JP2024001680A - Active-energy-ray-curable adhesive composition for plastic film or sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an active-energy-ray-curable adhesive composition especially excellent in adhesiveness between hydrophilic plastic films and between a hydrophobic plastic film and a hydrophilic plastic film, having good adhesive force even when adhered in a high humidity state, and also excellent in durability.

SOLUTION: There is provided an active-energy-ray-curable adhesive composition for plastic film or sheet comprises the following (A) to (C) as a curable component and the following (D) as a polymerization initiator. (A): a water-soluble compound having a nitrogen atom and one unsaturated group; (B): a urethane (meth)acrylate; (C): a compound having one unsaturated group other than (A); (D): a photo-radical polymerization initiator. The curable component contains, in 100 wt.% (hereinafter referred to as %) for the total amount of the curable component, (A) in a ratio of 20 to 75%, (B) in a ratio of 10 to 35%, and (C) in a ratio of 5 to 70%, and the active-energy-ray-curable adhesive composition contains, with reference to 100 pts.wt. of the total amount of the curable component, (D) in a ratio of 0.1 to 15 pts.wt..

SELECTED DRAWING: None

COPYRIGHT: (C)2024,JPO&INPIT

Description

The present invention relates to an active energy ray-curable adhesive composition that can bond various plastic films or sheets by irradiation with active energy rays such as electron beams or ultraviolet rays.
In the following, unless otherwise specified, plastic films or sheets are collectively referred to as "plastic films", and films or sheets are collectively referred to as "films".

Various displays such as liquid crystal displays and organic EL displays are thin, lightweight, and low power consumption, so they are used in mobile devices equipped with touch panels such as smartphones, tablets, and car navigation systems, as well as personal computers, televisions, and digital signage. Widely used in medium and large size image display devices.
Various optical films are used in the display, and optical films include polarizing plates, retardation films, viewing angle compensation films, brightness enhancement films, antireflection films, antiglare films, lens sheets, diffusion sheets, Examples include hard coat films with anti-fingerprint and anti-glare functionality, and front panels for touch panels.

These optical films include polyvinyl alcohol films, cellulose ester films such as triacetylcellulose, polyester films such as polyethylene terephthalate, acrylic films or sheets such as polymethyl methacrylate, and carbonate films or sheets such as polycarbonate. It is often used by laminating various types of plastic films together. Active energy ray-curable adhesives are widely used for bonding the plastic films together because of their fast curing speed and excellent productivity.

Active energy ray-curable adhesive compositions include photo-radical polymerizable compositions that utilize radical photopolymerization, photo-cationic polymerizable compositions that utilize photo-cationic polymerization, and hybrids that utilize both radical photopolymerization and cationic photopolymerization. Mold compositions are known.

The hybrid composition is used for laminating hydroxyl group-containing polyvinyl alcohol films and cellulose ester films, which are particularly used for polarizing plates.
This is because the above two types of plastic films are characterized by high hydrophilicity, and it is extremely difficult to obtain high adhesive strength even when using photo-radical polymerizable compositions or photo-cationic polymerizable compositions. .
In the present invention, highly hydrophilic plastic films such as the above two types of plastic films are referred to as "hydrophilic plastic films", and other plastic films are referred to as "hydrophobic plastic films". The contact angle of water is used as an index of hydrophilicity, and a plastic film with a water contact angle of less than 70° at 23°C is referred to as a "hydrophilic plastic film", and a plastic film with a water contact angle of 70° or more as a "hydrophobic plastic film". do.

Specific examples of hydrophilic plastic films include polyvinyl alcohol films and cellulose ester films.
Specific examples of hydrophobic plastic films include polycarbonate films, polyethylene terephthalate films, polyethylene naphthalate films, acrylic films, acrylic/styrene films, aliphatic polyamide (nylon) films, aromatic polyamide films, Polyurethane film, polyimide film, ethylene-vinyl acetate copolymer film, polyvinyl chloride film, polyvinylidene chloride film, polyethylene film, polypropylene film, polycycloolefin film, polystyrene film, ABS film , chlorinated polypropylene film, etc.

Patent Document 1 discloses a hybrid composition containing a (meth)acrylate having an isocyanuric ring skeleton, an alicyclic epoxy compound, a compound containing a hydroxyl group, and a photoacid generator.

Patent Document 2 describes an epoxy resin having two or more epoxy groups and at least one of the groups being an alicyclic epoxy group, and an epoxy resin having two or more epoxy groups and having an alicyclic epoxy group. A hybrid composition containing an epoxy resin, a photocationic polymerization initiator, and a polymerizable monomer is disclosed.

Patent Document 3 describes a compound having two or more (meth)acrylic groups, a compound having a hydroxyl group and one (meth)acrylic group, a cationic polymerizable compound having a (meth)acrylic group, a photoradical polymerization initiator, and a photoradical polymerization initiator. A hybrid composition containing a cationic polymerization initiator is disclosed.

Patent Document 4 describes an aromatic epoxy compound containing two or more epoxy groups in the molecule, at least one compound selected from the group consisting of 4-hydroxybutyl acrylate and 2-hydroxybutyl acrylate, and two or more epoxy groups in the molecule. A hybrid composition containing an ethylenically unsaturated compound constituted of at least one of the above compounds having an ethylenically unsaturated group and a photocationic polymerization initiator is disclosed.

Japanese Patent Application Publication No. 2008-233279 Japanese Patent Application Publication No. 2008-257199 Japanese Patent Application Publication No. 2008-260879 International Publication No. 2012/173055

However, when the hybrid compositions disclosed in Patent Documents 1 to 4 are bonded in a high humidity state or exposed to a high humidity state, the adhesive strength of the cured product decreases and the durability decreases. There was a problem.

The present invention has been made in view of the above problems, and has excellent adhesion to various plastic films, in particular, adhesion between hydrophilic plastic films such as cellulose ester films, and hydrophobic plastics such as polycarbonate films. The purpose is to provide an active energy ray-curable adhesive composition that has excellent adhesion between a film and a hydrophilic plastic film, has good adhesive strength even when bonded under high humidity conditions, and has excellent durability. shall be.

As a result of studies to solve the above-mentioned problems, the present inventors found that cationic polymerization components and their cured products are the cause of the decrease in adhesive strength and durability in high humidity conditions. We conducted extensive research based on the idea that the above problem could be solved by considering a composition containing only radical polymerization components.
As a result, water-soluble compounds containing a nitrogen atom and one unsaturated double bond in the molecule, urethane (meth)acrylates, compounds with one ethylenically unsaturated group, and photoradical polymerization initiators were identified as It has been discovered that an active energy ray-curable adhesive composition for plastic films, which contains a proportion of completed.

The present invention comprises at least a curable component and a polymerization initiator, the curable component comprises at least the following components (A) to (C), the polymerization initiator comprises at least the following component (D),
(A) component: water-soluble compound having a nitrogen atom and one ethylenically unsaturated group in the molecule (B) component: urethane (meth)acrylate (C) component: ethylenic compound other than component (A) Compound (D) component having one unsaturated group: photoradical polymerization initiator Contains the above-mentioned (A) to (C) components in the following proportions in 100% by weight of the total amount of curable components,
(A) Component: 20-75% by weight
(B) Component: 10 to 35% by weight
(C) Component: 5 to 70% by weight
The present invention relates to an active energy ray-curable adhesive composition for plastic films, which contains the component (D) in the following proportions based on 100 parts by weight of the total amount of curable components.
(D) Component: 0.1 to 15 parts by weight

The component (B) is preferably a urethane (meth)acrylate having a weight average molecular weight of 2,000 to 100,000.

The component (A) preferably contains at least one selected from the group consisting of (meth)acryloylmorpholine, N-vinylpyrrolidone, N-vinylcaprolactam, and N-vinylformamide.

As the component (C), a compound having one (meth)acryloyl group with a molecular weight of less than 300 is preferable.

The composition of the present invention preferably further contains the following component (E) as a curable component.
Component (E): Compound other than component (B) having two or more ethylenically unsaturated groups

As for the composition of the present invention, the plastic film is a hydrophilic plastic film, and an active energy ray-curable adhesive composition for a plastic film for manufacturing a polarizing plate is preferable.

The present invention also relates to a substrate, a cured material layer formed from any of the compositions described above, and a plastic film.
In this case, a laminate is preferred in which the base material is a plastic film, one of the two plastic films is a triacetyl cellulose plastic film or a polyvinyl alcohol plastic film, and the other is a hydrophobic plastic film. , it is preferable that the laminate is a polarizing plate.

