CN106189943B - Adhesive composition and adhesive film - Google Patents

Adhesive composition and adhesive film Download PDF

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Publication number
CN106189943B
CN106189943B CN201510249974.8A CN201510249974A CN106189943B CN 106189943 B CN106189943 B CN 106189943B CN 201510249974 A CN201510249974 A CN 201510249974A CN 106189943 B CN106189943 B CN 106189943B
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Prior art keywords
adhesive
adhesive layer
meth
weight
film
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CN106189943A (en
Inventor
长仓毅
长谷川良
吉田弘幸
菱沼昌世
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Fujimori Kogyo Co Ltd
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Fujimori Kogyo Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays

Abstract

Provided are an adhesive layer which is a thin film but has excellent reworkability and high adhesiveness, and an adhesive film using the adhesive layer. The adhesive layer comprises an acrylic polymer of a copolymer having an acid value of 0.1 or less and a weight average molecular weight of 100 ten thousand or more and (3) an isocyanate compound of a crosslinking agent, wherein the acrylic polymer contains (1) an alkyl (meth) acrylate monomer having an alkyl group of C1 to C14 and/or an aryl group-containing (meth) acrylate monomer, contains at least 30 parts by weight or more of butyl acrylate in the (1), does not contain a carboxyl group-containing copolymerizable vinyl monomer but contains 0.1 to 3.5 parts by weight of (2) a hydroxyl group-containing copolymerizable vinyl monomer based on the (1), and the crosslinking agent is contained in an amount of 0.01 to 0.8 parts by weight based on the (1), has a gel fraction after crosslinking of 40 to 75%, a thickness of 1 to 25 μm, and an adhesive force of 25 μm of 1.5 to 6.0N/25 mm.

Description

Adhesive composition and adhesive film
Technical Field
The present invention relates to an adhesive layer and an adhesive film used for bonding optical members such as a polarizing plate.
Background
Various adhesive films have been proposed for bonding optical members such as a polarizing plate and a retardation plate to an adherend such as a liquid crystal cell via an adhesive layer (see, for example, patent documents 1 to 2).
Patent document 1 describes an optical adhesive composition containing a monomer containing butyl acrylate or the like as a main component and an acrylamide compound or the like.
Patent document 2 describes an optical adhesive composition containing a (meth) acrylate ester having an alkyl group having 4 to 8 carbon atoms as a main component monomer, and a carboxyl group-containing monomer and a nitrogen-containing vinyl monomer.
In addition, many adhesive films have been proposed through repeated studies in order to increase the refractive index of the adhesive layer (for example, see patent documents 3 to 8).
Patent document 3 describes an optical adhesive composition containing a tackifier having an aromatic ring and having a refractive index of 1.51 to 1.75.
Patent document 4 describes an adhesive sheet including an adhesive composition containing a copolymerizable polymer of an aromatic ring-containing acrylic acid-modified monomer.
Patent document 5 describes an optical adhesive composition containing a tackifying resin containing an aromatic ring and an aromatic phosphate plasticizer.
Patent document 6 describes an adhesive obtained by curing an adhesive composition including: an acrylic resin; and an aromatic compound having one ethylenically unsaturated group.
Patent document 7 describes an optical member in which a retardation film and a birefringent plate are fixed to each other by an acrylic adhesive containing an aromatic monomer.
Patent document 8 describes an adhesive composition containing a urethane resin obtained by reacting an aromatic diisocyanate and an aromatic polyester diol.
In recent years, in order to reduce the thickness of optical members, adhesive films having a thin adhesive layer have been required as adhesive films used for interlayer bonding of optical members.
In general, the adhesive force of the adhesive layer is substantially proportional to the thickness of the adhesive layer, and therefore, if the thickness of the adhesive layer is reduced, the adhesive force is reduced.
However, in recent years, adhesive films are required to have the following properties: even when the thickness of the adhesive layer is reduced, the adhesive film has an adhesive force equivalent to that of a conventional adhesive film (the adhesive layer is a thick layer having a thickness of about 30 μm), and has a durability after being left for a long time in a high-temperature and high-humidity environment equal to or higher than that of a conventional adhesive film.
