TW201706381A - Adhesive, bonded object and bonded object manufacturing method - Google Patents

Abstract

Provided are: a bonding agent for bonding a film containing a PVA-based polymer and a protective film, which is an active energy ray curable bonding agent comprising a PVA-based polymer (A), a cationic polymerizable compound (B) and a cationic polymerization initiator (C); a bonded body comprising a film containing a PVA-based polymer, a protective film, and a bonding agent layer disposed between the film containing the PVA-based polymer and the protective film, with the bonding agent layer being formed from the bonding agent; and a method for manufacturing the bonded body in which the bonding agent is cured by being irradiated with an active energy ray, after affixing the film containing the PVA-based polymer and the protective film with the bonding agent interposed therebetween. Due to this configuration, the present invention can provide a bonding agent with which a high adhesive strength is demonstrated in the bonding between the film containing the PVA-based polymer and the protective film and which is capable of producing a bonded body such as a polarizing plate having excellent water resistance; a bonded body that can be produced using the bonding agent; and a method for manufacturing the bonded body.

Description

Subsequent agent, adhesion body, and method of manufacturing the same

The present invention relates to an adhesive, a battery obtained by using the adhesive, and a method for producing the adhesive, wherein the adhesive is a film comprising a polyvinyl alcohol polymer (hereinafter referred to as "polyvinyl alcohol" or "PVA"). A high adhesion force is exhibited in the subsequent step of the protective film, and a binder excellent in water resistance can be obtained.

A polarizing plate having a light penetrating and shielding function is a basic constituent element of a liquid crystal that changes a polarization state of light together with a liquid crystal display (LCD). Many polarizing plates have a structure in which a protective film such as a cellulose triacetate (TAC) film is bonded to the surface of a polarizing film, and a PVA-based polymer film is uniaxially stretched as a polarizing film constituting a polarizing plate. On the stretched film of the alignment, a dichroic dye which adsorbs an iodine dye (I ₃ ^- or I ₅ ^- or the like) or a dichroic organic dye is the mainstream. Such a polarizing film is usually obtained by uniaxially stretching a PVA-based polymer film containing a dichroic dye in advance, or adsorbing a dichroic dye while uniaxially stretching a PVA-based polymer film, or polymerizing a PVA-based polymer. After the film is uniaxially stretched, it is continuously produced by adsorbing a dichroic dye or the like.

LCD is used in a wide range of small devices such as electronic computers and watches, notebook computers, liquid crystal monitors, liquid crystal color projectors, liquid crystal televisions, car navigation systems, mobile phones, and measurement devices used indoors and outdoors. In recent years, there have been a large number of mobile users, such as small notebook computers and mobile phones, and the polarizing plate has been strongly required to be thinned.

In the case of reducing the thickness of the polarizing plate, the polarizing film or the protective film may be thinned. However, when the film is made thinner, the durability and water resistance of the polarizing plate are lowered. Therefore, in recent years, as a protective film, a (meth)acrylic polymer film, a polyester film, a polymer film containing an alicyclic structure, or the like has been proposed as a substitute for the conventional TAC film having high moisture permeability.

When a polarizing plate is produced by using such a protective film, a cationically polymerizable adhesive containing a multi-branched polyol having 10 or more hydroxyl groups is known as a binder to be used in connection with a polarizing film (see Patent Document 1). Or a radiation curable composition containing a compound having a number average molecular weight of 500 or more and containing two or more hydroxyl groups (refer to Patent Document 2).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2008-111105

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2009-227804

However, the adhesive described in Patent Document 1 contains a multi-branched polyol having poor solubility in a monomer, and the uniformity of the adhesive is deteriorated, and the adhesive force between the polarizing film in the surface of the polarizing plate and the protective film occurs. Uneven, the result is then easy to reduce. Further, the adhesive described in Patent Document 2 also has a problem that the adhesion between the polarizing film and the protective film is low, and the durability and water resistance of the polarizing plate are lowered.

An object of the present invention is to provide an adhesive, a battery obtained by using the adhesive, and a method for producing the adhesive, which is displayed in a film including a PVA polymer such as a polarizing film and a protective film. A high adhesion force and a laminate of a polarizing plate or the like excellent in water resistance can be obtained.

In order to achieve the above object, the inventors of the present invention have repeatedly conducted intensive studies and found that PVA polymerization such as unacetalized PVA or polyvinyl butyral is blended in an active energy ray-curable adhesive. The material (A), the cationically polymerizable compound (B), and the cationic polymerization initiator (C) can improve the adhesion between the film containing the PVA-based polymer and the protective film, and can also improve the water resistance. Based on such knowledge and knowledge, the present invention will be further repeated.

That is, the present invention relates to: [1] an active energy ray-curing type adhesive for a film comprising a PVA-based polymer and a protective film, comprising a PVA-based polymer (A), cationic polymerization. The compound (B) and the cationic polymerization initiator (C); [2] The above-mentioned [1], further comprising a radical polymerizable property The compound (D) and the radical polymerization initiator (E); [3] The above-mentioned [1] or [2], wherein at least a part of the cationically polymerizable compound (B) is cationically polymerizable and is also a radical (4) The adhesive agent according to any one of the above [1] to [3], wherein the polyvinyl alcohol-based polymer (A) is a content of the acetalized vinyl alcohol unit. a polyvinyl alcohol having a saponification degree of 80 mol% or less and a saponification degree of 80 mol% or less; [5] The adhesive according to any one of the above [1] to [3], wherein the polyvinyl alcohol polymer (A) a polyvinyl acetal having a acetalized vinyl alcohol unit content of 10 mol% or more; [6] an adhesive according to the above [5], wherein the polyvinyl acetal type polyvinyl butyral; The adhesive agent according to any one of the above [1] to [6] wherein the content of the polyvinyl alcohol-based polymer (A) is from 1 to 90% by mass; [8] a binder having a poly-containing group The film of the vinyl alcohol polymer, the film of the protective film and the adhesive layer, and the adhesive layer are disposed between the film containing the polyvinyl alcohol polymer and the protective film, and the adhesive layer will be as described above [1] Adhesive of any of ~[7] [9] The adherend of the above [8], wherein the film containing the polyvinyl alcohol-based polymer is an extended film.

[10] The above-mentioned [8] or [9], wherein the stretched film is a polarizing film or a retardation film; [11] the above-mentioned one of [8] to [10], Wherein the protective film comprises triacetyl cellulose, (meth)acrylic polymer, polyester or a polymer having an alicyclic structure; [12] The adhesive body according to any one of the above [8] to [11] wherein the film comprising the polyvinyl alcohol-based polymer and the protective film have an adhesion of 6.0 N/25 mm or more; [13] a bonding body In a method of producing a film comprising a polyvinyl alcohol polymer and a protective film by an adhesive according to any one of the above [1] to [7], the active energy ray is irradiated to cure the adhesive layer.

According to the present invention, it is possible to provide a bonding agent such as a polarizing plate which exhibits a high adhesion force in a film including a PVA-based polymer and a protective film, and which is excellent in water resistance, and is obtained by using the adhesive. a body; and a method of manufacturing the body.

1‧‧‧Continue

2‧‧‧PVA polymer film

3‧‧‧ adhesive layer

4‧‧‧Protective film

[Fig. 1] Fig. 1 is a cross-sectional view schematically showing an example of a laminate of the present invention.

[Formation of the Invention]

The invention is described in detail below.

<Binder>

The adhesive agent of the present invention is used for an active energy ray-curable adhesive comprising a film of a PVA-based polymer and a protective film, which comprises a PVA-based polymer (A), a cationically polymerizable compound (B), and cationic polymerization. Starting agent (C). Here, examples of the active energy ray include electromagnetic waves such as ultraviolet rays, infrared rays, X-rays, and gamma rays, and electron beams, proton wires, and neutron wires. Among these, from the curing speed, the irradiation device From the viewpoints of availability and price, it is preferably ultraviolet light or electron beam, and more preferably ultraviolet light. When the active energy ray is applied to the adhesive of the present invention, the cationic polymerization initiator (C) contained therein is excited, and the reaction of the cationically polymerizable compound (B) proceeds. In this process, the PVA-based polymer (A) can be cured together with the cationically polymerizable compound (B) and its polymer to form an adhesive layer. Further, in the present invention, in order to distinguish the PVA-based polymer contained in the adhesive from the PVA-based polymer constituting the film containing the PVA-based polymer which should be followed by the adhesive, it is convenient to use the adhesive in the adhesive. The PVA-based polymer contained is referred to as "PVA-based polymer (A)".

[PVA-based polymer (A)]

The PVA-based polymer (A) contained in the adhesive of the present invention can be used by using vinyl acetate, vinyl formate, vinyl propionate, vinyl butyrate, trimethyl vinyl acetate, and methadone. Saponification of a polyvinyl ester obtained by polymerizing one or more kinds of vinyl esters such as vinyl versatate, vinyl laurate, vinyl stearate, vinyl benzoate or isobutyl acrylate And the winner. Among the vinyl ester to, PVA polymer from manufacturing ease, ease of acquisition and cost point of view, preferably has an ethylene oxycarbonyl group (H ₂ C = in the molecule CH-O-CO- The compound is more preferably vinyl acetate.

The polyvinyl ester is preferably one or two or more kinds of vinyl esters as a monomer, and more preferably one type of vinyl ester is used as a monomer, but the present invention is not greatly impaired. Within the range of the effect, it may be a copolymer of one or more kinds of vinyl esters and other monomers copolymerizable therewith.

As the other monomer capable of copolymerizing with the vinyl ester, for example, Examples thereof include an α-olefin having 2 to 30 carbon atoms such as ethylene, propylene, 1-butene, and isobutylene; (meth)acrylic acid or a salt thereof; methyl (meth)acrylate or ethyl (meth)acrylate , n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tertiary butyl (meth)acrylate, (methyl) a (meth) acrylate such as 2-ethylhexyl acrylate, dodecyl (meth)acrylate or octadecyl (meth)acrylate; (meth) acrylamide; N-methyl (methyl) ) acrylamide, N-ethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, diacetone (meth) acrylamide, (meth) acrylamide a (meth) acrylamide derivative such as a sulfonic acid or a salt thereof, (meth)acrylamide propyl dimethylamine or a salt thereof, N-methylol (meth) acrylamide or a derivative thereof N-vinylguanamine such as N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone, methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl Ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, tertiary butyl a vinyl ether such as vinyl ether, dodecyl vinyl ether or octadecyl vinyl ether; acrylonitrile such as (meth)acrylonitrile; vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, etc. a vinylidene halide; an allyl compound such as allyl acetate or allyl chloride; maleic acid or a salt, ester or anhydride thereof; itaconic acid or a salt, ester or anhydride thereof; vinyl trimethoxynonane; A vinyl silyl compound; an unsaturated sulfonic acid or a salt thereof. The polyvinyl ester may have one or two or more kinds of structural units derived from the other monomers described above.