The present invention also relates to a method for manufacturing a laminate, in which the following steps 1 to 3 are performed sequentially.
・Step 1: Coating the composition on at least one of the bonding surfaces of the base material and the plastic film ・Step 2: Applying the composition to the base material and the plastic film via the composition layer obtained in Step 1 Step 3 of laminating: With the base material and the plastic film laminated via the composition layer, active energy rays are irradiated from either side of the base material or the plastic film to bond the composition. Further, the base material in step 1 is a plastic film, and further, one of the two plastic films is a triacetylcellulose plastic film or a polyvinyl alcohol plastic film, and the other is a hydrophobic plastic film. A method for manufacturing a laminate is preferred, and a method for manufacturing a polarizing plate comprising the method for manufacturing the laminate is preferred.

The active energy ray-curable adhesive composition of the present invention has excellent adhesion between hydrophilic plastics and between hydrophobic plastic films and hydrophilic plastic films, and also has excellent adhesion in high humidity conditions. It has good adhesive strength even when used, and has excellent durability.

Various embodiments of the technology disclosed in this specification will be described in detail below. In this specification, acrylate and/or methacrylate is referred to as (meth)acrylate, acryloyl group and/or methacryloyl group is referred to as (meth)acryloyl group, and acrylic acid and/or methacrylic acid is referred to as (meth)acrylic acid, acrylamide. /Methacrylamide is expressed as (meth)acrylamide.
In addition, the curable component is a component having one or more ethylenically unsaturated groups that is hardened by active energy rays, and refers to component (A), component (B), and component (C), and includes component (E) described below. ) component means (A) component, (B) component, (C) component, and (E) component.

The present invention relates to an active energy ray-curable adhesive composition for plastic films or sheets containing the components (A) to (D) in specific proportions.
Components (A) to (D), other components, the active energy ray-curable adhesive composition for plastic films, the method of use, the laminate and its manufacturing method will be described in detail below.

1. Component (A) Component (A) is a water-soluble compound having a nitrogen atom and one ethylenically unsaturated group in the molecule.
Water-soluble herein means that 100 g or more is dissolved in 100 g of water.
In addition, in the following, "monofunctional" means a compound having one ethylenically unsaturated group.
Examples of the ethylenically unsaturated group include a (meth)acryloyl group, a vinyl group, and a vinyl ether group.

Specific examples of component (A) include:
Nitrogen-containing monofunctional vinyl compounds such as N-vinylpyrrolidone, N-vinylcaprolactam, and N-vinylformamide; and diacetone (meth)acrylamide, isobutoxymethyl (meth)acrylamide, N,N-dimethyl (meth)acrylamide, t -butyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N-dimethylaminopropyl(meth)acrylamide, (meth)acryloylmorpholine, acrylamide-2-methylpropanesulfonic acid, and N-isopropyl(meth)acrylamide. ) Monofunctional (meth)acrylamide compounds such as acrylamide can be mentioned.

Among the above-mentioned compounds, as component (A), (meth)acryloylmorpholine, N-vinylpyrrolidone, N-vinylcaprolactam, and N-vinylformamide are preferred, with acryloylmorpholine being particularly preferred.

As component (A), only one type of the above-mentioned compounds can be used, or two or more types can be used in combination.

The content of component (A) is 20 to 75% by weight, preferably 25 to 70% by weight, based on 100% by weight of the total amount of curable components.
If the proportion of component (A) is less than 20% by weight, the adhesiveness of the composition to plastics will be reduced, and if it exceeds 75% by weight, the water resistance of the cured composition will be reduced.

2. Component (B) Component (B) is urethane (meth)acrylate, and is a (meth)acrylate compound having a urethane bond.
Component (B) includes a reaction product of a polyol, an organic polyisocyanate, and a hydroxyl group-containing (meth)acrylate [hereinafter referred to as "component (B-1)"], and a reaction product of an organic polyisocyanate and a hydroxyl group-containing (meth)acrylate. (so-called urethane adduct), and component (B-1) is preferred from the viewpoint of adhesive strength.
The raw material compound and manufacturing method of component (B-1) will be explained below.

2-1. raw material compound
A polyol, an organic polyisocyanate, a hydroxyl group-containing (meth)acrylate, and a metal catalyst are used as raw material compounds for component (B-1).

Specific examples of polyols include low molecular weight polyols, polyether polyols, polycarbonate polyols, polyester polyols, and diols having a polyene skeleton.

Examples of low molecular weight polyols include polyols having at least two hydroxyl groups with a molecular weight of about 50 to 300, and specific examples include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, , 4-butanediol, 1,6-hexanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, cyclohexanedimethanol, tricyclodecane dimethanol, neopentyl glycol, 3-methyl-1 , 5-pentanediol, and neopentyl glycol hydroxypivalate.

Examples of polyether polyols include polyalkylene glycols having two or more oxyalkylene units, and specific examples include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and the like.
Examples of polycarbonate polyols include reaction products of carbonate and diol. Specific examples of carbonates include diaryl carbonates such as diphenyl carbonate, and dialkyl carbonates such as dimethyl carbonate and diethyl carbonate.

Examples of the polyester polyol include a reaction product of at least one selected from the group consisting of the above-mentioned low molecular weight diols, polyether polyols, and polycarbonate polyols and an acid component.
Specific examples of acid components include dibasic acids such as adipic acid, sebacic acid, succinic acid, maleic acid, phthalic acid, hexahydrophthalic acid, and terephthalic acid, or their anhydrides, and ring-opening reaction products of polycarbonate diol and caprolactone. etc.
Examples of diols having a polyene skeleton include diols having a polybutadiene skeleton, diols having a polyisoprene skeleton, diols having a hydrogenated polybutadiene skeleton, and diols having a hydrogenated polyisoprene skeleton.
The above polyols may be used alone or in combination of two or more.

Examples of the organic polyisocyanate include diisocyanate and triisocyanate.
Specific examples of diisocyanates include aromatic diisocyanates such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylene diisocyanate and naphthalene diisocyanate; aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; isophorone diisocyanate; Examples include alicyclic diisocyanates such as '-dicyclohexylmethane diisocyanate, norbornene diisocyanate, and hydrogenated xylene diisocyanate.
Specific examples of triisocyanates include 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, and bicycloheptane triisocyanate.
The above organic polyisocyanates may be used alone or in combination of two or more.

Specific examples of hydroxyl group-containing (meth)acrylates include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate.
The above hydroxyl group-containing (meth)acrylates may be used alone or in combination of two or more.

Specific examples of the metal catalyst include tin compounds such as dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dioctate, and dibutyltin diacetylacetonate, and bismuth compounds such as bismuth dioctate.
The above metal catalysts may be used alone or in combination of two or more.

A preferred embodiment of component (B-1) is urethane (meth)acrylate containing two (meth)acryloyl groups from the viewpoint of improving adhesive strength. In addition, in terms of the ability to further improve adhesive strength, polyether-based urethane (meth)acrylate using polyether polyol as the raw material polyol, polyester-based urethane (meth)acrylate using polyester polyol, and polycarbonate-based using polycarbonate polyol. Urethane (meth)acrylate is preferred, and polyether urethane (meth)acrylate and polyester urethane (meth)acrylate are more preferred.

2-2. Production method
Component (B-1) can be produced by heating and stirring a polyol, an organic polyisocyanate, and a hydroxyl group-containing (meth)acrylate in the presence of a metal catalyst and, if necessary, a reaction solvent to form a urethane. .
In this case, the polyol, organic polyisocyanate, and hydroxyl group-containing (meth)acrylate can be charged all at once and reacted (hereinafter referred to as "one-stage reaction"), and the polyol and organic polyisocyanate are reacted to form an isocyanate group-containing prepolymer. After producing , a hydroxyl group-containing (meth)acrylate can also be added (hereinafter referred to as "two-stage reaction").

The ratio of the polyol to the organic polyisocyanate may be appropriately set depending on the structure of the urethane (meth)acrylate to be finally obtained. The total amount of isocyanate groups in the polyisocyanate is preferably 1.05 to 2 mol.
The proportion of the hydroxyl group-containing (meth)acrylate is preferably such that no isocyanate group remains in the resulting urethane (meth)acrylate.
When producing by the above two-stage reaction, the amount of hydroxyl group-containing (meth)acrylate is preferably 1.0 to 1.5 mol per 1 mol of the total amount of isocyanate groups in the isocyanate group-containing prepolymer.
In the case of manufacturing by the one-stage reaction described above, per mole of the total amount of isocyanate groups remaining in the isocyanate group-containing prepolymer calculated based on the structure of the urethane (meth)acrylate to be finally obtained, The proportion of the hydroxyl group-containing (meth)acrylate is preferably 1.0 to 1.5 moles.
In this case, the ratio of the total amount of hydroxyl groups in the polyol and acid group-containing (meth)acrylate to 1 mol of isocyanate groups in the organic polyisocyanate is preferably 1.0 to 1.5 mol.