In addition, from the viewpoint of being able to reduce the thickness of the adhesive layer and being able to form an adhesive layer that does not require aging treatment (curing at a constant temperature), it is required to be formed in the form of an NCF (Non Carrier Film) which is composed only of the adhesive layer from which the adhesive Film base material is removed and which has a member of "release Film (release Film)/adhesive layer/release Film".
In addition, in the conventional adhesive film, since the adhesive film is bonded to the adherend and then subjected to the aging treatment, the adhesion between the adherend and the adhesive layer can be improved.
However, in the adhesive film using the NCF form, since the aging treatment of the adhesive layer has been completed, the adhesion between the adherend and the adhesive layer is insufficient. Accordingly, there is a problem that surface treatment such as corona treatment is required for the surface of the adherend.
There is therefore a need for an adhesive film that meets these requirements and overcomes these problems.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2012-177022
Patent document 2: japanese patent laid-open No. 2012-201734
Patent document 3: japanese laid-open patent publication No. 2007-084762
Patent document 4: japanese patent laid-open publication No. 2011-153169
Patent document 5: japanese patent laid-open publication No. 2012-167188
Patent document 6: japanese patent laid-open publication No. 2012-021148
Patent document 7: japanese patent laid-open publication No. 2006-293281
Patent document 8: japanese laid-open patent publication No. 2009 + 091522
Disclosure of Invention
Problems to be solved by the invention
The present invention has been made in view of the above circumstances, and an object thereof is to provide an adhesive layer having excellent reworkability and high adhesiveness in spite of being a thin film, and an adhesive film using the adhesive layer.
Means for solving the problems
In order to solve the above problems, the adhesive layer of the present invention is characterized in that an isocyanate compound as a crosslinking agent is used as the adhesive composition, and a silane coupling agent is more preferably used in combination with a copolymer having a weight average molecular weight of 100 ten thousand or more, which contains butyl acrylate as an essential monomer and a hydroxyl group-containing copolymerizable vinyl monomer as a functional group-containing monomer, instead of a carboxyl group-containing copolymerizable vinyl monomer.
In order to solve the above problems, the present invention provides an adhesive layer obtained by crosslinking an adhesive composition containing an acrylic polymer,
the adhesive composition includes: an acrylic polymer which is a copolymer having an acid value of 0.1 or less and a weight-average molecular weight of 100 ten thousand or more; and (3) an isocyanate compound as a crosslinking agent,
the acrylic polymer contains (1) at least one or more selected from the group consisting of alkyl (meth) acrylate monomers having an alkyl group with carbon atoms of C1-C14 and aryl group-containing (meth) acrylate monomers as a (meth) acrylate monomer, and contains at least 30 parts by weight or more of butyl acrylate per 100 parts by weight of the (meth) acrylate monomer in total,
the acrylic polymer does not contain a carboxyl group-containing copolymerizable vinyl monomer, but contains (2) 0.1 to 3.5 parts by weight of a hydroxyl group-containing copolymerizable vinyl monomer per 100 parts by weight of the total (meth) acrylate monomer,
the content of the isocyanate compound (3) as a crosslinking agent is 0.01 to 0.8 part by weight based on 100 parts by weight of the total (meth) acrylate monomer,
and the gel fraction of the adhesive layer after crosslinking is 40-75%, the thickness of the adhesive layer is 1-25 μm, and the adhesive force of the adhesive layer with the thickness of 25 μm is 1.5-6.0N/25 mm.
In addition, the adhesive composition preferably contains 0.01 to 0.5 parts by weight of (4) a silane coupling agent per 100 parts by weight of the total (meth) acrylate monomer.
In addition, the isocyanate compound in the adhesive composition is preferably a trimethylolpropane adduct of toluene diisocyanate.
In addition, it is preferable that the hydroxyl group-containing copolymerizable vinyl monomer (2) in the adhesive composition is at least one selected from the group consisting of 8-hydroxyoctyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate.
Further, the adhesive layer preferably has an adhesive strength of 1.5 to 10N/25mm after being bonded to an adherend at 70 ℃ for 10 days.
The present invention also provides an adhesive film having a structure comprising a release film/adhesive layer/release film, wherein the adhesive layer is formed on one surface of the release film.
The present invention also provides an adhesive film comprising a substrate and the adhesive layer laminated on one surface of the substrate.