The ratio of the structural unit derived from the above other monomer to the above polyvinyl ester is based on the number of moles of all the structural units constituting the polyvinyl ester, preferably 15 mol% or less, more preferably 10 mol% or less. ,especially Good for 5 moles or less.

As the PVA-based polymer (A), a non-graft copolymerization can be preferably used. However, the PVA-based polymer (A) may be one type as long as it does not significantly impair the effects of the present invention. Or a modification of two or more monomers capable of graft copolymerization. The graft copolymerization can be carried out on at least one of a polyvinyl ester and a PVA-based polymer obtained by saponifying it. Examples of the graft copolymerizable monomer include an unsaturated carboxylic acid or a derivative thereof, an unsaturated sulfonic acid or a derivative thereof, and an α-olefin having 2 to 30 carbon atoms. The proportion of the structural unit derived from the monomer capable of graft copolymerization in the polyvinyl ester or PVA-based polymer is based on the number of moles of all structural units constituting the polyvinyl ester or PVA-based polymer, preferably 5 Mole% or less.

A preferred example of the PVA-based polymer (A) is an "acetalized vinyl alcohol unit" which does not include a structural unit corresponding to a acetalization of a vinyl alcohol unit with an aldehyde or a derivative thereof, or Even if it contains, it has a low content rate. The content of the acetalized vinyl alcohol unit in the PVA-based polymer (A) is preferably based on the number of moles of all structural units constituting the PVA-based polymer (A), preferably less than 10 More than 5% by mole, more preferably less than 5% by mole, more preferably less than 3% by mole, most preferably 0% by mole. Further, in the PVA-based polymer containing an acetal-containing vinyl alcohol unit, usually two vinyl alcohol units react with one aldehyde or a derivative thereof to form one acetal structure, but in the present specification, One of such acetal structures is composed of two "acetalized vinyl alcohol units" (structural units), and the above-mentioned "content of acetalized vinyl alcohol units" and "constituting PVA" are considered. The molar number of all the structural units of the polymer (A) and the like.

Does not include the "acetalized vinyl alcohol unit", or the saponification degree of the PVA-based polymer (A) having a low content rate even if it is contained, and the solubility in the adhesive, especially in the adhesive When a monomer such as a polymerizable compound or a radically polymerizable compound is used, the solubility of the monomer is preferably 80 mol% or less, more preferably 65 mol% or less, and particularly preferably 50 mol. The ear is below the ear%, and particularly preferably 40% or less. In addition, when the degree of saponification of the PVA-based polymer (A) is too low, the adhesion between the film containing the PVA-based polymer and the protective film tends to decrease, so the degree of saponification of the PVA-based polymer (A) is preferably 10 mol% or more, more preferably 15 mol% or more, particularly preferably 20 mol% or more, and particularly preferably 25 mol% or more. In addition, the degree of saponification of the PVA-based polymer (including the case of the PVA-based polymer (A)) in the present specification means a structural unit which can be converted into a vinyl alcohol unit with respect to saponification by a PVA-based polymer. The total number of moles (typically a vinyl ester unit) and a vinyl alcohol unit, and the ratio of the number of moles of the vinyl alcohol unit (% by mole). The degree of saponification can be measured in accordance with the description of JIS K 6726-1994.

Another preferable example of the PVA-based polymer (A) includes a "acetalized vinyl alcohol unit" containing a structural unit corresponding to a acetalization of a vinyl alcohol unit with an aldehyde or a derivative thereof. Ethylene acetal. Examples of the aldehyde include formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, valeraldehyde, hexanal, heptaldehyde, n-octanal, 2-ethylhexanal, cyclohexanal, furfural, Glyoxal, glutaraldehyde, benzaldehyde, 2-methylbenzaldehyde, 3-methylbenzaldehyde, 4-methylbenzaldehyde, p-hydroxybenzaldehyde, m-hydroxybenzaldehyde, phenylacetaldehyde, β-benzene Propionaldehyde and the like. Further, examples of the aldehyde derivative include an acetal (dioxane) capable of giving a corresponding aldehyde by hydrolysis. Alkyl acetal, etc.), vinyl ester, vinyl ether, vinyl halide, and the like. The acetalized vinyl alcohol unit system contained in the polyvinyl acetal may be one type or two or more types. Among the polyvinyl acetals, from the viewpoint of adhesion, availability, etc., it is preferred to include acetalization of a structural unit corresponding to acetalization of a vinyl alcohol unit with n-butyraldehyde or a derivative thereof. The vinyl alcohol unit (polyvinyl butyral).

The content of the vinyl alcohol unit (-CH ₂ -CH(OH)-) in all the structural units constituting the polyvinyl acetal is preferably 5 mol% or more, and more preferably 10 from the viewpoint of adhesion and the like. The molar percentage is more than 20%, more preferably 20% by mole or more, and is preferably 50% by mole or less, more preferably 40% by mole or less, and particularly preferably 30% by mole or less.

Further, the content of the acetalized vinyl alcohol unit in all the structural units constituting the polyvinyl acetal may be, for example, 10 mol% or more, but from the adhesive force or the solubility in the adhesive, especially in the adhesive. When a monomer such as a cationically polymerizable compound or a radically polymerizable compound is contained, the solubility of the monomer is preferably 40 mol% or more, and more preferably 50 mol% or more. Preferably, it is 60 mol% or more, and is preferably 90 mol% or less, more preferably 85 mol% or less, and particularly preferably 75 mol% or less.

Further, the content of the vinyl ester unit in the total structural unit constituting the polyvinyl acetal is preferably 0.1 mol% or more, more preferably 0.3 mol% or more, and particularly preferably 0.5 from the viewpoint of adhesion and the like. More than or equal to 5% by mole, more preferably 30% by mole or less, still more preferably 20% by mole or less, still more preferably 10% by mole or less, and particularly preferably 5% by mole or less. In addition, examples of the vinyl ester unit include an unsaponified vinyl ester unit contained in a PVA-based polymer before acetalization used for producing a polyvinyl acetal. Table example.

The degree of polymerization of the PVA-based polymer (A) is not particularly limited, and the polymerization of the PVA-based polymer is considered in consideration of the viscosity of the obtained adhesive and the coating property when the adhesive is applied to a protective film or the like. The degree is preferably 2,000 or less, more preferably 1,500 or less, still more preferably 1,000 or less, and particularly preferably 500 or less. Moreover, in consideration of the strength and the like of the adhesive layer in the obtained adherend, it is preferably 100 or more, more preferably 150 or more, and still more preferably 200 or more. In addition, the degree of polymerization of the PVA-based polymer (including the case of the PVA-based polymer (A)) as used in the present specification means the average degree of polymerization measured according to the description of JIS K 6726-1994. Further, in the polyvinyl acetal, since the degree of polymerization itself does not usually change before the acetalization in the production thereof, the polymerization of the PVA-based polymer before acetalization used for producing the polyvinyl acetal can be used. The degree is regarded as the degree of polymerization of the obtained polyvinyl acetal.

The content of the PVA-based polymer (A) in the adhesive of the present invention is preferably 90% by mass or less, more preferably from the viewpoint of the viscosity of the obtained adhesive and the coatability of the adhesive. It is 50% by mass or less, and particularly preferably 20% by mass or less. In addition, the content of the PVA-based polymer (A) in the adhesive of the present invention is preferably 1% by mass or more, and more preferably 2%, from the viewpoint of the strength of the adhesive layer in the obtained laminate. More than %, particularly preferably 3% by mass or more.

[Cationally polymerizable compound (B)]

As the cationically polymerizable compound (B), a compound having an oxetanyl group and/or an oxiranyl group in the molecule can be preferably used. The cationically polymerizable compound (B) can be used alone. One type may be used, or two or more types may be used in combination. Further, when a polyfunctional compound is used as at least a part of the cationically polymerizable compound (B), it can be preferably used as a crosslinking agent.

Examples of the compound having a propylene oxide group in the molecule include a compound having one propylene oxide group in the molecule and a compound having two or more propylene oxide groups in the molecule. In addition, examples of the compound having an oxirane group in the molecule include an aliphatic compound having an oxirane group in the molecule and an alicyclic compound having an oxirane group in the molecule.

Specific examples of the compound having one propylene oxide group in the molecule include 3-ethyl-3-hydroxymethyloxycyclobutane and (3-ethyl-3-epoxypropane methoxy). Methylbenzene, 4-fluoro-[1-(3-ethyl-3-epoxypropenylmethoxy)methyl]benzene, 4-methoxy-[1-(3-ethyl-3) -Epoxypropenylmethoxy)methyl]benzene, (3-ethyl-3-epoxypropanemethyl)phenyl ether, (3-ethyl-3-epoxypropenylmethyl)phenyl Ether, [1-(3-ethyl-3-epoxypropenylmethoxy)ethyl]phenyl ether, isobutoxymethyl (3-ethyl-3-epoxypropanemethyl)ether ,different Oxyethyl (3-ethyl-3-epoxypropanemethyl) ether, different (3-ethyl-3-epoxypropanemethyl)ether, 2-ethylhexyl (3-ethyl-3-epoxypropanemethyl)ether, ethyldiethylene glycol (3-ethyl 3-benzylpropanemethyl)ether, tetrahydroindenyl (3-ethyl-3-epoxypropanemethyl)ether, tetrabromophenyl (3-ethyl-3-epoxypropanyl) Methyl)ether, 2-tetrabromophenoxyethyl (3-ethyl-3-epoxypropanemethyl)ether, tribromophenyl (3-ethyl-3-epoxypropenylmethyl) Ether, 2-tribromophenoxyethyl (3-ethyl-3-epoxypropanemethyl)ether, 2-hydroxyethyl (3-ethyl-3-epoxypropanemethyl)ether, 2-hydroxypropyl (3-ethyl-3-epoxypropanemethyl)ether, butoxyethyl (3-ethyl-3-epoxypropanemethyl)ether, pentachlorophenyl (3 -ethyl-3-epoxypropanemethyl)ether, pentabromophenyl (3-ethyl-3-epoxypropanemethyl)ether, Alkyl (3-ethyl-3-epoxypropanemethyl)ether or the like.

