active energy ray-curable adhesive film or sheet according to claim 14, wherein only one of the substrates has been subjected to a release treatment, the release-treated substrate of the sheet is peeled off, and the exposed composition surface and plastic film or A step of adhering the sheet-made adherend, and
The manufacturing method of a laminated body which includes the process of irradiating an active energy ray from the base material or the to-be-adhered body side which is not release-processed in this order. The active energy ray-curable adhesive film or sheet according to claim 15, wherein both of the substrates are release-treated, and the release-treated substrate and the plastic film are peeled off. Or a step of adhering the sheet-made adherend,
Peeling off the other release-treated substrate and adhering the exposed surface of the composition to another adherend; and
The manufacturing method of a laminated body which includes the process of irradiating an active energy ray from the side of either adherend in this order. A step of peeling off one release-treated substrate of the active energy ray-curable adhesive film or sheet according to claim 15, and sticking the exposed surface of the composition and the adherend; and
Including the step of irradiating active energy rays in this order from the side of the base or adherend while the other base is attached,
The manufacturing method of the laminated body whose arithmetic mean roughness Ra of the base material with which the said active energy ray hardening-type adhesive film or sheet was left is 30 nm or less.

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