The present invention also provides an adhesive film for bonding a polarizing plate and a display panel, which uses the adhesive film.
The present invention also provides a polarizing plate with an adhesive layer, which uses the adhesive film.
The present invention also provides a polarizing plate with an adhesive layer, which uses the adhesive film and uses a retardation film having a retardation of λ/4 or λ/2 as a constituent material.
The present invention also provides an optical film with an adhesive layer, wherein the adhesive layer is laminated on at least one surface of the optical film.
Effects of the invention
The present invention provides an adhesive layer having flexibility, hardness, durability, and reworkability, and an adhesive film using the adhesive layer, wherein the adhesive layer has a high gel fraction even after crosslinking, when the amount of crosslinking agent and the amount of functional group are reduced as compared with conventional adhesive layers.
The adhesive film of the present invention is a thin film but has excellent reworkability and high adhesiveness.
Detailed Description
The present invention will be described below based on preferred embodiments.
The adhesive layer of the present invention is obtained by crosslinking an adhesive composition containing an acrylic polymer,
the adhesive composition includes: an acrylic polymer which is a copolymer having an acid value of 0.1 or less and a weight average molecular weight of 100 ten thousand or more; and (3) an isocyanate compound as a crosslinking agent,
the acrylic polymer contains (1) at least one or more selected from the group consisting of alkyl (meth) acrylate monomers having an alkyl group with carbon atoms of C1-C14 and aryl group-containing (meth) acrylate monomers as a (meth) acrylate monomer, and contains at least 30 parts by weight or more of butyl acrylate per 100 parts by weight of the (meth) acrylate monomer in total,
the acrylic polymer does not contain a carboxyl group-containing copolymerizable vinyl monomer, but contains (2) 0.1 to 3.5 parts by weight of a hydroxyl group-containing copolymerizable vinyl monomer per 100 parts by weight of the total (meth) acrylate monomer,
the content of the isocyanate compound (3) as a crosslinking agent is 0.01 to 0.8 part by weight based on 100 parts by weight of the total (meth) acrylate monomer,
and the gel fraction of the adhesive layer after crosslinking is 40-75%, the thickness of the adhesive layer is 1-25 μm, and the adhesive force of the adhesive layer with the thickness of 25 μm is 1.5-6.0N/25 mm.
In the adhesive composition of the present invention, examples of the alkyl (meth) acrylate monomer having an alkyl group with a carbon number of C1 to C14 include: at least one member selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, cyclopentyl (meth) acrylate, and cyclohexyl (meth) acrylate. The alkyl group in the alkyl (meth) acrylate monomer may be linear, branched, or cyclic.
The total content of the alkyl (meth) acrylate ester monomers having an alkyl group having from C1 to C14 is preferably 70 parts by weight or more, and may be 100 parts by weight, based on 100 parts by weight of the total (meth) acrylate ester monomers. The ratio of the alkyl (meth) acrylate monomer having an alkyl group with a carbon number of C1-C14 is preferably 50-99.9 parts by weight based on 100 parts by weight of the acrylic polymer (copolymer) of the adhesive composition. In the present invention, butyl acrylate is used as an essential monomer. The content of butyl acrylate is preferably at least 30 parts by weight or more per 100 parts by weight of the total (meth) acrylate monomer.
In the present invention, the adhesive composition can increase the refractive index of the adhesive layer to 1.47 or more by setting the content of the methyl acrylate monomer in 100 parts by weight in total of the (meth) acrylate monomer composed of one or more alkyl (meth) acrylate monomers having an alkyl group having from C1 to C14 to 20 parts by weight or more.
The adhesive composition of the present invention may further contain, as the (meth) acrylate monomer, at least one kind of aryl group-containing (meth) acrylate monomer. Examples of the aryl group-containing (meth) acrylate monomer include benzyl (meth) acrylate, naphthyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxybutyl (meth) acrylate, 2- (1-naphthyloxy) ethyl (meth) acrylate, 2- (2-naphthyloxy) ethyl (meth) acrylate, 6- (1-naphthyloxy) hexyl (meth) acrylate, 6- (2-naphthyloxy) hexyl (meth) acrylate, 8- (1-naphthyloxy) octyl (meth) acrylate, and 8- (2-naphthyloxy) octyl (meth) acrylate. In order to obtain a binder layer having a high refractive index, at least one aromatic group-containing (meth) acrylate monomer is preferably blended.