As a commercial item of the above-mentioned compound which has one propylene oxide group in a molecule, OXT-101, OXT-211, OXT-212 (The

Specific examples of the compound having two or more propylene oxide groups in the molecule include 3,7-bis(3-epoxypropenyl)-5-oxa-decane and 3,3'-. (1,3-(2-methylene)propanediylbis(formaldehyde)) bis-(3-ethyloxycyclobutane), 1,4-bis[(3-ethyl-3-epoxypropane) Methoxy)methyl]benzene, 1,2-bis[(3-ethyl-3-epoxypropenylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl- 3-epoxypropenylmethoxy)methyl]propane, ethylene glycol bis(3-ethyl-3-epoxypropanemethyl)ether, dicyclopentenyl bis(3-ethyl-3- Propylene oxide methyl)ether, triethylene glycol bis(3-ethyl-3-epoxypropanemethyl)ether, tetraethylene glycol bis(3-ethyl-3-epoxypropanemethyl) Ether, tricyclodecanediyldimethylene (3-ethyl-3-epoxypropanemethyl)ether, 1,4-bis(3-ethyl-3-epoxypropenylmethoxy) Butane, 1,6-bis(3-ethyl-3-epoxypropenylmethoxy)hexane, polyethylene glycol bis(3-ethyl-3-epoxypropanemethyl)ether, Ethylene oxide (EO) modified bisphenol A bis(3-ethyl-3-epoxypropanemethyl)ether, propylene oxide (PO) modified bisphenol A bis(3-ethyl-3- Epoxypropane methyl ether, EO modification Hydrogenated bisphenol A bis(3-ethyl-3-epoxypropanemethyl)ether, PO modified hydrogenated bisphenol A bis(3-ethyl-3-epoxypropanemethyl)ether, EO modification Bisphenol F (3-ethyl-3-epoxypropanemethyl)ether or the like.

The commercially available product having two or more propylene oxide groups in the molecule may, for example, be OXT-121 or OXT-221 (manufactured by Toagosei Co., Ltd.).

Specific examples of the aliphatic compound having an oxirane group in the molecule include, for example, 1,4-butanediol diepoxypropyl ether and 1,6-hexanediol diepoxypropyl ether. , neopentyl glycol diepoxypropyl ether, trimethylolpropane triepoxypropyl ether, polyethylene glycol diepoxypropyl ether, glycerol triepoxypropyl ether, polypropylene glycol diepoxypropyl Ethers; polyepoxypropyl ethers of polyether polyols obtained by adding one or more kinds of alkylene oxides to aliphatic polyols such as ethylene glycol, propylene glycol and glycerin; aliphatic long chain binary Acidic diepoxypropyl esters; monoepoxypropyl ethers of aliphatic higher alcohols; glycidyl esters of higher fatty acids; epoxidized soybean oil; butyl hydroxystearate; epoxy groups Octyl stearate; epoxidized linseed oil; epoxidized polybutadiene.

Examples of the commercial product of the above-mentioned aliphatic compound having an oxirane group in the molecule include SR-NPG, SR-16H, SR-PG, and SR-TPG (above, manufactured by Sakamoto Pharmaceutical Co., Ltd.); PG-202 PG-207 (above, Dongdu Chemical System).

Specific examples of the alicyclic compound having an oxirane group in the molecule include 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, and 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-intermediate Alkane, bis(3,4-epoxycyclohexylmethyl)adipate, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, 3,4-epoxy 6-methylcyclohexyl-3',4'-epoxy-6'-methylcyclohexanecarboxylate, ε-caprolactone modified 3,4-epoxycyclohexylmethyl-3 ',4'-epoxycyclohexane carboxylate, trimethylcaprolactone modified 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylate, β- Methyl-δ-valerolactone modified 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, methylenebis(3,4-epoxycyclohexane , bis(3,4-epoxycyclohexylmethyl)ether of ethylene glycol, ethyl bis(3,4-epoxycyclohexanecarboxylate), dioctyl epoxide hexahydrophthalate Epoxy hexahydrophthalic acid di-2-ethylhexyl ester and the like.

Commercial products of the alicyclic compound having an oxirane group in the molecule include Celloxide 2021, Celloxide 2021P, Celloxide 2081, Celloxide 2083, Celloxide 2085, Epolead GT-300, Epolead GT-301, and Epolead. GT-302, Epolead GT-400, Epolead 401, Epolead 403 (above, manufactured by DAICEL Co., Ltd.), etc.

The content of the cationically polymerizable compound (B) in the adhesive of the present invention is not particularly limited, but is preferably 98% by mass or less from the viewpoint of the strength of the adhesive layer in the obtained laminate. It is more preferably 95% by mass or less, particularly preferably 90% by mass or less, and particularly preferably 70% by mass or less. In addition, the content of the cationically polymerizable compound (B) in the adhesive of the present invention is preferably 10% by mass or more, more preferably from the viewpoint of the viscosity of the adhesive to be obtained, and the coating property of the adhesive. It is 20% by mass or more, and particularly preferably 30% by mass or more.

[cationic polymerization initiator (C)]

As the cationic polymerization initiator (C), a compound which can promote the reaction of the PVA-based polymer (A) and the cationically polymerizable compound (B) contained in the adhesive can be used by irradiating the active energy ray. Examples of such a cationic polymerization initiator (C) include a sulfonium salt-based initiator and an iodonium salt-based initiator. a sulfonium salt-based initiator; a sulfonic acid derivative, a carboxylic acid ester, an aryl diazonium salt, an iron-arene complex, a pyridinium salt, a quinolinium salt, and an O-containing A nitrobenzyl group-based compound or the like; a sulfonium salt-based initiator is preferred, and an onium salt-based initiator and an iodonium-based initiator are more preferred. These cationic polymerization initiators (C) may be used alone or in combination of two or more.

Examples of the onium salt-based initiator include p-hydroxyl groups such as p-phenylbenzylmethylsulfonium salt, p-phenyldimethylhydrazine salt, and benzylmethyl p-hydroxyphenylphosphonium hexafluoroantimonate. a phenylbenzylmethyl phosphonium salt; a triphenylsulfonium salt; a triphenylsulfonium salt such as a diphenyl[4-(phenylthio)phenyl]phosphonium salt; a 4,4'-bis[di(β-hydroxyl) group A ruthenium salt having a bis[4-(diphenylfluorenyl)phenyl] sulfide skeleton such as ethoxy)phenyl fluorenyl]diphenyl sulfide bishexafluoroantimonate or the like.

Examples of the relative anion of the onium salt in the onium salt-based initiator include SbF ₆ ^- , AsF ₆ ^- , PF ₆ ^- , BF ₄ ^-, etc., among them, from the viewpoint of reactivity or stability. Preferably, it is SbF ₆ ^- , PF ₆ ^- .

Examples of the iodonium salt-based initiator include diphenyl iodonium, bis(4-tributylphenyl) iodonium, and (4-tertiary butoxyphenyl) phenyl iodonium. An iodonium salt such as (4-methoxyphenyl)phenyliodonium or the like.

As the cationic polymerization initiator (C), a triarylsulfonium salt such as a diphenyl[4-(phenylthio)phenyl]phosphonium salt is particularly preferable from the viewpoint of thermal stability.

As a commercial item of the above-mentioned cationic polymerization initiator (C), for example, "CPI-100P" (manufactured by Sun-Apro), "CPI-101A" (manufactured by Sun-Apro), and "IRGACURE 250" (manufactured by BASF) ), "Adkoptomer SP-172" (made by Adeka), "Adkoptomer SP-170" (ADEKA) "Adkoptomer SP-152" (made by Adeka), "Adkoptomer SP-150" (made by Adeka), "Sunaid SI-60L" (made by Sanshin Chemical Industry), "Sunaid SI-80L" (Sanshin Chemical Industry) "Sunaid SI-100L" (made by Sanshin Chemical Industry Co., Ltd.) and "Sunaid SI-150L" (made by Sanshin Chemical Industry Co., Ltd.).

The content of the above cationic polymerization initiator (C) in the adhesive of the present invention is not particularly limited, but an acid derived from the cationic polymerization initiator (C) is considered for a film containing a PVA-based polymer, and a protective film. The influence of the adhesive layer is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 3% by mass or less. In addition, the content of the cationic polymerization initiator (C) in the adhesive of the present invention is preferably 0.01% by mass or more, and more preferably 0.05% by mass, in consideration of the curing rate of the adhesive and the adhesion after curing. The above is particularly preferably 0.1% by mass or more.

The adhesive of the present invention preferably further comprises a radical polymerizable compound (D) and a radical polymerization initiator (E). When the active energy ray is applied to the adhesive, the cationic polymerization initiator (C) and the radical polymerization initiator (E) contained therein are excited, and the cationic polymerizable compound (B) reacts or radically polymerizes with each other. The reaction of the compounds (D) with each other is carried out. In this process, the PVA-based polymer (A), the cationically polymerizable compound (B), the radically polymerizable compound (D), and the like can be cured together to form an adhesive layer. Further, the cationically polymerizable compound (B) may be a compound (BD) which is at least partially cationically polymerizable and also radically polymerizable. When at least a part of the cationically polymerizable compound (B) is a compound having a cationic polymerizability and a radical polymerizable property (BD), it is preferred to further contain a radical polymerization initiator (E).

The adhesive of the present invention contains a cationically polymerizable compound (B) and is excellent in adhesion to a film containing a PVA-based polymer. Further, when the adhesive of the present invention further contains the radical polymerizable compound (D), the adhesion to the protective film is further increased. The adhesive agent of the present invention preferably further comprises a PVA-based polymer (A) and a cationically polymerizable compound from the viewpoint of further improving the adhesion of both the film containing the PVA-based polymer and the protective film. B), a cationic polymerization initiator (C), a radical polymerizable compound (D), and an adhesive of a radical polymerization initiator (E), or a PVA-based polymer (A), and a cationic polymerizability An adhesive of a radically polymerizable compound (BD), a cationic polymerization initiator (C), and a radical polymerization initiator (E).