Incidentally, if the molecular weight of the component (B-1) produced by this reaction becomes high, the reaction mixture becomes highly viscous and stirring may become difficult, so a reaction solvent may also be blended into the reaction components.
The reaction solvent is preferably one that does not participate in the urethanization reaction, and includes organic solvents such as aromatic solvents such as toluene and xylene, and ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone.
When using an organic solvent, the amount to be blended may be set appropriately depending on the viscosity of the component (B-1) to be produced, but it is preferably set so that it is 0 to 70% by weight in the reaction solution. .
Here, the reaction solution means the total amount of the raw material compounds when only the raw material compounds are used, and the total amount including these when using the reaction solvent in addition to the raw material compounds. Specifically, it is used to mean a solution containing a polyol, an organic polyisocyanate, a hydroxyl group-containing (meth)acrylate, a reaction solvent used as necessary, and the like.

Component (B-1) and (meth)acrylate compounds other than component (B-1) (hereinafter referred to as "other (meth) ) can also be blended. As the other (meth)acrylates, compounds listed as other components described below except those involved in the reaction such as hydroxyl group-containing polyfunctional (meth)acrylates can be used. When blending other (meth)acrylates and performing a urethanization reaction, and blending the obtained urethane (meth)acrylate into an active energy ray-curable adhesive composition, unlike the case where the organic solvent is blended, the composition This is preferable because there is no need to dry the product after applying it.
The amount of other (meth)acrylates to be added to the reaction component may be determined as appropriate depending on the proportion of other (meth)acrylates to be finally added to the composition. It is preferably set to 70% by weight, more preferably 10 to 50% by weight.

The amount of the metal catalyst to be blended may be a catalytic amount, for example, preferably 0.01 to 1,000 wtppm, more preferably 0.1 to 1,000 wtppm, based on the reaction solution. By setting the blending amount of the metal compound to 0.01 wtppm or more, the urethanization reaction can proceed preferably, and by setting it to 1,000 wtppm or less, coloring of the obtained component (B) can be suppressed. .

In the case of a one-stage reaction, the metal catalyst can be added at the time of charging the polyol, organic polyisocyanate, and hydroxyl group-containing (meth)acrylate, and in the case of a two-stage reaction, it can be added at the time of charging the polyol and the organic polyisocyanate.

In the urethanization reaction, a small amount of a chain extender may be added for the purpose of molecular weight adjustment.
As the chain extender, those commonly used in urethanization reactions can be used, including those similar to the above-mentioned low molecular weight polyols.

In the urethanization reaction, it is preferable to use a polymerization inhibitor for the purpose of preventing polymerization of the (meth)acryloyl group of the raw material or product, and furthermore, an oxygen-containing gas may be introduced into the reaction solution.
Specific examples of polymerization inhibitors include hydroquinone, tert-butylhydroquinone, hydroquinone monomethyl ether, 2,6-di-tert-butyl-4-methylphenol, 2,4,6-tri-tert-butylphenol, benzoquinone, and phenothiazine. Examples include organic polymerization inhibitors such as, inorganic polymerization inhibitors such as copper chloride and copper sulfate, and organic salt polymerization inhibitors such as copper dibutyldithiocarbamate. The polymerization inhibitors may be used alone or in any combination of two or more. The proportion of the polymerization inhibitor in the reaction solution is preferably 5 to 20,000 wtppm, more preferably 25 to 3,000 wtppm.
Examples of the oxygen-containing gas include air, a mixed gas of oxygen and nitrogen, a mixed gas of oxygen and helium, and the like.

The reaction temperature may be appropriately set depending on the raw materials used and the structure and molecular weight of the desired component (B-1), but is usually preferably 25 to 150°C, more preferably 30 to 120°C. The reaction time may be appropriately set depending on the raw materials used and the structure and molecular weight of the target urethane (meth)acrylate, but it is usually preferably 1 to 70 hours, more preferably 2 to 30 hours.

2-3. In addition, the weight average molecular weight (hereinafter referred to as "Mw") of component (B-1) in the present invention is from 2,000 to 2,000, since the composition has excellent coating properties and the adhesive strength of the cured composition is improved. It is preferably 100,000, more preferably 5,000 to 50,000.

In the present invention, Mw is a value obtained by converting the molecular weight measured by gel permeation chromatography (hereinafter referred to as "GPC") into polystyrene, and means a value measured under the following conditions.
・Detector: Differential refraction system (RI detector)
・Column type: Cross-linked polystyrene column ・Column temperature: 40℃
・Eluent: Tetrahydrofuran ・Molecular weight standard: Polystyrene

As the component (B), only one type can be used or two or more types can be used in combination.

The content of component (B) is 10 to 35% by weight, more preferably 15 to 35% by weight, based on 100% by weight of the total amount of curable components. If the proportion of component (B) is less than 5% by weight, the durability of the cured composition after adhesion will decrease, and if it exceeds 35% by weight, the composition will become highly viscous and the coatability will decrease. I end up.

3. Component (C) Component (C) is a compound other than component (A) that has one ethylenically unsaturated group.

Examples of compounds having one ethylenically unsaturated group other than component (A) include compounds having one (meth)acryloyl group in the molecule [hereinafter referred to as "monofunctional (meth)acrylate"], vinyl compounds , and allyl compounds.

Specific examples of monofunctional (meth)acrylates include:
2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate Acrylate, polytetramethylene glycol mono(meth)acrylate, polyethylene glycol-polypropylene glycol mono(meth)acrylate, polyethylene glycol-polytetramethylene glycol mono(meth)acrylate, polypropylene glycol-polytetramethylene glycol mono(meth)acrylate, 2 -Hydroxy-3-phenoxypropyl (meth)acrylate, 2-hydroxy-3-butoxypropyl (meth)acrylate, 2-(meth)acryloyloxyethyl-2-hydroxyethyl phthalate, and 2-(meth)acryloyloxyethyl- Hydroxyl group-containing (meth)acrylates such as 2-hydroxypropyl phthalate;
(meth)acrylic acid, (meth)acrylic acid dimer, 2-(meth)acryloyloxyethylsuccinic acid, 2-(meth)acryloyloxyethyl phthalic acid, 2-(meth)acryloyloxyethylhexahydrophthalic acid , and compounds having a carboxy group and a (meth)acryloyl group such as ω-carboxypolycaprolactone (meth)acrylate;
Methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, amyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, Pentyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, Decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, alkyl (meth)acrylate having 12 to 13 carbon atoms, cetyl (meth)acrylate, stearyl ( aliphatic (meth)acrylates such as meth)acrylate, isostearyl (meth)acrylate, and isomyristyl (meth)acrylate;
Methoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, ethyl carbitol (meth)acrylate, 2-ethylhexyl carbitol (meth)acrylate, butoxyethyl (meth)acrylate, methoxyethylene glycol (meth)acrylate, ethoxy Alkoxyalkyl (meth)acrylates such as diethylene glycol (meth)acrylate, ethoxyethyl (meth)acrylate, methoxytriethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, and methoxypolypropylene glycol (meth)acrylate;
Bornyl (meth)acrylate, isobornyl (meth)acrylate, tricyclodecanyl (meth)acrylate, dicyclopentanyl (meth)acrylate, 4-butylcyclohexyl (meth)acrylate, cyclohexyl (meth)acrylate, t-butylcyclohexyl ( meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, cyclic trimethylolpropane formal (meth)acrylate, dicyclopentenyl (meth)acrylate, adamantyl (meth)acrylate, tricyclodecane (meth)acrylate, and Alicyclic (meth)acrylates such as dicyclopentenyloxyethyl (meth)acrylate;
Phenyl (meth)acrylate, (meth)acrylate of phenol derivatives, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, (meth)acrylate of alkylene oxide modified phenol, (meth)acrylate of alkylene oxide modified cresol , (meth)acrylate of alkylene oxide modified p-cumylphenol, (meth)acrylate of alkylene oxide modified nonylphenol, (meth)acrylate of alkylene oxide modified o-phenylphenol, alkylene of p-phenylphenol (meth)acrylates of oxide-modified products, (meth)acrylates of alkylene oxide-modified tribromophenols, and aromatic (meth)acrylates such as neopentyl glycol (meth)acrylic acid benzoate;
Tetrahydrofurfuryl (meth)acrylate, and (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate cyclic ether group-containing (meth)acrylate;
Carbonate group-containing (meth)acrylates such as glycerin carbonate (meth)acrylate;
N-(meth)acryloyloxyethylhexahydrophthalimide, 2-(1,2-cyclohexa-1-enedicarboximide)ethyl(meth)acrylate, Fancryl FA-502A [manufactured by Showa Denko Materials Co., Ltd.], etc. and phosphoric acid (meth)acrylates such as 2-(meth)acryloyloxyethyl acid phosphate.