By mixing these aryl group-containing (meth) acrylate monomers with alkyl (meth) acrylate monomers having an alkyl group with a carbon number of C1 to C14, the refractive index of the obtained adhesive layer can be increased and adjusted, the refractive index difference between optical members can be reduced, and total reflection can be reduced, thereby increasing the total light transmittance. In the adhesive layer of the present invention, when the adhesive composition includes the aryl group-containing (meth) acrylate monomer, the aryl group-containing (meth) acrylate monomer is preferably contained in an amount of 5 to 30 parts by weight, based on 100 parts by weight of the total (meth) acrylate monomer.
Further, by copolymerizing the aryl group-containing (meth) acrylate monomer, the refractive index of the adhesive layer can be further increased as compared with the effect of increasing the refractive index of the adhesive layer by including 20 parts by weight or more of the methyl acrylate monomer in 100 parts by weight in total of the above (meth) acrylate monomers.
As described above, as a method for increasing the refractive index of the adhesive layer, the following two methods are included: a method comprising adding 20 parts by weight or more of a methyl acrylate monomer to 100 parts by weight of a total amount of (meth) acrylate monomers; and a method of copolymerizing an aryl group-containing (meth) acrylate monomer. Each method may be used alone, but it is more preferable to use both methods.
In the adhesive composition of the present invention, the acrylic polymer does not include a carboxyl group-containing copolymerizable vinyl monomer as the functional group-containing monomer, but includes a hydroxyl group-containing copolymerizable vinyl monomer. As the functional group-containing monomer, only a copolymerizable vinyl monomer containing a hydroxyl group may be used.
Examples of the hydroxyl group-containing copolymerizable vinyl monomer include: hydroxyl group-containing alkyl (meth) acrylates such as 8-hydroxyoctyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate; at least one kind of hydroxyl group-containing (meth) acrylamides such as N-hydroxy (meth) acrylamide, N-methylol (meth) acrylamide, and N-hydroxyethyl (meth) acrylamide.
Among them, the hydroxyl group-containing copolymerizable vinyl monomer is preferably at least one selected from the group consisting of 8-hydroxyoctyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate.
In the adhesive layer of the present invention, the hydroxyl group-containing copolymerizable vinyl monomer contained in the adhesive composition can be used as a copolymerizable vinyl monomer for reducing the content of the carboxyl group-containing copolymerizable vinyl monomer, which exerts a corrosive influence on an adherend susceptible to corrosion, such as an ITO surface of a transparent conductive film, in the resulting adhesive layer. Therefore, the hydroxyl group-containing copolymerizable vinyl monomer can contribute to improvement in adhesion of the adhesive layer and reduction in corrosiveness. In the adhesive layer of the present invention, the content of the hydroxyl group-containing copolymerizable vinyl monomer in the adhesive composition is preferably 0.1 to 3.5 parts by weight with respect to 100 parts by weight of the total (meth) acrylate monomer.
The acrylic polymer of the adhesive composition used in the adhesive layer of the present invention is a copolymer having an acid value of 0.1 or less and a weight average molecular weight of 100 ten thousand or more, which comprises (1) at least one or more selected from the group consisting of alkyl (meth) acrylate monomers having an alkyl group with a carbon number of C1 to C14 and aryl group-containing (meth) acrylate monomers as the (meth) acrylate monomers, and has a butyl acrylate content of at least 30 parts by weight or more per 100 parts by weight of the (meth) acrylate monomers in total,
the acrylic polymer does not contain a carboxyl group-containing copolymerizable vinyl monomer, but contains 0.1 to 3.5 parts by weight of (2) a hydroxyl group-containing copolymerizable vinyl monomer per 100 parts by weight of the total (meth) acrylate monomer.
The polymerization method of the copolymer is not particularly limited, and a suitable known polymerization method such as a solution polymerization method or an emulsion polymerization method can be used. The acrylic polymer preferably contains 50 to 100% by weight of an acrylic monomer such as a (meth) acrylate monomer or a (meth) acrylamide monomer.
The adhesive composition can be adjusted in properties such as desired physical property values by blending a crosslinking agent and any suitable additive to the acrylic polymer.