[Radical polymerizable compound (D)]

As the radical polymerizable compound (D), a compound having a (meth)acrylinyl group in the molecule can be preferably used. The radically polymerizable compound (D) may be used alone or in combination of two or more. Further, when a polyfunctional compound is used as at least a part of the radically polymerizable compound (D), it can be preferably used as a crosslinking agent.

Specific examples of the compound having a (meth)acryloyl group in the molecule include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and (methyl). Isopropyl acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, butyl (meth)acrylate, amyl (meth)acrylate, isoamyl (meth)acrylate , (meth) hexyl acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (methyl) Ethyl acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, lauryl (meth) acrylate, lauryl (meth) acrylate, (methyl) ) octadecyl acrylate, isostearyl (meth) acrylate, benzyl (meth) acrylate, (meth) acrylate Ester, (meth)acrylic acid Ester, tricyclodecyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, 4-butylcyclohexyl (meth)acrylate, ( 2-hydroxyethyl methacrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-(meth) acrylate Hydroxy-3-phenoxypropyl ester, butoxyethyl (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, benzyl (meth)acrylate, phenoxy (meth)acrylate Ethyl ethyl ester, tetrahydrofurfuryl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, methoxyethylene glycol (meth)acrylate, Ethoxyethyl methacrylate, methoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, dimethylaminoethyl (meth)acrylate, ( Diethylaminoethyl methacrylate, 7-amino-3,7-dimethyloctyl (meth) acrylate, 4-propenyl morpholine, trimethylolpropane tri(methyl) Acrylate, trimethylolpropane trioxyethyl (meth) acrylate, Pentaerythritol tri(meth)acrylate, ethylene glycol di(meth)acrylate, triethylene glycol diacrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(methyl) Acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, tripropylene glycol di Methyl acrylate, bisphenol A diglycidyl ether two-terminal (meth) acrylate adduct, pentaerythritol tri (meth) acrylate, neopentyl alcohol tetra (meth) acrylate , polyester di(meth) acrylate, tris(2-hydroxyethyl)isocyanate tri(meth) acrylate, tris(2-(2,3-dihydroxypropoxy)ethyl Isocyanurate tri(meth)acrylate, tris(2-hydroxyethyl)isocyanate di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, Tricyclodecane dimethanol di(meth)acrylate, di(meth)acrylate of diol as an adduct of ethylene oxide or propylene oxide of bisphenol A, ring as hydrogenated bisphenol A a di(meth)acrylate of a diol of an oxyethylene or propylene oxide adduct, Additional (meth) acrylate of epoxy (meth) acrylate, the diglycidyl ether of bisphenol A.

Further, examples of the radical polymerizable compound (D) include a bisphenol A epoxy acrylate resin, a phenol novolak epoxy acrylate resin, and a cresol novolak epoxy group. An epoxy (meth) acrylate resin such as an acrylate resin; a carboxyl group-modified epoxy (meth) acrylate resin; a urethane resin obtained from a polyol and an organic isocyanate and a hydroxyl group-containing ( a urethane (meth) acrylate resin obtained by reacting a methyl group acrylate; a resin having a (meth) acryl fluorenyl group introduced through a polyester bond in a polyhydric alcohol; a polyester (meth) acrylate A resin; a (meth) acrylamide compound such as N-hydroxyethyl (meth) acrylamide or the like.

The content of the radically polymerizable compound (D) in the adhesive of the present invention is not particularly limited, but is preferably 98% by mass from the viewpoint of the strength of the adhesive layer in the obtained laminate. In the following, it is more preferably 95% by mass or less, particularly preferably 90% by mass or less, and particularly preferably 70% by mass or less. In addition, the content of the radically polymerizable compound (D) in the adhesive of the present invention is preferably 10% by mass or more, and more preferably from the viewpoint of the viscosity of the adhesive to be obtained, and the coating property of the adhesive. Good for 20% by mass or more, and particularly preferably 30% by mass or more.

[Free radical polymerization initiator (E)]

As the radical polymerization initiator (E), a compound which can promote the reaction of the radical polymerizable compound (D) contained in the adhesive by irradiation with an active energy ray can be used. Examples of such a radical polymerization initiator (E) include carbonyl compounds such as acetophenones, diphenylketones, rice ketones, and benzoin; tetramethylthiuram monosulfide A sulfur compound such as tetramethyl thiuram monosulfide or thioxanthone is preferably a carbonyl compound. These radical polymerization initiators (E) may be used alone or in combination of two or more.

Examples of the acetophenones include 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, and 2-hydroxy-2-methyl group. 1-phenylpropan-1-one and the like.

Examples of the diphenyl ketone include benzophenone, benzhydrylbenzoic acid, hydroxybenzophenone, 3,3'-dimethyl-4-methoxybenzophenone, and acrylic acid. Dibenzophenone and the like.

Examples of the benzoin include benzoin, benzoin methyl ether, and benzoin isopropyl ether.

The radical polymerization initiator (E) is more preferably an acetophenone or a diphenyl ketone from the viewpoints of reactivity, transparency, etc., and particularly preferably 1-hydroxycyclohexyl phenyl ketone.

As a commercial item of the above-mentioned radical polymerization initiator (E), "IRGACURE 184" (1-hydroxycyclohexyl phenyl ketone; manufactured by BASF), "Sorubasuron BIPE" (made by Heijin Chemicals Co., Ltd.), and "Sorubasuron" are mentioned, for example. BIBE" (black gold chemical system), "IRGACURE 651" (2,2-dimethoxy group) -1,2-diphenylethan-1-one; manufactured by BASF), "DAROCUR 1173" (2-hydroxy-2-methyl-1-phenylpropan-1-one; manufactured by BASF), "IRGACURE 2959" (BASF), "IRGACURE 127" (made by BASF), "IRGACURE 907" (made by BASF), "IRGACURE 369" (made by BASF), "KAYACURE BP" (made by Nippon Kasei Co., Ltd.), "IRGACURE 379" (BASF system) ), "DAROCUR TPO" (made by BASF), "IRGACURE 819" (made by BASF), "IRGACURE 819DW" (made by BASF), "IRGACURE 784" (made by BASF), "IRGACURE OXE 01" (made by BASF), "IRGACURE" OXE 02" (made by BASF), "IRGACURE 754" (made by BASF), "IRGACURE 500" (made by BASF), "IRGACURE 1800" (made by BASF), "IRGACURE 1870" (made by BASF), "DAROCUR 4265" (BASF) "), "KAYACURE DETX-S" (made by Nippon Kasei Co., Ltd.), "ESACURE KIP 150" (made by Lamberti), "S-121" (Shinko Technology Development), "Seikuol BEE" (Seiko Chemical Co., Ltd.).

The content of the radical polymerization initiator (E) in the adhesive of the present invention is not particularly limited, but the low molecular weight of the cured product and the heat resistance due to the excessively high rate of hardening are prevented. From the viewpoint of the decrease in the properties, etc., it is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 3% by mass or less. In addition, the content of the radical polymerization initiator (E) in the adhesive of the present invention is preferably 0.01% by mass or more, and more preferably 0.05%, in consideration of the curing rate of the adhesive and the adhesion after curing. More than %, particularly preferably 0.1% by mass or more.

[Cation polymerization property is also a radical polymerizable compound (BD)]

As described above, the cationically polymerizable compound (B) is at least a part thereof It is a compound (BD) which is cationically polymerizable and also radically polymerizable. When the cation polymerization property is a compound (BD) which is also a radical polymerizable property, the cationic polymerizable property is also a radical polymerizable compound (BD), a PVA-based polymer (A), and a cationically polymerizable compound (B). The crosslinking reaction system of the radically polymerizable compound (D) or the like is carried out, and the strength of the adhesive layer in the obtained binder is further increased, and as a result, the adhesion of the film containing the PVA-based polymer and the protective film is further increased. High and better. As the compound (BD) which is also cationically polymerizable and radically polymerizable, a compound having an oxypropylene group and/or an oxirane group in the molecule and further having a (meth)acryl fluorenyl group can be preferably used. The compound having a cationically polymerizable property and a radical polymerizable property (BD) may be used alone or in combination of two or more.

Specific examples of the compound having a cationically polymerizable property and a radical polymerizable property (BD) include an alicyclic epoxy group such as 3,4-epoxycyclohexylmethyl (meth)acrylate (A). (meth)acrylate containing an aliphatic chain epoxy group such as glycidyl (meth)acrylate; 3-ethyl-3-(methyl)propenyloxymethyloxycarbonyl ring An oxyalkylene group-containing (meth) acrylate or the like such as butane.

The content of the cationically polymerizable compound (BD) in the adhesive agent of the present invention is not particularly limited, but from the viewpoint of the strength of the adhesive layer in the obtained adherend, and the like, It is preferably 90% by mass or less, more preferably 85% by mass or less, still more preferably 80% by mass or less, and particularly preferably 60% by mass or less. Moreover, the cationic polymerizability in the adhesive of the present invention is also a radical polymerizable property from the viewpoint of the viscosity of the obtained adhesive, the coatability of the adhesive, and the like. The content of the compound (BD) is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 15% by mass or more.

[other optional ingredients]

The adhesive may further contain the PVA polymer (A), the cationically polymerizable compound (B), the cationic polymerization initiator (C), the radical polymerizable compound (D), and a radical polymerization initiator (E). (In addition, the cationically polymerizable compound (B) is a component other than the case where the cationically polymerizable compound (B) is also a cationically polymerizable compound (BD). Examples of the other component include a crosslinking agent, a sensitizer, a diluent, a tackifier, a softener, a filler, a stabilizer, a pigment, a dye, and the like. The other components may be organic compounds or inorganic compounds.

(crosslinking agent)

The cross-linking agent is a cross-linking agent in which a PVA-based polymer (A), a cationically polymerizable compound (B), a radically polymerizable compound (D), or the like is crosslinked, and the strength of the adhesive layer in the obtained adherend is obtained. Further, as a result, the adhesion force of the film containing the PVA-based polymer and the protective film was further increased. The above-mentioned crosslinking agent may be used alone or in combination of two or more.