Specific examples of vinyl compounds include aromatic vinyl compounds such as styrene and vinyltoluene;
Heterocycle-containing vinyl compounds such as vinyl imidazole and vinylpyridine; and n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, 2-hydroxyethyl vinyl ether, cyclohexanedimethanol monovinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether, Examples include vinyl ethers such as cyclohexyl vinyl ether, dodecyl vinyl ether, octadecyl vinyl ether, lauryl vinyl ether, cetyl vinyl ether, and 2-ethylhexyl vinyl ether.
Specific examples of allyl compounds include monofunctional allyl compounds such as allyl alcohol.

Among the above-mentioned, monofunctional (meth)acrylates having a molecular weight of less than 300 are more preferable in order to provide a composition with low viscosity and excellent adhesive properties.
Preferred specific examples include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 2-hydroxy-3-phenoxy Hydroxyl group-containing (meth)acrylates such as propyl (meth)acrylate;
(meth)acrylic acid, (meth)acrylic acid dimer, 2-(meth)acryloyloxyethylsuccinic acid, 2-(meth)acryloyloxyethyl phthalic acid, 2-(meth)acryloyloxyethylhexahydrophthalic acid , and compounds having a carboxy group and a (meth)acryloyl group such as ω-carboxypolycaprolactone (meth)acrylate;
Octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, and aliphatic (meth)acrylates such as lauryl (meth)acrylate;
Alkoxyalkyl (meth)acrylates such as ethyl carbitol (meth)acrylate;
Isobornyl (meth)acrylate, tricyclodecanyl (meth)acrylate, dicyclopentanyl (meth)acrylate, 4-butylcyclohexyl (meth)acrylate, cyclohexyl (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate acrylate, cyclic trimethylolpropane formal (meth)acrylate, dicyclopentenyl (meth)acrylate, adamantyl (meth)acrylate, and alicyclic (meth)acrylate such as tricyclodecane (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, etc. meth)acrylate;
Aromatic compounds such as phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, (meth)acrylate of alkylene oxide modified phenol, and (meth)acrylate of o-phenylphenol modified with alkylene oxide. (meth)acrylate;
Cyclic ether group-containing (meth)acrylates such as tetrahydrofurfuryl (meth)acrylate and (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate;
Carbonate group-containing (meth)acrylates such as glycerin carbonate (meth)acrylate;
N-(meth)acryloyloxyethylhexahydrophthalimide, 2-(1,2-cyclohexa-1-enedicarboximide)ethyl(meth)acrylate, Fancryl FA-502A [manufactured by Showa Denko Materials Co., Ltd.], etc. and 2-(meth)acryloyloxyethyl acid phosphate.
Among these compounds, 4-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, and tetrahydrofurfuryl (meth)acrylate are used because the cured composition has excellent adhesive strength and water resistance. is particularly preferred.

The content of component (C) is 5 to 70% by weight, preferably 5 to 65% by weight, based on 100% by weight of the total amount of curable components.
If the proportion of component (C) is less than 5% by weight, the curability of the composition will decrease or the adhesive strength of the cured composition will decrease, while if it exceeds 70% by weight, the composition will be cured. The water resistance of objects decreases.

4. Component (D) Component (D) is a photoradical polymerization initiator. Component (D) is a compound that generates radicals upon irradiation with active energy rays and initiates polymerization of components (A), (B), and (C), which are compounds having ethylenically unsaturated groups.

Specific examples of component (D) include benzyl dimethyl ketal, benzyl, benzoin, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane. 1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1- on, oligo[2-hydroxy-2-methyl-1-[4-1-(methylvinyl)phenyl]propanone, 2-hydroxy-1-[4-[4-(2-hydroxy-2-methyl-propionyl)] -benzyl]-phenyl]-2-methylpropan-1-one, 2-methyl-1-[4-(methylthio)]phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino -1-(4-morpholinophenyl)butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one , ADEKA Optomer N-1414 [manufactured by ADEKA Corporation], aromatic ketone compounds such as phenylglyoxylic acid methyl ester, ethyl anthraquinone, and 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)phenylphosphine and bis(2, Acyl phosphine oxide compounds such as 6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide;
Thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 1-chloro-4-propylthioxanthone, 3-[3,4-dimethyl-9-oxo-9H-thioxanthon-2-yl]oxy]- Thioxanthone compounds such as 2-hydroxypropyl-N,N,N-trimethylammonium chloride and fluorothioxanthone;
Acridone compounds such as acridone and 10-butyl-2-chloroacridone;
1,2-octanedione 1-[4-(phenylthio)-2-(O-benzoyloxime)], ethanone 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl] -1-(O-acetyloxime) and other oxime esters, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(m-methoxy) phenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-phenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2-(p- methoxyphenyl)-4,5-diphenylimidazole dimer, 2,4-di(p-methoxyphenyl)-5-phenylimidazole dimer and 2-(2,4-dimethoxyphenyl)-4,5-diphenyl Examples include 2,4,5-triarylimidazole dimers such as imidazole dimers; and acridine derivatives such as 9-phenylacridine and 1,7-bis(9,9'-acridinyl)heptane.

Among the above, it is more preferable in order to make the composition excellent in curability and adhesiveness. Preferred specific examples include aromatic ketone compounds, acylphosphine oxide compounds, and thioxanthone compounds.

As component (D), the above-mentioned compounds may be used alone or in combination of two or more.

The proportion of component (D) is 0.1 to 15 parts by weight, more preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the total amount of curable components.
If the proportion of component (D) is less than 0.1 part by weight, the active energy ray curability of the composition will be insufficient and the adhesiveness will decrease, while if it exceeds 15 parts by weight, the inside of the adhesive layer Curability becomes poor and adhesiveness decreases.

5. Other components The active energy ray-curable adhesive composition for plastic films of the present invention has components (A) to (D) as essential components, but various other components may be added depending on the purpose. I can do it.

Other components include compounds other than component (B) having two or more ethylenically unsaturated groups [hereinafter referred to as "component (E)"]. ], ultraviolet absorbers, polymerization inhibitors, silane coupling agents, antioxidants, and surface modifiers.

5-1． Component (E) Component (E) is a compound having two or more (meth)acryloyl groups in the molecule [hereinafter referred to as "polyfunctional (meth)acrylate"], a compound having two or more vinyl groups in the molecule. (hereinafter referred to as "polyfunctional vinyl compound"). Furthermore, various molecular weights can be selected, and they may be monomers, oligomers, or polymers.

Specific examples of polyfunctional (meth)acrylates include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1 , 6-hexanediol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 2-butyl-2-ethyl-1,3-propanediol di(meth)acrylate and 1,9 - di(meth)acrylates of aliphatic diols, such as nonanediol di(meth)acrylates;
Di(meth)acrylates of alicyclic diols such as cyclohexane dimethylol di(meth)acrylate and tricyclodecane dimethyloldi(meth)acrylate;
Alkylene glycol di(meth)acrylates such as diethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate and tripropylene glycol di(meth)acrylate;
The esterification reaction product of neopentyl glycol, hydroxypivalic acid, and (meth)acrylic acid (hereinafter referred to as "neopentyl hydroxypivalate glycol di(meth)acrylate"), caprolactone-modified neopentyl glycol di(meth)acrylate hydroxypivalate, ) acrylate;
Di(meth)acrylate of alkylene oxide adduct of bisphenol compound such as di(meth)acrylate of bisphenol A alkylene oxide adduct;
Di(meth)acrylates of hydrogenated bisphenol compounds such as di(meth)acrylates of hydrogenated bisphenol A;
Di(meth)acrylate of isocyanuric acid alkylene oxide adduct, tri(meth)acrylate of isocyanuric acid alkylene oxide adduct, di(meth)acrylate of caprolactone-modified isocyanuric acid alkylene oxide adduct, caprolactone-modified isocyanuric acid alkylene oxide adduct Poly(meth)acrylates of isocyanuric acid alkylene oxide adducts such as tri(meth)acrylates;
Polyol poly(meth)acrylates such as trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri- or tetra(meth)acrylate, dipentaerythritol penta- or hexa(meth)acrylate;
Tri(meth)acrylate of trimethylolpropane alkylene oxide adduct, tetra(meth)acrylate of ditrimethylolpropane alkylene oxide adduct, tri- or tetra(meth)acrylate of pentaerythritol alkylene oxide adduct, dipentaerythritol alkylene oxide adduct Poly(meth)acrylates of polyol alkylene oxide adducts such as penta- or hexa(meth)acrylates:
Urethane (meth)acrylate;
Examples include epoxy (meth)acrylate; and polyester (meth)acrylate.
The polyester (meth)acrylate may be a dendrimer type (meth)acrylate.
In the alkylene oxide adduct, examples of the alkylene oxide include ethylene oxide and propylene oxide.