Examples of the crosslinking agent (3) include: at least one of a biuret modified product or an isocyanurate modified product of diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, toluene diisocyanate, and xylylene diisocyanate, and a polyisocyanate compound such as an adduct of a trivalent or higher polyhydric alcohol such as trimethylolpropane or glycerol. The acrylic polymer preferably contains a hydroxyl group as a functional group capable of undergoing a crosslinking reaction with an isocyanate compound of a crosslinking agent, and further preferably contains a monomer having these functional groups in a side chain. The adhesive composition preferably contains 0.01 to 0.8 parts by weight of an isocyanate compound per 100 parts by weight of the total (meth) acrylate monomer. As the crosslinking agent (3), only an isocyanate compound may be used. The isocyanate compound is preferably an adduct of toluene diisocyanate, and particularly preferably a trimethylolpropane adduct of toluene diisocyanate.
Preferably, the adhesive composition further contains (4) a silane coupling agent. Examples of the silane coupling agent (4) include: a compound having at least one organic functional group and at least one hydrolyzable group in 1 molecule, wherein the hydrolyzable group is an alkoxy group bonded to a silicon atom or the like. Preferably, the silane coupling agent has at least one organic functional group selected from the group consisting of an epoxy group, (meth) acryloyloxy group, mercapto group, and amino group. Here, (meth) acryloyloxy means acryloyloxy (CH) 2CHCOO-) or methacryloxy (CH) 2＝C(CH 3)COO-)。
Examples of the silane coupling agent having an epoxy group include: 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethylmethyldimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethylmethyldiethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltriethoxysilane, 5, 6-epoxyhexyltrimethoxysilane, 5, 6-epoxyhexylmethyldimethoxysilane, 5, 6-epoxyhexylmethyldiethoxysilane, 5, 6-epoxyhexyltriethoxysilane, etc.
Examples of the silane coupling agent having a (meth) acryloyloxy group include: 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 3- (meth) acryloyloxypropylmethyldiethoxysilane, 3- (meth) acryloyloxypropyldimethylethoxysilane, 3- (meth) acryloyloxypropyldimethylmethoxysilane and the like.
Examples of the silane coupling agent having a mercapto group include: 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 3-mercaptopropyltriethoxysilane, etc.
Examples of the silane coupling agent having an amino group include: 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3- (methylamino) propyltrimethoxysilane, 3- (methylamino) propyltriethoxysilane, and the like.
Further, an alkoxy oligomer (siloxy oligomer) which contains the organic functional group and has been subjected to oligomerization, or the like may be used as the silane coupling agent.
The content of the silane coupling agent (4) is preferably 0.01 to 0.5 parts by weight based on 100 parts by weight of the total (meth) acrylate monomer.
As other optional components, known additives such as an antioxidant, a surfactant, a curing accelerator, a plasticizer, a filler, a crosslinking catalyst, a crosslinking inhibitor, a curing inhibitor, a processing aid, and an antioxidant can be suitably blended. These may be used alone or in combination of two or more.
The adhesive layer of the present invention can be obtained by coating the adhesive composition on a substrate or a release film and then crosslinking the adhesive composition. The gel fraction of the crosslinked adhesive layer is preferably 40 to 75%.
When the pressure-sensitive adhesive layer is used for interlayer bonding of optical members or the like, the pressure-sensitive adhesive layer is desirably thin, and the thickness of the pressure-sensitive adhesive layer is preferably 1 to 25 μm, more preferably 5 to 25 μm. The adhesive strength of the adhesive layer is generally substantially proportional to the thickness of the adhesive layer, but preferably the adhesive strength of an adhesive layer having a thickness of 25 μm is 1.5 to 6.0N/25 mm. The adhesive layer preferably has an adhesive strength of 1.5 to 10N/25mm after being bonded to an adherend at 70 ℃ for 10 days. Examples of the adherend include a glass plate such as alkali-free glass, and a resin film.
When the adhesive layer of the present invention is used for interlayer bonding of an optical member, etc., it is desirable that the refractive index difference is as small as possible in order to reduce light reflection at the interface between the adhesive layer and the optical member. Therefore, the refractive index of the adhesive layer is preferably 1.47 to 1.50.
The adhesive film of the present invention can be produced by forming the adhesive layer of the present invention on one surface of a substrate or a release film.