As the above crosslinking agent, for example, poly A nitrogen compound such as an oxazoline, an isocyanate compound such as diphenylmethane diisocyanate, an aldehyde compound such as glutaraldehyde, a zirconium compound such as ammonium zirconium carbonate, or a titanium compound such as titanium lactate.

The content of the crosslinking agent in the adhesive of the present invention is not particularly limited, but the content of the crosslinking agent is preferably 20 from the viewpoint of the viscosity of the resulting adhesive, the coatability of the adhesive, and the like. The mass% or less is more preferably 15% by mass or less. Further, the content ratio of the crosslinking agent is, for example It can be 1% by mass or more.

(sensitizer)

The sensitizer is promoted by the sensibility of moving or expanding the active energy ray. Examples of such a sensitizer include n-butylamine, di-n-butylamine, tri-n-butylphosphine, allylthiouric acid, and triethylamine, and triethylamine is preferred.

The above sensitizer is preferably a cationic polymerization initiator (C) or a radical polymerization initiator (E). The mass ratio of the sensitizer is preferably 5% by mass or more, more preferably 5% by mass or more based on the total of the cationic polymerization initiator (C) and the radical polymerization initiator (E) and the sensitizer. It is 10% by mass or more. The upper limit of the mass ratio of the sensitizer is not particularly limited, but may be, for example, 90% by mass or less.

(diluent)

The above diluent is used to adjust the viscosity of the adhesive and the mechanical strength after curing of the adhesive. Examples of the diluent include a compound having no active energy ray-curable group, and specific examples thereof include esters of phthalic acid esters, non-aromatic dibasic acid esters, aliphatic esters, and polyalkylene glycols. , phosphates, trimellitates, chlorinated paraffins, hydrocarbon oils, processing oils, polyethers, polyester plasticizers derived from dibasic acids and glycols, and polymerization of vinyl monomers A vinyl polymer or the like is obtained. These inactive compounds may be used alone or in combination of two or more. Further, the diluent may have a functional group (hydroxy group, carboxyl group, halogen group or the like) other than the active energy ray-curable group.

Examples of the phthalic acid esters include dibutyl phthalate, diheptyl phthalate, di(2-ethylhexyl) phthalate, and butyl benzyl citrate.

Examples of the non-aromatic dibasic acid ester include dioctyl adipate, dioctyl sebacate, dibutyl sebacate, and isodecyl succinate.

Examples of the aliphatic esters include butyl oleate and methyl phthalic acid ricinoleate.

Examples of the ester of the polyalkylene glycol include diethylene glycol dibenzoate, triethylene glycol dibenzoate, and neopentyl glycol ester.

Examples of the phosphate esters include tricresyl phosphate and tributyl phosphate.

Examples of the hydrocarbon-based oil include alkylbiphenyl and partially hydrogenated terphenyl.

Examples of the polyethers include polyether polyols; and conversion of a hydroxyl group of a polyether polyol into a derivative such as an ester group or an ether group. Here, examples of the polyether polyol include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.

Examples of the dibasic acid include sebacic acid, adipic acid, sebacic acid, and citric acid. Examples of the above-mentioned glycol include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, and dipropylene glycol.

Examples of the vinyl polymer include a (meth)acrylic polymer, polybutene, polyisobutylene, a styrene polymer (polystyrene, poly-α-methylstyrene, etc.), and a diene. Examples of polymers (polybutadiene, polychloroprene, etc.), vinyl ether polymers, copolymers of these (butadiene-acrylonitrile copolymers, etc.).

The number average molecular weight (Mn) of the diluent is preferably 15,000 or less, more preferably 10,000 or less, still more preferably 8,000 or less, and further preferably It is 400 or more, more preferably 800 or more, and particularly preferably 1,000 or more. Since the number average molecular weight (Mn) of the diluent is not more than the above upper limit, the viscosity of the obtained adhesive can be made into an appropriate range, and the handleability of the adhesive is increased. In addition, since the number average molecular weight (Mn) of the diluent is at least the above lower limit, it is possible to suppress the outflow of the cured material from the cured material after the adhesive has passed through the adhesive, and the initial physical properties can be maintained for a long period of time.

When the diluent is a polymer, the molecular weight distribution (Mw/Mn) thereof is not particularly limited, but is usually less than 1.8, preferably 1.7 or less, more preferably 1.5 or less, and still more preferably 1.3 or less.

The content of the diluent in the adhesive of the present invention is not particularly limited, but is preferably 70% by mass or less, and more preferably 50% from the viewpoint of the strength of the adhesive layer in the obtained laminate. % or less is particularly preferably 30% by mass or less, and may be 10% by mass or less.

(tackifier)

The tackifier is for imparting adhesion to a cured product after curing of the adhesive. As the tackifier, for example, 唍-茚 resin, phenol resin, p-tert-butylphenol-acetylene resin, phenol-formaldehyde resin, terpene resin, synthetic terpene resin, aromatic modified terpene resin, xylene-formaldehyde resin, aromatic hydrocarbon resin , aliphatic cyclic hydrocarbon resin, oligomer of monoolefin or diolefin, hydrocarbon resin, hydrogenated hydrocarbon resin, polybutene, polyol ester of rosin, hydrogenated rosin, hydrogenated wood rosin, hydrogenated rosin and monool or polyol Ester, resin, etc. Among these, preferred are terpene resins, synthetic terpene resins, aromatic modified terpene resins, aliphatic saturated petroleum resins, rosin esters, disproportionated rosin esters, hydrogenated rosin esters, and aliphatic petroleum resins ( C5 is an aliphatic petroleum resin, a C5‧C9 aliphatic petroleum resin, or the like, or a modified aliphatic petroleum resin.

[Method of manufacturing adhesive]

The method for producing the adhesive of the present invention is not particularly limited, but for example, by mixing and stirring the PVA-based polymer (A), the cationically polymerizable compound (B), the cationic polymerization initiator (C), and the like. The radically polymerizable compound (D), the radical polymerization initiator (E), and other components to be added (further, the cationically polymerizable compound (B) is a compound which is cationically polymerizable and also radically polymerizable (BD) In the case of one or two or more of arbitrary components, etc., it is easy to manufacture.

[Film containing PVA polymer]

The adhesive agent of the present invention is used for a film comprising a PVA-based polymer (also referred to as "a film containing a PVA-based polymer" or a "PVA-based polymer film") and a protective film. As the PVA-based polymer contained in the PVA-based polymer film, vinyl acetate, vinyl formate, vinyl propionate, vinyl butyrate, trimethyl vinyl acetate, and visastatin can be used. A polyvinyl ester obtained by polymerizing one or more kinds of vinyl esters such as vinyl ester, vinyl laurate, vinyl stearate, vinyl benzoate or isopropenyl acetate is saponified. Among the above-mentioned vinyl esters, it is preferred to have a vinyloxycarbonyl group (H ₂ C=CH-O-CO- in the molecule) from the viewpoints of easiness of production, availability, cost, and the like of the PVA-based polymer. The compound is more preferably vinyl acetate.

The polyvinyl ester is preferably one or two or more kinds of vinyl esters as a monomer, and more preferably one type of vinyl ester is used as a monomer, but the present invention is not greatly impaired. Within the range of the effect, one or two or more vinyl esters may be copolymerized with the same. Copolymer of other monomers.

Examples of the other monomer copolymerizable with the vinyl ester include an α-olefin having 2 to 30 carbon atoms such as ethylene, propylene, 1-butene or isobutylene; and (meth)acrylic acid or a salt thereof; Methyl acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, (meth) acrylate such as (meth)acrylic acid tert-butyl acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, octadecyl (meth)acrylate; Base acrylamide; N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, diacetone (methyl a acrylamide, (meth) acrylamide sulfonate or a salt thereof, (meth) acrylamide propyl dimethylamine or a salt thereof, N-methylol (meth) acrylamide or its a (meth) acrylamide derivative such as a derivative; N-vinyl decylamine such as N-vinylformamide, N-vinylacetamide or N-vinylpyrrolidone; methylvinyl Ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, a vinyl ether of butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, dodecyl vinyl ether, octadecyl vinyl ether or the like; acrylonitrile such as (meth)acrylonitrile ; vinyl halides such as vinyl chloride, vinylidene chloride, vinyl fluoride and vinylidene fluoride; allyl compounds such as allyl acetate and allyl chloride; maleic acid or its salts, esters or anhydrides; An acid or a salt, ester or acid anhydride thereof; a vinyl fluorenyl compound such as vinyltrimethoxy decane; an unsaturated sulfonic acid or a salt thereof. The polyvinyl ester may have one or two or more kinds of structural units derived from the other monomers described above.

The above structural unit derived from other monomers accounts for the above polyethylene The ratio of the ester is preferably 15 mol% or less, more preferably 10 mol% or less, and particularly preferably 5 mol% or less based on the number of moles of all structural units constituting the polyvinyl ester.

As the PVA-based polymer, a non-graft copolymerization can be preferably used. However, the PVA-based polymer may have one or two or more kinds of energy as long as it does not significantly impair the effects of the present invention. Modified by graft copolymerized monomers. The graft copolymerization can be carried out on at least one of a polyvinyl ester and a PVA-based polymer obtained by saponifying it. Examples of the graft copolymerizable monomer include an unsaturated carboxylic acid or a derivative thereof, an unsaturated sulfonic acid or a derivative thereof, and an α-olefin having 2 to 30 carbon atoms. The proportion of the structural unit derived from the monomer capable of graft copolymerization in the polyvinyl ester or PVA-based polymer is based on the number of moles of all structural units constituting the polyvinyl ester or PVA-based polymer, preferably 5 Mole% or less.

The PVA-based polymer may be partially crosslinked or not crosslinked. Further, a part of the hydroxyl group of the PVA polymer may be reacted with an aldehyde compound such as acetaldehyde or butyraldehyde to form an acetal structure, or may be formed without reacting with such a compound to form an acetal structure.

The degree of polymerization of the PVA-based polymer is not particularly limited, but is preferably 1,000 or more. Since the degree of polymerization of the PVA-based polymer is 1,000 or more, the polarizing performance of the obtained polarizing film can be further improved. When the degree of polymerization of the PVA-based polymer is too high, the production cost of the PVA-based polymer increases, and the process passability at the time of film formation tends to be poor. Therefore, the polymerization degree of the PVA-based polymer is preferably 1,000 to 10,000. Within the range of 1,500 to 8,000, especially 2,000 to 5,000. Within the scope.