Specific examples of hydroxyl group-containing polyfunctional (meth)acrylates include trimethylolpropane mono- or di-(meth)acrylate, pentaerythritol mono-, di- or tri-(meth)acrylate, and di-trimethylolpropane mono-, di- or tri-(meth)acrylate. Mention may be made of acrylates and dipentaerythritol mono-, di-, tri-, tetra- or penta(meth)acrylates, epoxy(meth)acrylates.

Epoxy (meth)acrylate is a compound obtained by adding (meth)acrylic acid to an epoxy resin, and is described in the literature "UV/EB Curing Materials" [CMC Co., Ltd., published in 1992], pages 74-75. Examples include compounds such as those described.

Examples of the epoxy resin include aromatic epoxy resins and aliphatic epoxy resins.
Specific examples of the aromatic epoxy resin include resorcinol diglycidyl ether; di- or polyglycidyl ether of bisphenol A, bisphenol F, bisphenol S, bisphenol fluorene or its alkylene oxide adduct; phenol novolak type epoxy resin and cresol novolak type epoxy resin. Examples include novolac type epoxy resins such as epoxy resins; glycidyl phthalimide; o-phthalic acid diglycidyl ester;
In addition to these, there are also two chapters of the literature "Epoxy Resins - Recent Advances" (Shokodo, published in 1990), and the literature "Kobunshi Processing" Special Volume 9, Volume 22 Extra Issue Epoxy Resins [Kobunshi Publishing Co., Ltd., Compounds such as those described on pages 4 to 6 and pages 9 to 16 of ``Published in 1972'' can be mentioned.

Specific examples of aliphatic epoxy resins include diglycidyl ethers of alkylene glycols such as ethylene glycol, propylene glycol, 1,4-butanediol and 1,6-hexanediol; diglycidyl ethers of polyethylene glycol and polypropylene glycol, etc. diglycidyl ether of polyalkylene glycol; diglycidyl ether of neopentyl glycol, dibromoneopentyl glycol and its alkylene oxide adduct; di- or triglycidyl ether of trimethylolethane, trimethylolpropane, glycerin and its alkylene oxide adduct; and polyglycidyl ethers of polyhydric alcohols such as di-, tri- or tetraglycidyl ethers of pentaerythritol and its alkylene oxide adducts; di- or polyglycidyl ethers of hydrogenated bisphenol A and its alkylene oxide adducts; diglycidyl tetrahydrophthalate Ethers include hydroquinone diglycidyl ether and the like.
In addition to these, compounds described on pages 3 to 6 of the above-mentioned document "Polymer Processing" special edition of epoxy resins can be mentioned.

In addition to these aromatic epoxy resins and aliphatic epoxy resins, there are epoxy compounds having a triazine nucleus in the skeleton, such as TEPIC [Nissan Chemical Co., Ltd.], Denacol EX-310 [Nagase Kasei Co., Ltd.], etc. Compounds such as those described on pages 289 to 296 of the above-mentioned literature "Polymer Processing" special edition of epoxy resins may be mentioned.
In the above, the alkylene oxide of the alkylene oxide adduct is preferably ethylene oxide, propylene oxide, or the like.

Examples of the allyl compound include monofunctional allyl compounds such as allyl alcohol, and polyfunctional allyl compounds such as diallyl phthalate, triallyl isocyanurate, and triallyl cyanurate.

In addition to these, compounds such as those described on pages 53 to 56 of the document "Latest UV Curing Technology" [Printing Information Association Co., Ltd., published in 1991] may be mentioned.

Among component (E), 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, and 1,6-hexanediol di(meth)acrylate are used because they can increase heat resistance and adhesive strength. acrylate, neopentyl glycol hydroxypivalic acid di(meth)acrylate, caprolactone-modified neopentyl glycol hydroxypivalic acid di(meth)acrylate, bisphenol A type epoxy (meth)acrylate, and caprolactone-modified neopentyl glycol hydroxypivalic acid di(meth)acrylate are preferred. ) acrylate (the amount modified with caprolactone is preferably 1 to 10 mol) and bisphenol A type epoxy (meth)acrylate are particularly preferred.

The content of component (E) in the curable component is preferably 1 to 30% by weight, more preferably 2 to 20% by weight based on 100% by weight of the total amount of the curable component. When the proportion of component (E) is 1% by weight or more, it has excellent heat resistance, and when the proportion of component (E) is 30% by weight or less, a decrease in adhesive strength can be suppressed.

5-2． Ultraviolet absorber The composition of the present invention can improve adhesive strength by containing an ultraviolet absorber. Although the reason is unknown, it is presumed that by blocking ultraviolet rays in the low wavelength range, the curing speed is suppressed and the residual stress at the adhesive interface is reduced.

Examples of the ultraviolet absorber include triazine ultraviolet absorbers such as TINUVIN400, TINUVIN405, TINUVIN460, and TINUVIN479 manufactured by BASF, and benzotriazole ultraviolet absorbers such as TINUVIN900, TINUVIN928, and TINUVIN1130.

The content ratio of the ultraviolet absorber may be appropriately set depending on the purpose, and is preferably 0.1 to 5 parts by weight, more preferably 0.5 to 2 parts by weight, based on 100 parts by weight of the total amount of curable components. It is. When the content is 0.1 parts by weight or more, the adhesive strength can be increased, and when the content is 5 parts by weight or less, deterioration in curability can be suppressed.

5-3． Polymerization inhibitor Examples of the polymerization inhibitor include organic polymerization inhibitors, inorganic polymerization inhibitors, and organic salt polymerization inhibitors.
Specific examples of organic polymerization inhibitors include hydroquinone, tert-butylhydroquinone, hydroquinone monomethyl ether, 2,6-di-tert-butyl-4-methylphenol, 2,4,6-tri-tert-butylphenol, 4- Phenol compounds such as tert-butylcatechol, quinone compounds such as benzoquinone, galvinoxyl, 2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1 Examples include stable radicals such as -oxyl, phenothiazine, N-nitroso-N-phenylhydroxylamine ammonium, and the like.
Specific examples of inorganic polymerization inhibitors include copper chloride, copper sulfate, and iron sulfate.
Specific examples of organic salt-based polymerization inhibitors include nitroso compounds such as N-nitroso-N-phenylhydroxylamine aluminum salt, ammonium N-nitrosophenylhydroxylamine, and copper dibutyldithiocarbamate.

Among these, stable radicals and nitroso compounds are preferred because they cause little coloring of the adhesive, prevent thickening and gelation of the composition, and improve storage stability.
The content ratio of the polymerization inhibitor may be appropriately set depending on the purpose, and is preferably 0.0001 to 1 part by weight, more preferably 0.0005 to 0.5 parts by weight, based on 100 parts by weight of the total amount of curable components. Parts by weight. When the content is 0.0001 part by weight or more, the thermal stability and photostability of the composition can be improved, and when the content is 1 part by weight or less, the photocurability of the composition is excellent. I can do it.

5-4. Silane coupling agent Specific examples of the silane coupling agent include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-(meth)acryloxypropylmethyldiethoxysilane, 3-(meth)acrylic Roxypropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3 -Aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-amino Examples include propyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 3-mercaptopropyltrimethoxysilane. These may be used alone or in combination of two or more.