As a base film for forming the adhesive layer or a release film (separator) for protecting the adhesive surface, a resin film such as a polyester film can be used.
The base film may be subjected to an anti-fouling treatment with a silicone or fluorine-based release agent, a coating agent, silica fine particles, or the like on the surface of the resin film opposite to the side on which the adhesive layer is formed, or may be subjected to an antistatic treatment by coating or mixing with an antistatic agent.
The release film is subjected to a release treatment with a silicone-based or fluorine-based release agent or the like on the surface thereof to be bonded to the adhesive surface of the adhesive layer.
The structure of "release film/adhesive layer/release film" can be formed by bonding the release-treated surfaces of the release films to both surfaces of one adhesive layer. In this case, the release films on both sides are peeled off sequentially or simultaneously to expose the adhesive surface, whereby the optical member such as an optical film can be bonded. Examples of the optical film include a polarizing film, a retardation film, an antireflection film, an anti-glare (anti-glare) film, an ultraviolet absorbing film, an infrared absorbing film, an optical compensation film, and a brightness enhancement film.
The adhesive film of the present invention can be used for bonding various optical films for peripheral members of liquid crystal displays including polarizing plates, various optical films for touch panels, various optical films for electronic paper, various optical films for organic EL, and the like.
The adhesive layer may be laminated on at least one surface of these optical films to produce an optical film with an adhesive layer. Specifically, the optical film may have a configuration such as "optical film/adhesive layer/optical film", "optical film/adhesive layer/release film", "optical film/adhesive layer/optical film", "optical film/adhesive layer/release film", "release film/adhesive layer/optical film/adhesive layer/release film", and the like.
For example, in the case of an optical film/adhesive layer/release film having an adhesive layer protected by a release film, the release film is peeled off to expose the adhesive layer such as the optical film/adhesive layer, and the adhesive layer is bonded to another optical film, whereby a configuration such as the optical film/adhesive layer/optical film in which the adhesive layer is used for interlayer bonding can be obtained.
The adhesive film of the present invention can be preferably used for bonding a polarizing plate and a display panel. For example, it is used as an adhesive layer of a polarizing plate with an adhesive layer. As a constituent material of the polarizing plate, a retardation film having a retardation of lambda/4 or lambda/2 can be used.
Examples
The present invention will be specifically described below based on examples.
< production of acrylic Polymer >
[ example 1]
Nitrogen gas was introduced into a reaction apparatus equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen introduction tube, thereby replacing the air in the reaction apparatus with nitrogen gas. Then, 100 parts by weight of butyl acrylate, 0.2 parts by weight of 8-hydroxyoctyl acrylate, and 60 parts by weight of a solvent (ethyl acetate) were added to the reaction apparatus. Then, 0.1 part by weight of azobisisobutyronitrile as a polymerization initiator was added dropwise over 2 hours, and reacted at 65 ℃ for 6 hours to obtain acrylic polymer solution 1 having a weight average molecular weight of 100 ten thousand or more used in example 1. A part of the acrylic polymer was used as a sample for measuring an acid value described later.
Examples 2 to 5 and comparative examples 1 to 3
Acrylic polymer solutions used in examples 2 to 5 and comparative examples 1 to 3 were obtained in the same manner as in the acrylic polymer solution 1 used in example 1, except that the compositions of the respective monomers were adjusted as in the groups (1) and (2) in table 1. Although the measurement results are not particularly shown, the weight average molecular weight of the acrylic polymer contained in the acrylic polymer solutions of examples 2 to 5 and comparative examples 1 to 3 is 100 ten thousand or more.
< production of adhesive composition, adhesive layer and adhesive film >
[ example 1]
To the acrylic polymer solution 1 of example 1 prepared as described above, 0.2 parts by weight of Coronate L (コロネート L) (a Trimethylolpropane (TMP) adduct of a Toluene Diisocyanate (TDI) compound) and 0.05 parts by weight of KBM-403 (3-glycidoxypropyltrimethoxysilane) were added and mixed with stirring to obtain an adhesive composition of example 1. The adhesive composition was applied to a release film made of a polyethylene terephthalate (PET) film coated with a silicone resin, dried at 90 ℃ to remove the solvent, and then cured at 23 ℃ and 50% RH for 7 days, thereby obtaining an adhesive film of example 1 having an adhesive layer of 25 μm thickness formed by crosslinking the adhesive composition on one surface of the release film.