The saponification degree of the PVA-based polymer is preferably 95% by mole or more, more preferably 98% by mole or more, and particularly preferably 99% by mole or more, from the viewpoint of improving the moist heat resistance of the obtained polarizing film. Particularly good is 99.3% or more.

The PVA-based polymer film may comprise the above PVA-based polymer together with a plasticizer. Since the PVA-based polymer film contains a plasticizer, it is possible to improve the handleability and elongation of the PVA-based polymer film. As the plasticizer, a polyhydric alcohol is preferably used, and specific examples thereof include ethylene glycol, glycerin, propylene glycol, diethylene glycol, diglycerin, triethylene glycol, tetraethylene glycol, and trimethylolpropane. The PVA-based polymer film may contain one or more of these plasticizers. Among these, glycerin is preferred from the viewpoint of improving the elongation of the PVA-based polymer film.

The content of the plasticizer in the PVA-based polymer film is preferably 2 to 20 parts by mass, more preferably 3 to 17 parts by mass, and particularly preferably 4 to 14 parts by mass based on 100 parts by mass of the PVA-based polymer. Share. The content of the plasticizer in the PVA-based polymer film is 2 parts by mass or more with respect to 100 parts by mass of the PVA-based polymer, and the elongation of the PVA-based polymer film is increased. On the other hand, when the content of the plasticizer in the PVA-based polymer film is 20 parts by mass or less based on 100 parts by mass of the PVA-based polymer, the plasticizer can be prevented from oozing out to the surface of the PVA-based polymer film. The operability of the polymer film is lowered.

In addition, when a PVA-based polymer film is produced by using a film forming stock solution for producing a PVA-based polymer film, the film forming property is improved, and the thickness unevenness of the film is suppressed, and a metal roll or a belt is used. In the case of a film, in order to facilitate the peeling of the PVA-based polymer film from such a metal roll or belt, it is preferred to incorporate a surfactant in the film forming stock solution. When a PVA-based polymer film is produced by blending a film-forming stock solution containing a surfactant, the PVA-based polymer film may contain a surfactant. The surfactant to be blended in the film-forming stock solution for producing the PVA-based polymer film, and the type of the surfactant contained in the PVA-based polymer film are not particularly limited, but are derived from a metal roll or a belt. From the viewpoint of peelability, an anionic surfactant or a nonionic surfactant is preferred, and a nonionic surfactant is particularly preferred.

The anionic surfactant is preferably, for example, a carboxylic acid type such as potassium laurate; a sulfate type such as octyl sulfate; or a sulfonic acid type such as dodecylbenzenesulfonate.

The nonionic surfactant is preferably, for example, an alkyl ether type such as polyoxyethylene oleyl ether; an alkylphenyl ether type such as polyoxyethylene octylphenyl ether; or an alkane such as polyoxyethylene laurate. Base type; alkylamine type such as polyoxyethylene lauryl amine ether; alkyl guanamine type such as polyoxyethylene lauric acid decylamine; polypropylene glycol ether type such as polyoxyethylene polyoxypropylene ether; lauric acid An alkanolamine type such as diethanolamine or oleic acid diethanolamine; an allylphenyl ether type such as a polyoxyalkylene allyl ether or the like.

These surfactants may be used alone or in combination of two or more.

When the surfactant is blended in the film forming stock solution for producing the PVA-based polymer film, the content of the surfactant in the film forming stock solution, and further the content of the surfactant in the PVA-based polymer film is relative to 100 The PVA-based polymer contained in the film-forming stock solution or the PVA-based polymer film of the mass part is preferably in the range of 0.01 to 0.5 part by mass, more preferably Preferably, it is in the range of 0.02 to 0.3 parts by mass. When the content of the surfactant is 0.01 parts by mass or more with respect to 100 parts by mass of the PVA-based polymer, film formability and peelability can be improved. On the other hand, when the content of the surfactant is 0.5 parts by mass or less based on 100 parts by mass of the PVA-based polymer, it is possible to suppress the surfactant from oozing out to the surface of the PVA-based polymer film, causing adhesion and lowering workability.

The PVA-based polymer film may be composed only of a PVA-based polymer, or may be composed only of a PVA-based polymer and the above-mentioned plasticizer and/or surfactant, but may contain an antioxidant or an anti-freezing agent as needed. And a pH adjuster, a concealing agent, a coloring inhibitor, an oil agent, and the like, the PVA-based polymer, a plasticizer, and other components other than the surfactant.

The content of the PVA-based polymer in the PVA-based polymer film is preferably in the range of 50 to 100% by mass, more preferably in the range of 80 to 100% by mass, still more preferably in the range of 85 to 100% by mass.

The thickness of the PVA-based polymer film is not particularly limited, but is preferably 60 μm or less, more preferably 50 μm or less, and still more preferably 30 μm or less. On the other hand, the thickness is preferably 1 μm or more, and more preferably 3 μm or more, from the viewpoint of producing the polarizing film more smoothly.

The shape of the PVA-based polymer film is not particularly limited, but a long film is preferable from the viewpoint of continuously producing a polarizing film with good productivity. The length of the long film is not particularly limited, and can be appropriately set depending on the use of the polarizing film to be produced, and the like, and can be, for example, in the range of 5 to 20,000 m. The width of the long film is not particularly limited, but may be, for example, 50 cm or more. From the viewpoint of requiring a wide polarizing film in recent years, it is preferably 1 m or more, more preferably 2 m or more, and particularly preferably 4 m. the above. The upper limit of the width of the long film is not particularly limited. However, if the width is too wide, it tends to be difficult to uniformly extend when a polarizing film is produced by a practical device, so that the width of the PVA polymer film is preferable. It is 7m or less.

The form of the PVA-based polymer film is not particularly limited, and may be in the form of a single layer, or may be, for example, a laminate form in which a PVA-based polymer film is formed on a thermoplastic resin film by a coating method or the like. However, it is preferable that it is a single layer form from the viewpoint of the complexity of the lamination (coating, etc.) operation, the cost of a thermoplastic resin film, and the like.

The method for producing the PVA-based polymer film is not particularly limited, and a film or a film having a thickness and a width after film formation can be preferably used. For example, the PVA-based polymer constituting the PVA-based polymer film can be used. And a film-forming stock solution in which one or more of a plasticizer, a surfactant, and other components are dissolved in a liquid medium, or a PVA-based polymer and, if necessary, a plasticizer or a surfactant, One or two or more kinds of PVA-based polymers of the other components and the liquid medium are produced by melting the film-forming stock solution. When the film forming stock solution contains at least one of a plasticizer, a surfactant, and other components, the components are preferably uniformly mixed.

Examples of the liquid medium used in the preparation of the film forming solution include water, dimethyl hydrazine, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and ethylene. Alcohol, glycerin, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, trimethylolpropane, ethylenediamine, diethylenetriamine, etc., one or two of these may be used. More than one species. Among them, from the point of giving a small load to the environment or recycling, it is preferred For water.

The volatilization ratio of the film forming solution (the content of the volatile component in the film forming solution such as the liquid medium removed by volatilization or evaporation during film formation) also differs depending on the film forming method, the film forming conditions, and the like. Preferably, it is in the range of 50 to 95% by mass, more preferably in the range of 55 to 90% by mass, and particularly preferably in the range of 60 to 85% by mass. Since the volatilization ratio of the film forming solution is 50% by mass or more, the viscosity of the film forming solution is not excessively high, and the filtration or defoaming at the time of preparing the film forming solution is smoothly performed, and the PVA-based polymer film having less foreign matter or defects is used. Manufacturing systems are easy. On the other hand, since the volatility of the film forming stock solution is 95% by mass or less, the concentration of the film forming stock solution is not excessively lowered, and the production of the industrial PVA polymer film is easy.

The film forming method for producing a PVA-based polymer film using the film-forming raw material solution may, for example, be a casting film forming method, an extrusion film forming method, a wet film forming method, a gel film forming method, or the like, and is preferably cast. Film forming method, extrusion film forming method. These film forming methods may be used alone or in combination of two or more. Among these film forming methods, from the viewpoint of obtaining a PVA-based polymer film having uniform thickness and width and good physical properties, it is more preferably a casting film forming method or an extrusion film forming method. For the PVA-based polymer film, drying or heat treatment may be carried out as needed.

As an example of a specific production method of the PVA-based polymer film, for example, industrially, it is preferable to use a T-die slit die, a hopper plate, an I-die, a lip coater die, etc. Evenly ejected or cast onto the circumferential surface of the first heated roll (or belt) located on the most upstream side, and one side of the film discharged or cast from the circumferential surface of the first roll (or belt) Volatile components are evaporated and dried, then placed downstream The side surface of one or a plurality of rolls for heating and heating is further dried, or passed through a hot air drying device, and then taken up by a winding device. The drying by the heated rolls and the drying by the hot air drying means can also be carried out in a suitable combination.

According to the above-described production method, a PVA-based polymer film which does not substantially extend (without elongation treatment) can be easily obtained. The PVA-based polymer film may be directly bonded to the protective film using the adhesive of the present invention, but the PVA-based polymer film which is followed by the protective film in the present invention is preferably an extended film, particularly preferably a polarizing film, phase. An optical film such as a film.

[Method of Manufacturing Polarized Film]

The method for producing a polarizing film using the above-described substantially non-extended PVA-based polymer film as a raw material film is not particularly limited, and any method conventionally employed may be employed, for example, by applying a swelling treatment to a PVA-based polymer film. A polarizing film is produced by dyeing, stretching, and, if necessary, further crosslinking treatment, fixing treatment, drying treatment, heat treatment, and the like. In this case, the order of each treatment such as the swelling treatment, the dyeing treatment, the stretching treatment, and the fixation treatment is not particularly limited, and one or two or more treatments can be simultaneously performed. Further, one or two or more of the respective treatments of two or more times may be performed.

The swelling treatment can be carried out by immersing a PVA-based polymer film in water. The temperature of the water when immersed in water is preferably in the range of 20 to 40 ° C, more preferably in the range of 22 to 38 ° C, and particularly preferably in the range of 25 to 35 ° C. Further, the time of immersion in water is, for example, preferably in the range of 0.1 to 5 minutes, more preferably in the range of 0.5 to 3 minutes. Furthermore, water immersion The water system at the time is not limited to pure water, and may be an aqueous solution in which various components have been dissolved, or a mixture of water and an aqueous medium.