5-5． Antioxidants Examples of antioxidants include phenolic antioxidants, phosphorus antioxidants, and sulfur antioxidants.
Specific examples of phenolic antioxidants include hindered phenols such as di-t-butylhydroxytoluene. Commercially available products include AO-20, AO-30, AO-40, AO-50, AO-60, AO-70, and AO-80 manufactured by ADEKA Corporation.
Specific examples of phosphorus-based antioxidants include phosphines such as trialkylphosphines and triarylphosphines, trialkyl phosphites, and triaryl phosphites. Commercially available derivatives of these include, for example, ADEKA STAB PEP-4C, PEP-8, PEP-24G, PEP-36, HP-10, 260, 522A, 329K, 1178, 1500, 135A, 3010 manufactured by ADEKA Co., Ltd. etc.
Specific examples of sulfur-based antioxidants include thioether-based compounds, and commercially available products include ADEKA Corporation's AO-23, AO-412S, and AO-503A.
These may be used alone or in combination of two or more. Preferred combinations of these antioxidants include combinations of phenolic antioxidants and phosphorus antioxidants, and combinations of phenolic antioxidants and sulfur antioxidants.

5-6． Surface modifiers Surface modifiers include surface conditioning agents, surfactants, leveling agents, antifoaming agents, slippery agents, antifouling agents, etc. These known surface modifiers are used. can do.
Among these, silicone-based surface modifiers and fluorine-based surface modifiers are preferably mentioned.
Specific examples include silicone polymers and oligomers having silicone chains and polyalkylene oxide chains, silicone polymers and oligomers having silicone chains and polyester chains, and fluorine polymers having perfluoroalkyl groups and polyalkylene oxide chains. and oligomers, and fluorine-based polymers and oligomers having perfluoroalkyl ether chains and polyalkylene oxide chains.
Furthermore, in order to improve durability, a surface modifier having an ethylenically unsaturated group, preferably a (meth)acryloyl group, in the molecule may be used. These may be used alone or in combination of two or more.

6. Active energy ray curable adhesive composition for plastic films or sheets The present invention relates to an active energy ray curable adhesive composition for plastic films or sheets containing the components (A) to (D) in specific proportions. It is.
The composition can be produced by stirring and mixing the components (A) to (D) and, if necessary, other components according to a conventional method.
In this case, heating can be performed if necessary. The heating temperature may be appropriately set depending on the composition, substrate, purpose, etc. used, but is preferably 30 to 80°C.
The proportion of the curable component in the composition is preferably 70 to 99.9% by weight, more preferably 90 to 99% by weight.

The viscosity of the composition is preferably 10 to 1,000 mPa·s in terms of excellent coating properties on substrates.

7. Method of Use The composition of the present invention can be used for adhesion between plastic films and for adhesion between plastic films and various other base materials (hereinafter referred to as other base materials). Examples include a method of coating, bonding with another base material, and irradiating with active energy rays.
In addition, in the present invention, when simply written as "base material", it means a general term for plastic films and other base materials.
Other base materials include paper and metal.

Plastic films include hydrophilic plastic films and hydrophobic plastics.
Specific examples of hydrophilic plastic films include polyvinyl alcohol films, and cellulose ester films such as triacetyl cellulose films and diacetyl cellulose films.
Specific examples of hydrophobic plastic films include polycarbonate films, polyethylene terephthalate films, polyethylene naphthalate films, acrylic films, acrylic/styrene films, aliphatic polyamide (nylon) films, aromatic polyamide films, Polyurethane film, polyimide film, ethylene-vinyl acetate copolymer film, polyvinyl chloride film, polyvinylidene chloride film, polyethylene film, polypropylene film, polycycloolefin film, polystyrene film, ABS film , and chlorinated polypropylene films.
Examples of the paper include imitation paper, high-quality paper, kraft paper, art coated paper, caster coated paper, pure white roll paper, parchment paper, waterproof paper, glassine paper, and corrugated paper.
Examples of the metal foil include aluminum foil.

Coating to the substrate can be done using conventionally known methods such as natural coater, knife belt coater, floating knife, knife over roll, knife on blanket, spray, dip, kiss roll, squeeze roll, reverse roll, and air blade. , curtain flow coater, comma coater, gravure coater, microgravure coater, die coater and curtain coater.
Further, the coating thickness of the composition of the present invention may be selected depending on the substrate used and the application, but is preferably 0.1 to 100 μm, more preferably 1 to 25 μm.

Examples of active energy rays include visible light, ultraviolet rays, X-rays, and electron beams, but ultraviolet rays are preferred because inexpensive equipment can be used.
Various light sources can be used for curing with ultraviolet rays, such as pressurized or high-pressure mercury lamps, metal halide lamps, xenon lamps, electrodeless discharge lamps, carbon arc lamps, and LEDs. Among these, high-pressure mercury lamps and metal halide lamps are preferred, and metal halide lamps are particularly preferred. The amount of ultraviolet ray irradiation is preferably 200 to 2,000 mJ/cm ² in the UV-A region (near 365 nm), more preferably 300 to 1,500 mJ/cm ² .

In the case of curing with an electron beam, various EB irradiation devices can be used, such as Cockroft-Waltsin type, Vandegraaf type, and resonant transformer type devices. The absorbed dose of the electron beam is preferably 1 to 200 kGy, more preferably 10 to 100 kGy. The accelerating voltage of the electron beam may be appropriately set in the range of 80 to 300 kV depending on the thickness of the base material, and for example, if the thickness of the base material is 100 μm, 200 kV is preferable. The oxygen concentration of the electron beam irradiation atmosphere is preferably 500 ppm or less, more preferably 300 ppm or less.

8. Laminate and method for manufacturing the same The laminate of the present invention is a laminate comprising a base material, a cured material layer formed from the above-described composition, and another base material, wherein the base material and the other base material Both or one of the materials is a plastic film.
The composition of the present invention is suitable for bonding thin layer adherends as a base material, and the method of use when bonding thin layer adherends is in accordance with the method commonly used in the manufacture of laminates. Bye. For example, a method in which the composition is applied to a first thin layer adherend, dried if necessary, and then a second thin layer adherend is bonded thereto and irradiated with active energy rays. can be mentioned.
The coating method of the composition, the film thickness of the composition, the irradiation conditions such as the type of active energy ray, etc. are also as described above.

Examples of thin layer adherends include plastic films, paper, and metal foils.
The plastic film must be able to transmit active energy rays, and the film thickness may be selected depending on the thin layer adherend used and the application, but preferably the thickness is 0.2 mm or less. .

Among these thin layer adherends, the composition of the present invention is suitably used for adhesion between plastic films, and is further suitable for adhesion between hydrophilic plastics and hydrophobic plastic films and hydrophilic plastic films. It can be used for.

Furthermore, before bonding the adherend, activation treatment can be performed on one or both surfaces in order to increase the interlayer adhesion force. Examples of the surface activation treatment include plasma treatment, corona discharge treatment, chemical treatment, surface roughening treatment, etching treatment, flame treatment, etc., and these may be used in combination.

Coating to the thin layer adherend may be done by any conventionally known method, including the same methods as mentioned above.
Further, the coating thickness of the composition of the present invention may be selected depending on the thin layer adherend to be used and the application, but the same coating thickness as described above is preferable.

Further, in this case, bonding can be performed not only in a flat state but also in a curved state.
That is, a method may be mentioned in which the base material is bent into a concave or convex state, the composition is applied in this state, the other base material is bonded, and active energy rays are irradiated.
Another method is to apply the composition of the present invention to a flat base material, bond the other base material together, bend it into a concave or convex state, and bond it by irradiating it with active energy rays. Can be mentioned.
In this case, the method described above may be followed as a method for applying the composition in a flat state. Examples of methods for applying the composition on a curved surface include methods using spray, dip, curtain flow coater, screen printing, slot die coater, and the like.

By the above method, a laminate composed of a plastic film/a cured product layer formed from the composition of the present invention/a plastic film, a plastic film/a cured product layer formed from the composition of the present invention/another base material A laminate consisting of:
The laminate film obtained from the composition of the present invention has excellent adhesive strength under high temperature and high humidity conditions, so it can be used as polarizing plates and protective films for liquid crystal displays, optical films such as retardation films, and It can be suitably used for polarized lenses used in polarized glasses and the like.
Furthermore, in a laminate composed of a plastic film/a cured material layer formed from the composition of the present invention/a plastic film, one of the plastic films is a triacetylcellulose film or a polyvinyl alcohol-based plastic film, and the other A laminate in which is a hydrophobic plastic film is preferable, and it is preferable that the laminate is a polarizing plate.
Incidentally, in the present invention, the term "polarizing plate" includes a polarizing lens as a concept.