Examples 2 to 5 and comparative examples 1 to 3
Adhesive films of examples 2 to 5 and comparative examples 1 to 3 were obtained in the same manner as in the adhesive film of example 1, except that the additive composition was adjusted as in the group (3) and the group (4) in table 1.
TABLE 1
In table 1, the values in parentheses represent the values of parts by weight of groups (2) to (4) obtained by setting the total weight of group (1) to 100 parts by weight, and are added as the ratio of groups (2) to (4).
In addition, compound names corresponding to abbreviations of the respective components used in table 1 are shown in table 2. Furthermore, Coronate (コロネート, registered trademark) L is a trade name of Nippon polyurethane Industrial Co., Ltd, D-110N is a trade name of Mitsui chemical Co., Ltd, and KBM-403 and KBM-803 are trade names of shin-Etsu chemical Co., Ltd. TDI refers to phenylene diisocyanate, TMP refers to trimethylolpropane, and XDI refers to xylylene diisocyanate. In tables 1 and 2, the copolymerizable vinyl monomer having a carboxyl group and the copolymerizable vinyl monomer having a hydroxyl group are shown in group (2).
TABLE 2
Figure BDA0000717805580000131
< test methods and evaluations >
The release film (silicone resin-coated PET film) was peeled off from the adhesive films of examples 1 to 5 and comparative examples 1 to 3 to expose the adhesive layer, and the adhesive layer was transferred to one surface of the polarizing plate (film).
< method for measuring adhesion >
An adhesive film (optical film with an adhesive layer) as a sample was obtained by transferring an adhesive layer having a thickness of 25 μm to one surface of a polarizing plate (film) having a thickness of 180 μm.
The obtained adhesive film was bonded to a non-tin surface of alkali-free glass cleaned with acetone by a pressure roller, and after autoclave treatment at 50 ℃ for 0.5MPa × 20 minutes, the pressure roller was returned to an environment of 23 ℃ × 50% RH for 1 hour. The peel strength of the adhesive film after that was measured by a tensile tester in accordance with JIS Z0237 "test method for adhesive tape and adhesive sheet", and the peel strength when peeled in the 180 ° direction at a speed of 300mm/min was taken as the adhesive force (N/25mm) of the adhesive layer of the adhesive film.
< method for measuring acid value >
The acid value of the acrylic polymer was determined as follows: the sample was dissolved in a solvent (a solvent in which diethyl ether and ethanol were mixed AT a volume ratio of 2: 1), and subjected to potentiometric titration with a potassium hydroxide ethanol solution having a concentration of about 0.1mol/L using a potentiometric automatic titrator (AT-610, manufactured by Kyoto electronics industries, Ltd.), and the amount of the potassium hydroxide ethanol solution required for neutralizing the sample was measured. Then, the acid value was determined by the following equation.
Acid value (B × f × 5.611)/S
Amount of 0.1mol/L ethanol solution of potassium hydroxide (mL) used in titration
Coefficient of potassium hydroxide ethanol solution (factor) of 0.1mol/L
Mass (g) of solid content of sample
< method for measuring gel fraction >
The mass of the test sample after aging and before the polarizing plate was attached was measured accurately, and the test sample was immersed in toluene for 24 hours and then filtered through a 200-mesh wire mesh. Then, after drying the filtrate at 100 ℃ for 1 hour, the mass of the residue was accurately measured, and the gel fraction of the binder layer (crosslinked binder) was calculated according to the following formula.
Gel fraction (%) — mass of insoluble fraction (g)/mass of binder (g) × 100
< method for testing durability >
A 10cm square adhesive film prepared in the same manner as in the case of measuring the adhesive force was bonded to the non-tin surface of the alkali-free glass in the same manner to prepare a sample, the sample was left in a predetermined environment (a dry environment at 80 ℃ or an environment at 60 ℃ x 90% RH) for 250 hours, and then taken out to an environment at 23 ℃ x 50% RH, and the state of the adhesive film after 1 hour was visually observed to determine the durability.
○ the adhesive film showed no peeling or foaming at all.
△ A portion of the adhesive film peeled off and foamed.
X: peeling and foaming occurred in the entirety of the adhesive film.