The dyeing treatment can be carried out using an iodine-based dye, and the dyeing period can be any stage before stretching treatment, stretching treatment, and stretching treatment. The dyeing is generally carried out by immersing the PVA-based polymer film in a solution (especially an aqueous solution) containing iodine-potassium iodide as a dyeing bath, and such a dyeing method is also suitably employed in the present invention. The concentration of iodine in the dyeing bath is preferably in the range of 0.01 to 0.5% by mass, and the concentration of potassium iodide is more preferably in the range of 0.01 to 10% by mass. Further, the temperature of the dye bath is 20 to 50 ° C, and particularly preferably 25 to 40 ° C.

The crosslinking treatment can be carried out by immersing the PVA-based polymer film in an aqueous solution containing a crosslinking agent. When the crosslinking treatment is carried out, cross-linking is introduced into the PVA-based polymer film, and when the stretching treatment is carried out in a wet manner at a relatively high temperature, the PVA-based polymer can be effectively prevented from eluting in water. From such a viewpoint or the like, the crosslinking treatment is preferably carried out after the dyeing treatment. As the crosslinking agent, one type or two or more types of boron compounds such as a borate such as boric acid or borax can be used. The concentration of the crosslinking agent in the aqueous solution containing the crosslinking agent is preferably in the range of from 1 to 15% by mass, more preferably from 2 to 7% by mass. The aqueous solution containing a crosslinking agent may also contain an auxiliary agent such as potassium iodide. The temperature of the aqueous solution containing the crosslinking agent is preferably in the range of 20 to 50 ° C, more preferably in the range of 25 to 40 ° C.

The elongation treatment can be carried out by any of a wet stretching method or a dry stretching method. In the case of the wet stretching method, it may be carried out in an aqueous solution containing boric acid, or in a dye bath as described above or in a fixed treatment bath to be described later. Also, in the case of the dry extension method, water absorption can be used. The subsequent PVA-based polymer film was carried out in the air. Among these, a wet stretching method is preferred, and it is more preferred to uniaxially extend in an aqueous solution containing boric acid. The concentration of boric acid in the aqueous boric acid solution is preferably in the range of 0.5 to 6.0% by mass, more preferably in the range of 1.0 to 5.0% by mass, particularly preferably in the range of 1.5 to 4.0% by mass. Further, the aqueous boric acid solution may further contain potassium iodide, and the concentration thereof is preferably in the range of 0.01 to 10% by mass.

The extension temperature of the stretching treatment is preferably in the range of 30 to 90 ° C, more preferably in the range of 40 to 80 ° C, and particularly preferably in the range of 50 to 70 ° C.

Further, the stretching ratio of the stretching treatment is preferably 5 times or more, more preferably 5.5 times or more, and particularly preferably 6 times or more from the viewpoint of the polarizing performance of the obtained polarizing film. The upper limit of the stretching ratio is not particularly limited, but the stretching ratio is preferably 8 times or less.

In the production of the polarizing film, in order to make the adsorption of the dye (iodine or the like) to the PVA-based polymer film strong, it is preferred to carry out a fixing treatment. As the fixed treatment bath used in the fixation treatment, one type or two or more types of aqueous solutions containing a boron compound such as an acid or borax can be used. Further, an iodine compound or a metal compound may be added to the fixed treatment bath as needed. The concentration of the boron compound in the fixed treatment bath is generally preferably from 2 to 15% by mass, particularly preferably from about 3 to 10% by mass. The temperature of the fixed treatment bath is preferably from 15 to 60 ° C, particularly preferably from 25 to 40 ° C.

The drying treatment is preferably carried out at 30 to 150 ° C, particularly preferably at 50 to 130 ° C. Drying at a temperature within the above range makes it easy to obtain a polarizing film excellent in dimensional stability.

[Other PVA-based polymer films]

In the PVA-based polymer film which is bonded to the protective film using the adhesive of the present invention, examples of the PVA-based polymer film other than the polarizing film and the retardation film include optical films other than the polarizing film and the retardation film. Film, conductive film, photosensitive film, protective film, release film, rust-proof film, cover film, transfer film, abrasive film, window film, decorative film, adhesive film, film for vibration-damping steel, biodegradable film, antibacterial Film and the like. Examples of the optical film other than the polarizing film and the retardation film include an antireflection film, an alignment film, a polarizing layer protective film, a viewing angle improving film, a brightness improving film, an electromagnetic wave shielding film, a light shielding film, an infrared blocking film, and an ultraviolet blocking film. Film, filter lens, optical low pass filter (OLPF) film, weather resistant film, etc.

[protective film]

The protective film to be bonded to the PVA-based polymer film using the adhesive of the present invention is not particularly limited, and examples thereof include an ionic polymer, polyethylene, cellulose, triacetyl cellulose (TAC), and (methyl). Acrylic polymer, polymer containing alicyclic structure, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polypropylene, polyester, polycarbonate, polystyrene, polyacrylonitrile, ethylene-acetic acid A film of a polymer of a vinyl ester copolymer, an ethylene-vinyl alcohol copolymer, an ethylene-methacrylic acid copolymer, nylon, or the like. In the case of using a polarizing film or a retardation film as a PVA-based polymer film, it is preferable to use a film containing triacetyl cellulose, including (a methyl group), and a function of a protective film. A film of an acrylic polymer, a film comprising a polyester, or a film comprising a polymer having an alicyclic structure. The content of the above polymer in the above film It is preferably 50% by mass or more, more preferably 80% by mass or more, and still more preferably 85% by mass or more.

Further, in order to further improve the adhesion between the protective film and the adhesive layer, the surface of the protective film may be modified by a known corona treatment, plasma treatment, UV treatment, flame treatment or the like as needed.

The thickness of the protective film is not particularly limited, but is preferably 200 μm or less, and more preferably 100 μm or less. On the other hand, the thickness is preferably 5 μm or more, and more preferably 10 μm or more, from the viewpoint of an increase in mechanical strength of the obtained laminate.

[Use of adhesive]

The use of the adhesive agent of the present invention includes the use of a polarizing film or a retardation film and a protective film as described above (manufacture of a polarizing plate or a phase difference plate), and production of an electronic component or an electronic device. The use of synthetic resin, rubber, and the like in connection with a PVA-based polymer film is particularly useful for the production of a polarizing plate or a phase difference plate, and particularly for the production of a polarizing plate.

The adhesive of the present invention exhibits a high adhesion force in the subsequent step of the PVA-based polymer film and the protective film. The adhesion of the PVA-based polymer film after curing of the adhesive to the protective film is preferably 6.0 N/25 mm or more, more preferably 6.5 N/25 mm or more, and particularly preferably 7.0 N/25 mm or more. Further, the peeling force can be obtained by a method described later in the examples.

<Continue>

Next, an embodiment of the laminate of the present invention will be described. The adherend 1 of the first embodiment includes a PVA-based polymer film 2, a protective film 4, and an adhesive layer 3 disposed between the PVA-based polymer film 2 and the protective film 4. Here, The subsequent agent layer 3 is formed of the adhesive of the present invention.

[adhesive layer]

The layer 3 is then formed from the adhesive. Specifically, it can be formed by irradiating the adhesive with an active energy ray. The subsequent agent layer 3 may contain an additive depending on the use of the carrier 1.

The thickness of the layer 3 is not particularly limited, but if it is too thin, the adhesion force of the PVA-based polymer film 2 and the protective film 4 tends to decrease, and if it is too thick, the thickness of the bonding body 1 is unnecessarily increased. The thickness of the adhesive layer 3 is preferably 0.1 μm or more, more preferably 0.2 μm or more, still more preferably 0.3 μm or more, particularly preferably 0.5 μm or more, and more preferably 500 μm or less, and still more preferably 50 μm or less. It is preferably 20 μm or less, and particularly preferably 10 μm or less.

<Manufacturing method of the body>

Next, the body 1 can be produced by a production method having the following steps: a step of bonding the PVA-based polymer film 2 and the protective film 4 via the adhesive of the present invention (a bonding step), and after the bonding step, irradiation A step of hardening the adhesive by an active energy ray (irradiation step).

[Finishing step]

In the bonding step, the PVA-based polymer film 2 and the protective film 4 are bonded via the adhesive of the present invention. The bonding method is not particularly limited, but from the viewpoint of easier bonding, it is preferred to apply the present invention to one or both of the surface of the PVA-based polymer film and the surface of the protective film. After the agent, the PVA-based polymer film and the protective film are laminated. The coating method when the adhesive of the present invention is applied to one or both of the surface of the PVA-based polymer film and the surface of the protective film is not particularly For example, methods such as die coating, roll coating, air knife coating, gravure coating, doctor roll coating, blade coating, curtain coating, spraying, wire bar, bar coating, dipping, brush coating, and the like can be exemplified.

Further, as the bonding method, in addition to the above, a method in which a PVA-based polymer film and a protective film are laminated and a primer of the present invention is infiltrated between the two may be employed.

Further, the laminate obtained by the bonding step may be pressed by a roll or the like. In this case, examples of the material of the roller include metal, rubber, and the like. The roller on the side of the PVA-based polymer film and the roller on the side of the protective film may be the same material or different materials.

[Irradiation step]

The adherend of the present invention can be obtained by irradiating the laminated body after bonding with an active energy ray to cure the uncured adhesive. The active energy ray can be appropriately selected according to the kind of various components contained in the adhesive of the present invention. Examples of the active energy ray include electromagnetic waves such as ultraviolet rays, infrared rays, X-rays, and gamma rays, and electron beams, proton wires, and neutron wires, etc., from the curing rate, the availability of the irradiation device, and the price. From the viewpoint, it is preferably ultraviolet light or electron beam, and more preferably ultraviolet light.

The above active energy ray can be irradiated using well known devices. When ultraviolet rays are used as the active energy ray, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, a chemical lamp, an LED, or the like which emits light in a wavelength range of 450 nm or less can be used. Further, when an electron beam (EB) is used as the active energy ray, the acceleration voltage is preferably in the range of 0.1 to 10 MeV, and the irradiation line amount is preferably in the range of 1 to 500 kGy.