As a method for manufacturing the laminate, a manufacturing method in which the following steps 1 to 3 are performed sequentially is preferred.
・Step 1: Coating the composition on at least one of the bonding surfaces of the base material and the plastic film ・Step 2: Applying the composition to the base material and the plastic film via the composition layer obtained in Step 1 Step 3 of laminating: With the base material and the plastic film laminated via the composition layer, active energy rays are irradiated from either side of the base material or the plastic film to bond the composition. The base material in step 1 is preferably a plastic film. In this case, it is preferable that one of the two plastic films is a hydrophilic plastic film and the other is a hydrophobic plastic film, and the hydrophilic plastic film is preferably a triacetylcellulose plastic film or a polyvinyl alcohol-based plastic film. Plastic films are preferred.
Examples of the method for applying the composition in step 1 include the methods described above.
The active energy ray irradiation conditions and irradiation method in Step 3 include the methods described above.

8-1. Preferred form The composition of the present invention can be particularly preferably used for producing polarizing plates (polarizing lenses) and polarizing plates with retardation films. Hereinafter, a method for manufacturing a polarizing plate will be explained.

In this specification, the term "polarizer" refers to a film or film having a polarizing function as described below, and the term "polarizing plate" refers to a polarizer with a protective layer, in which one or both sides of the polarizer are protected with a film or film. represents something. In addition, a polarizing plate with a retardation film refers to a polarizer or a polarizing plate in which a retardation film is laminated or coated to form a film having a retardation function.

As mentioned above, the composition of the present invention can be preferably used for bonding hydrophilic plastics and hydrophobic plastics, and in the production of polarizing plates, polyvinyl alcohol used as a polarizer and cellulose ester used as a protective film for the polarizer are used. Polycarbonate, acrylic, cycloolefin polymer, etc. are equivalent to hydrophobic plastics.

The composition of the present invention can be used for adhesion between a polarizer and a protective film, between a polarizing plate and a retardation film, between protective films, and the like.

A polarizer has a function of selectively transmitting linearly polarized light in one direction from natural light.
Specific examples of polarizers include iodine-based polarizers in which iodine is adsorbed and oriented on polyvinyl alcohol-based films, dye-based polarizers in which dichroic dyes are adsorbed and oriented in polyvinyl alcohol-based films, and (lyotropic) liquid crystals. Examples include coated polarizers coated with a state dye, oriented and fixed.
These iodine-based polarizers, dye-based polarizers, and coated polarizers have the function of selectively transmitting linearly polarized light in one direction from natural light and absorbing linearly polarized light in the other direction. It is called a type polarizer.

The above-mentioned iodine-based polarizer and dye-based polarizer are usually provided with a protective layer on one or both sides thereof, and the composition of the present invention can be used for adhesion between a polarizer and a protective film.

Specific examples of protective films used in the protective layer include cellulose ester films such as triacetylcellulose and diacetylcellulose, acrylic films, polyethylene terephthalate films, polyarylate films, polyethersulfone films, and norbornene films. Examples include a cyclic polyolefin film containing a cyclic olefin as a monomer, an aliphatic polyamide (nylon) film, and a polycarbonate film.

Next, the composition of the present invention can also be used for adhering polarizing plates and other optical films.
In this case, a polarizing plate having a protective layer on one or both sides can be used.
In this case, a specific example of the protective layer may be one in which the above-mentioned protective film is laminated, or a protective film formed by coating.
In a polarizing plate provided with a protective layer only on one side, the surface to be adhered to the retardation film may be the surface with the protective layer or the surface without the protective layer.

Various other optical films can be used, such as optical films for adjusting birefringence that have been subjected to processing such as uniaxial or biaxial stretching, or liquid crystalline compounds, etc., which are applied to the base material and oriented and fixed. An example of this is an optical film that has been processed in such a way that the three-dimensional refractive index magnitude relationship (refractive index ellipsoid) is controlled according to the conditions of use. It is mainly used to compensate for coloring of the liquid crystal layer of a liquid crystal display and to compensate for changes in phase difference due to viewing angle.
The other optical film may be a protective film.

To give specific examples of retardation films, materials for optical films that undergo processing such as stretching include polyolefins such as polyethylene, polypropylene, and cyclic polyolefins, polycarbonate, polyvinyl alcohol, polystyrene, polymethyl methacrylate, and polyarylate. Examples include polyamide and polyamide.
The above-mentioned cyclic polyolefin is a general term for resins obtained from cyclic olefins such as norbornene, tetracyclododecene, and derivatives thereof. Examples include those described in .
Specifically, ring-opening polymers of cyclic olefins, addition polymers of cyclic olefins, random copolymers of cyclic olefins and α-olefins such as ethylene and propylene, and modifications of these with unsaturated carboxylic acids or derivatives thereof, etc. Examples include graft modified products. Further examples include hydrides of these. Examples of the products include Zeonex and Zeonor manufactured by Zeon Corporation, Arton manufactured by JSR Corporation, and Topus manufactured by TICONA.

In addition, as optical films in which a liquid crystalline compound, etc. is applied to a base material and subjected to orientation and fixation processing, there are "WV film" (manufactured by Fuji Film Co., Ltd.), "LC film", and "NH film". [All manufactured by JX Nippon Oil & Energy Corporation] and the like.

A method for producing a polarizing plate or a polarizing plate with a retardation film using the composition of the present invention will be described below.
Examples of the manufacturing method include methods including the following steps [1] to [3].
[1] A step of applying the composition of the present invention to any one of a polarizer, a polarizing plate, a protective film, a protective film, a retardation film, and a retardation film as an adherend;
[2] A step of laminating any one of a polarizer, a polarizing plate, a protective film, a protective film, a retardation film, or a retardation film, which is the other adherend, to the film coated with the composition;
[3] After laminating the films, a step of irradiating active energy rays through the base material coated with the composition of the present invention.
When laminating a protective film or retardation film on only one side, a polarizing plate or a polarizing plate with a retardation film can be manufactured by the above procedure, but when laminating on both sides, steps [1] and [2] ] may be repeated twice, and then step [3] may be carried out, or steps [1], [2] and [3] may be repeated twice.

The coating method in step [1] and the active energy ray irradiation method in step [3] may be performed in the same manner as described above.
Further, as described above, it is also possible to bond the curved surface.

When using a polarizing plate with a retardation film as a circularly polarizing plate, in order to achieve a circularly polarized state over a wide range, a retardation film with a different retardation must be further attached to the retardation film side of the polarizing plate with a retardation film. It can also be combined.
Specifically, there is a method of laminating a retardation film having a 1/2 wavelength for each wavelength to a polarizer film, and then laminating a retardation film having a 1/4 wavelength for each wavelength. be. In this case, step [3] may be carried out after repeating steps [1] and [2] three times, or steps [1], [2] and [3] may be repeated three times.

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples below. In addition, "parts" in each of the following examples means parts by weight.

1. Examples 1 to 13, Comparative Examples 1 to 4
1-1. Preparation of active energy ray curable adhesive composition Components (A) to (E) shown in Table 1 below and other components were dissolved by heating and stirring at 60°C for 1 hour to prepare an active energy ray curable adhesive composition. was manufactured.
The obtained compositions shown in Table 1 were used to perform the evaluations described below. The results are shown in Table 1.

Note that the numbers in Table 1 mean parts by weight. Moreover, the abbreviations in Table 1 mean the following.

◆(A) Component /ACMO: Acryloylmorpholine, ACMO (product name) manufactured by KJ Chemicals Co., Ltd.
・NVP: N-vinylpyrrolidone, V-Pyrol manufactured by Ashland (trade name)
・NVC: N-vinyl caprolactam, V-Cap manufactured by Ashland (product name)
◆(B) Component
・UN6305: Polyether-based bifunctional urethane acrylate (Mw27,000), Art Resin UN-6305 (product name) manufactured by Negami Kogyo Co., Ltd.
・M1200: Polyester urethane acrylate (Mw3,000), Aronix M-1200 (product name) manufactured by Toagosei Co., Ltd.
・UN9200A: Polycarbonate-based bifunctional urethane acrylate (Mw 15,000), Art Resin UN-9200A (product name) manufactured by Negami Kogyo Co., Ltd.
◆(C) Component
・THFA: Tetrahydrofurfuryl acrylate, Viscoat #150 (trade name) manufactured by Osaka Organic Chemical Industry Co., Ltd.
・M101A: Phenol EO modified (n=2) acrylate, Aronix M-101A (trade name) manufactured by Toagosei Co., Ltd.
・4HBA: 4-Hydroxybutyl acrylate, Viscoat 4-HBA (product name) manufactured by Osaka Organic Chemical Industry Co., Ltd.
・IBXA: Isobornyl acrylate, IBXA (product name) manufactured by Osaka Organic Chemical Industry Co., Ltd.
◆(D) Component
・TPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide, Omnirad TPO (product name) manufactured by IGM Resin Co., Ltd.
◆(E) Component
FM400: Hydroxypivalic acid neopentyl glycol diacrylate, Kayarad FM-400 (trade name) manufactured by Nippon Kayaku Co., Ltd.
・M313: Isocyanuric acid EO modified triacrylate, Aronix M-313 (trade name) manufactured by Toagosei Co., Ltd.
・VR77: Bifunctional epoxy acrylate, Lipoxy VR-77 (product name) manufactured by Showa Denko K.K.