Integrated light amount of the active energy ray system is not particularly limited, but is preferably in the range of 10 ~ 20,000mJ / cm ² of, more preferably within a range of 30 ~ 5,000mJ / cm ² of. When the total amount of light of the active energy ray is too small, the adhesion between the cured PVA polymer film and the protective film tends to decrease. On the other hand, if the total amount of light of the active energy ray is too large, excessive heat is generated in the adherend, and the adhesive layer or the PVA-based polymer film tends to be deteriorated.

The hardening of the adhesive can also be promoted by heating as needed during or after the irradiation of the active energy ray. The heating temperature is preferably in the range of 40 to 130 ° C, more preferably in the range of 50 to 100 ° C from the viewpoint of the curing speed or the influence on each layer.

The adhesive layer of the present invention is formed by hardening of the adhesive of the present invention to obtain a laminate of the present invention.

<Other Embodiments>

The adhesive of the present invention may also have a plurality of adhesive layers. For example, in the PVA-based polymer film, an adhesive layer may be further provided on the side opposite to the side on which the adhesive layer is formed as described above, and the adhesive layer is laminated on the side opposite to the PVA-based polymer film. A protective film or the like may have a structure of a protective film/adhesive layer/PVA-based polymer film/adhesive layer/protective film.

When the adhesive of the present invention is a polarizing plate, an adhesive such as an acrylic resin is applied onto the polarizing plate, and then bonded to a glass substrate to be used as a component of the LCD. At the same time, it is also possible to bond with a retardation film, a viewing angle enhancement film, a brightness enhancement film, and the like.

[Examples]

The invention is more specifically illustrated by the following examples, but the invention is not limited by the examples. In addition, each evaluation or measurement method used in the following examples and comparative examples is shown below.

Then the evaluation of force

After the polarizing plate obtained in each of the following Examples and Comparative Examples was further allowed to stand at a temperature of 23 ° C and a relative humidity of 50% for 24 hours, the longitudinal direction (the direction in which the polarizing film was extended) was 250 mm from the polarizing plate × the width direction was A 25 mm rectangular film sheet was cut out in each of the examples or comparative examples. Next, peeling was performed between the polarizing film of each film sheet and the polymethyl methacrylate film of one side in accordance with the T-die peeling test based on JIS K 6854-3:1999, and the peeling force obtained (5 pieces) The average value is taken as the adhesion force. The measurement conditions of this test were a peeling speed of 30 mm/min. Further, when the adhesion between the two films was too high and the polymethyl methacrylate film was broken, it was evaluated as "material destruction".

Evaluation of water resistance

The polarizing plates obtained in each of the following Examples or Comparative Examples were immersed in water at 60 ° C for 48 hours. Then, the polarizing plate was lifted from the water, and the presence or absence of peeling between the polarizing film and the polymethyl methacrylate film was evaluated based on the following criteria.

A: no peeling

B: There is stripping

Method for determining water contact angle

A film sheet of 50 mm square was cut out from the polymethyl methacrylate film to be measured, and the side of the film sheet in contact with the adhesive was measured in accordance with JIS R 3257:1999 (Test method for wettability of the surface of the substrate glass). The water contact angle of the face. That is, 4 μl or less of water droplets are allowed to stand on the horizontally placed film sheet, and the radius r (mm) of the surface of the water droplet contacting the film sheet and the height h (mm) from the surface of the film sheet to the apex of the water droplet are measured from the shape of the water droplet. The water contact angle θ (°) was obtained by the following formula (1).

θ=2tan ^-1 (h/r)(1)

Further, the measurement system was carried out 5 times, and the average value was taken as the water contact angle of the film. Further, the measurement was carried out under the conditions of a temperature of 25 ° C and a humidity of 50% RH.

[Examples 1 to 4 and Comparative Examples 1 to 5]

<Manufacture of adhesive>

Each of the materials was placed in a container having a stirring device and sealed at a mixing ratio shown in Table 1, and stirred for 24 hours to uniformly mix to obtain an adhesive. Furthermore, the contents of each material are as follows.

"PVA-based polymer (A)"

PVA: saponified product of homopolymer of vinyl acetate (saponification degree: 40 mol%, content of acetalized vinyl alcohol unit: 0 mol%, degree of polymerization: 250).

PVB: a saponified product of a homopolymer of vinyl acetate by polyvinyl butyral which is acetalized with n-butyraldehyde (content of vinyl alcohol unit: 28 mol%, content of acetalized vinyl alcohol unit: 70 mol %, content of vinyl ester unit: 2 mol %, degree of polymerization: 500).

"Polyol"

PO-1: Polyester polyol ("Kuraray Polyol P-5010" manufactured by Kuraray Co., Ltd.)

PO-2: Polycarbonate polyol (made by Kuraray Co., Ltd.) Kuraray Polyol C-2090")

"Cationally polymerizable compound (B)" (other than the cationically polymerizable compound (BD) which will be described later)

B-1: 3-ethyl-3-hydroxymethyloxetane ("OXT-101" manufactured by Toagosei Co., Ltd.)

B-2: 3', 4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate ("Celloxide 2021P" manufactured by DAICEL Co., Ltd.)

"Cationic polymerization initiator (C)"

C-1: 50% by mass of a propylene carbonate diphenyl [4-(phenylthio)phenyl]phosphonium hexafluorophosphate ("CPI-100P" manufactured by Sun-Apro Co., Ltd.)

"Radical Polymerizable Compound (D)"

D-1: benzyl acrylate ("Viscoat 160" manufactured by Osaka Organic Chemical Industry Co., Ltd.)

D-2: ginseng (2-hydroxyethyl) isocyanurate triacrylate ("Aronix M-315" manufactured by Toagosei Co., Ltd.)

"Radical Polymerization Starter (E)"

E-1:1-hydroxycyclohexyl phenyl ketone ("IRGACURE 184" manufactured by BASF)

"Cationally polymerizable compound which is also a radical polymerizable property (BD)"

BD-1: 3-ethyl-3-propenyloxymethyloxycyclobutane ("OXE-10" manufactured by Osaka Organic Chemical Industry Co., Ltd.)

<Manufacture of a bonding body (polarizing plate)>

Polymethacrylic acid having a thickness of 50 μm and a size of 300 mm × 100 mm A methyl ester film (manufactured by Kuraray Co., Ltd.) was used as a protective film, and the above-mentioned adhesive was applied to one surface of the polymethyl methacrylate film using a bar coater. Then, a polarizing film having a thickness of 10 μm, an extending direction of 280 mm, and a width direction of 80 mm (manufactured by dyeing and uniaxially extending the iodine-based dye to the PVA-based polymer film) was laminated with the adhesive. On the above protective film. Then, on the surface of the polarizing film which is not in contact with the adhesive, the same adhesive as described above was applied using a bar coater to obtain a polymethacrylic acid having a thickness of 50 μm and a size of 300 mm × 100 mm as another protective film. A methyl ester film (manufactured by Kuraray Co., Ltd.) was laminated on the polarizing film via the adhesive. The laminate of the thus obtained layer having a polymethyl methacrylate film/adhesive/polarizing film/adhesive/polymethyl methacrylate film was pressed by a laminator, and the thickness of the adhesive portion was 1 μm each.

Then, an ultraviolet ray irradiation device (a metal halide lamp of GS YUASA Co., Ltd.) was used, and the laminated body was irradiated with ultraviolet rays so that the integrated light amount was 700 mJ/cm ² . Further, the cumulative amount of light was measured using a UV measuring instrument (GS YUASA Co., Ltd.). After the ultraviolet irradiation, the mixture was allowed to stand at a temperature of 23 ° C and a relative humidity of 50% for 24 hours to obtain a polarizing plate as a binder. In each of the examples and the comparative examples, two polarizing plates were produced in order to evaluate the adhesion, and one polarizing plate was produced in order to evaluate the water resistance. Further, in Examples 3 and 4, two sheets of polymethyl methacrylate film used for the production of the respective polarizing plates were used, and both of them were corona-coated on the side in contact with the adhesive. Treated polymethyl methacrylate film.

<evaluation>

With respect to the above polarizing plate, evaluation of adhesion and water resistance was performed by the above method. The results are shown in Table 1.

Claims (13)

An active energy ray-curing type adhesive for a film comprising a polyvinyl alcohol-based polymer and a protective film, comprising a polyvinyl alcohol-based polymer (A) and a cationically polymerizable compound (B) And a cationic polymerization initiator (C). The adhesive of claim 1, which further comprises a radical polymerizable compound (D) and a radical polymerization initiator (E). The adhesive of claim 1 or 2, wherein at least a part of the cationically polymerizable compound (B) is a compound which is cationically polymerizable and is also a radical polymerizable compound (BD). The adhesive according to any one of claims 1 to 3, wherein the content of the acetalized vinyl alcohol unit of the polyvinyl alcohol-based polymer (A) is less than 10 mol% and the degree of saponification is 80 mol% The following polyvinyl alcohol. The adhesive agent according to any one of claims 1 to 3, wherein the polyvinyl alcohol-based polymer (A) is a polyvinyl acetal having a content of the acetalized vinyl alcohol unit of 10 mol% or more. An adhesive according to claim 5, wherein the polyvinyl acetal is polyvinyl butyral. The adhesive agent according to any one of claims 1 to 6, wherein the content of the polyvinyl alcohol-based polymer (A) is from 1 to 90% by mass. A binder comprising a film comprising a polyvinyl alcohol polymer, a protective film, and a binder layer, wherein the adhesive layer is disposed between the film containing the polyvinyl alcohol polymer and the protective film, and then The agent layer is obtained by hardening the adhesive of any one of claims 1 to 7. The adherend of claim 8, wherein the film comprising the polyvinyl alcohol-based polymer is an extended film. The adherend of claim 8 or 9, wherein the stretched film is a polarizing film or a retardation film. The adhesive body according to any one of claims 8 to 10, wherein the protective film comprises triacetyl cellulose, a (meth)acrylic polymer, a polyester or a polymer having an alicyclic structure. The adhesive body according to any one of claims 8 to 11, wherein the film containing the polyvinyl alcohol-based polymer and the protective film have an adhesion of 6.0 N/25 mm or more. A method for producing a laminate, comprising laminating a film comprising a polyvinyl alcohol-based polymer and a protective film via an adhesive according to any one of claims 1 to 7, and then irradiating the active energy ray to harden the adhesive layer .