1-2. Evaluation of Active Energy Ray Curable Adhesive Composition The obtained composition was evaluated according to the following test method. The results are shown in Table 1.

1) Evaluation of composition
◆25°C Viscosity The viscosity of the active energy ray-curable adhesive composition at 25°C was measured using an E-type viscometer.

◆Coating properties The obtained composition was coated with a triacetyl cellulose film containing a UV absorber (trade name: FUJITAC, manufactured by Fuji Film Co., Ltd., hereinafter referred to as "TAC") with a width of 300 mm and a length of 300 mm so that the film thickness was 5 μm. That's what it means. ] with an applicator to form a coating film, and the coating properties at this time were evaluated using the following three criteria.
○: The film thickness of the coating film is uniform with no variation within the surface.
△: The film thickness of the coating film has small variations within the surface.
×: The film thickness of the coating film varies widely within the surface and is non-uniform.

2) Evaluation of laminate
(1) Production of laminate As a hydrophilic plastic film, corona treatment (Polydyne 1 manufactured by Navitas, output 0.1 kW, processing speed 1 second/cm) was performed on TAC as an adhesion treatment. At this time, the contact angle of water on TAC at 23°C was 66°.
Subsequently, the obtained active energy ray-curable adhesive composition was applied to a thickness of 5 μm using a bar coater, and a polycarbonate film with a thickness of 125 μm [trade name Panlite PC-2151, Teijin Ltd. ), hereinafter referred to as "PC". ] was laminated. Note that the contact angle of water at 23° C. on the PC at this time was 80°.
After that, a conveyor-type ultraviolet irradiation device (160 W/cm metal halide lamp, UV-A region irradiation intensity 500 mW/cm ² , cumulative light amount 1,000 mJ/cm ² manufactured by I-Graphics Co., Ltd., both manufactured by Heraeus Co., Ltd.) was used. Using UV POWER PUCK (measured value of UV POWER PUCK), the front and back surfaces of the laminate film were irradiated with ultraviolet light in one pass each to be cured.

(2) Evaluation method of laminate
◆Peel strength The laminate obtained above was attached to glass via double-sided tape, and the peel strength was measured under the following conditions.
・Tensile tester: Instron 5564 manufactured by Instron Japan Company Limited
・Test piece: width 25mm x 100mm
・Test method: 90° peeling ・Peeling speed: 200mm/min

◆Environmental test The laminate obtained above was cut into 5 cm square or A4 size pieces, placed in a constant temperature and humidity chamber at 60°C and 90% RH, and taken out after 500 hours to observe the appearance. Based on the presence or absence of changes, the following Durability was evaluated on three levels.
〇: No change △: Peeling and foaming occur, and the area is less than 10% of the sample size ×: Peeling and foaming occur, and the area exceeds 10% of the sample size

3) Evaluation Results As is clear from the results of Examples 1 to 13, the active energy ray-curable adhesive composition of the present invention has excellent peel strength and environmental tests, and has excellent properties in hydrophilic plastic film (TAC). It had excellent adhesion to hydrophobic plastic film (PC).
On the other hand, the adhesive composition (Comparative Example 1) in which the content ratio of component (A) is less than the lower limit of 20% by weight of the content ratio of the present invention has a lower peel strength and lower environmental test durability. The composition (Comparative Example 2) in which the content ratio of component (A) exceeds the upper limit of 75% by weight of the content ratio of the present invention has poor durability in an environmental test over a large area, and (B) A composition (Comparative Example 3) in which the content ratio of the component is less than the lower limit of 10% by weight of the content ratio of the present invention has poor durability in an environmental test, and the content ratio of the component (B) is less than the lower limit of the content ratio of the present invention (Comparative Example 3). The composition exceeding the upper limit of 35% by weight (Comparative Example 4) had high viscosity and poor coating properties.

The composition of the present invention can be used as an adhesive for various plastic films, especially between hydrophilic plastic films, and between hydrophobic plastic films and hydrophilic plastic films, such as liquid crystal displays, organic EL displays, etc. It can be suitably used for various optical films used in. Specifically, polarizing plates, retardation films, viewing angle compensation films, brightness enhancement films, anti-reflection films, anti-glare films, lens sheets, diffusion sheets, hard coat films with anti-fingerprint and anti-glare functions, Examples include optical films such as front plates of touch panels and polarized lenses such as polarized glasses, and can be particularly suitably used for manufacturing polarizing plates.

Claims (12)

It is composed of at least a curable component and a polymerization initiator, the curable component is composed of at least the following components (A) to (C), and the polymerization initiator is composed of at least the following component (D),
(A) component: water-soluble compound having a nitrogen atom and one ethylenically unsaturated group in the molecule (B) component: urethane (meth)acrylate (C) component: ethylenic compound other than component (A) Compound (D) component having one unsaturated group: photoradical polymerization initiator Contains the above-mentioned (A) to (C) components in the following proportions in 100% by weight of the total amount of curable components,
(A) Component: 20-75% by weight
(B) Component: 10 to 35% by weight
(C) Component: 5 to 70% by weight
An active energy ray-curable adhesive composition for plastic films or sheets, which contains the component (D) in the following proportions based on 100 parts by weight of the total amount of curable components.
(D) Component: 0.1 to 15 parts by weight The active energy ray-curable adhesive composition for plastic films or sheets according to claim 1, wherein the component (B) contains urethane (meth)acrylate having a weight average molecular weight of 2,000 to 100,000. . Claim 1 or Claim 2, wherein the component (A) contains at least one selected from the group consisting of (meth)acryloylmorpholine, N-vinylpyrrolidone, N-vinylcaprolactam, and N-vinylformamide. The active energy ray-curable adhesive composition for plastic films or sheets as described above. The active energy ray for a plastic film or sheet according to any one of claims 1 to 3, wherein the component (C) is a compound having one (meth)acryloyl group with a molecular weight of less than 300. Curable adhesive composition. The active energy ray-curable adhesive composition for plastic films or sheets according to any one of claims 1 to 4, further comprising the following component (E) as a curable component.
Component (E): Compound other than component (B) having two or more ethylenically unsaturated groups The active energy ray-curable adhesive for a plastic film or sheet for producing a polarizing plate according to any one of claims 1 to 5, wherein the plastic film or sheet is a hydrophilic plastic film or sheet. Composition. A laminate comprising a base material, a cured material layer formed from the composition according to any one of claims 1 to 6, and a plastic film or sheet, which are laminated in this order. The base material is a plastic film or sheet, and further, one of the two plastic films or sheets is a triacetyl cellulose plastic film or sheet, or a polyvinyl alcohol plastic film or sheet, and the other is a plastic film or sheet. The laminate according to claim 7, which is a hydrophobic plastic film or sheet. A polarizing plate comprising the laminate according to claim 8. A method for manufacturing a laminate, which sequentially carries out the following steps 1 to 3.
・Step 1: A step of coating the composition according to any one of claims 1 to 6 on at least one of the bonding surfaces of the base material and the plastic film or sheet. ・Step 2: In step 1. Step 3 of laminating the base material and the plastic film or sheet through the obtained composition layer: With the base material and the plastic film or sheet laminated through the composition layer, A step of curing the composition by irradiating active energy rays from either side of the base material or the plastic film or sheet. The base material in step 1 is a plastic film or sheet, and further, either of the two plastic films or sheets is a triacetyl cellulose plastic film or sheet, or a polyvinyl alcohol plastic film or sheet. 11. The method for producing a laminate according to claim 10, wherein the other is a hydrophobic plastic film or sheet. A method for manufacturing a polarizing plate comprising the method for manufacturing a laminate according to claim 10.