< method for testing reworkability >
A 10cm square adhesive film prepared in the same manner as in the measurement of adhesive force was bonded to the non-tin surface of alkali-free glass in the same manner to prepare a sample, the sample was left at 70 ℃ for 10 days, and then taken out to 23 ℃ for 1 hour, and the adhesive force of the adhesive film after leaving was measured to determine reworkability.
○, the adhesive force is 1.5-10N/25 mm after being multiplied by 70 ℃ for 10 days.
△ the cohesive force after 70 ℃ for 10 days is more than 10N/25mm but less than 20N/25 mm.
X: the adhesive force after 70 ℃ for 10 days is more than 20N/25mm (cannot be peeled off).
The evaluation results are shown in table 3. With respect to the acid value, it was confirmed that: the acid value of the acrylic polymer of examples 1 to 5 and comparative examples 2 and 3, which do not have a carboxyl group-containing copolymerizable vinyl monomer, is 0.1 or less, and the acid value of the acrylic polymer of comparative example 1, which has a carboxyl group-containing copolymerizable vinyl monomer, is greater than 0.1.
TABLE 3
Figure BDA0000717805580000151
In the adhesive films of examples 1 to 5, the adhesive force of the adhesive layer having a thickness of 25 μm was in the range of 1.5 to 6.0N/25mm, and the gel fraction of the crosslinked adhesive layer was 40 to 75%, and the adhesive film was excellent in adhesiveness and durability. Further, the adhesive strength after bonding to an adherend at 70 ℃ for 10 days is in the range of 1.5 to 10N/25mm, and therefore, the reworkability is also excellent. That is, the adhesive films of examples 1 to 5 can satisfy the required requirements and overcome the problems of the prior art.
The adhesive film of comparative example 1 was excellent in adhesive strength of an adhesive layer having a thickness of 25 μm and poor in durability and reworkability under an environment of 60 ℃ x 90% RH, probably because it contained no butylacrylate as the (meth) acrylate monomer, contained a carboxyl group-containing copolymerizable vinyl monomer as the functional group-containing monomer, and had a high gel fraction.
The adhesive film of comparative example 2 is inferior in durability in an environment of 60 ℃ x 90% RH, and also slightly inferior in durability and reworkability in a dry environment of 80 ℃ because the gel fraction is high because the amount of the hydroxyl group-containing copolymerizable vinyl monomer blended in the adhesive composition is too large.
The adhesive film of comparative example 3, which had neither a carboxyl group-containing copolymerizable vinyl monomer nor a hydroxyl group-containing copolymerizable vinyl monomer in the adhesive composition, had an acrylic polymer that was not crosslinked and had a gel fraction of 0, and the adhesive layer of 25 μm in thickness had very strong adhesion. As a result, the durability and reworkability are poor.
Thus, the adhesive films of comparative examples 1 to 3 could not satisfy the requirements proposed in the prior art and overcome the problems of the prior art.

Claims (9)

1. An adhesive layer obtained by crosslinking an adhesive composition containing an acrylic polymer, (C) a crosslinking agent and (D) a silane coupling agent,
the acrylic polymer is a copolymer having an acid value of 0.1 or less and a weight average molecular weight of 100 ten thousand or more,
the copolymer is obtained by copolymerizing 0.1-3.5 parts by weight of (B) hydroxyl group-containing copolymerizable vinyl monomer with respect to 100 parts by weight of (A) (methyl) acrylic ester monomer in total in a manner that carboxyl group-containing copolymerizable vinyl monomer is not contained, wherein in 100 parts by weight of (A) (methyl) acrylic ester monomer in total, the total of at least one or more alkyl (methyl) acrylate monomers with alkyl group having carbon atoms of C1-C14 is 80-95 parts by weight, the total of at least one or more aryl group-containing (methyl) acrylic ester monomers is 5-20 parts by weight,
butyl acrylate is contained in a proportion of at least 30 parts by weight or more based on 100 parts by weight in total of the (meth) acrylic ester monomer (A),
the adhesive composition contains 0.01 to 0.8 parts by weight of an isocyanate compound as the crosslinking agent (C) and 0.01 to 0.5 parts by weight of the silane coupling agent (D) per 100 parts by weight of the (meth) acrylate monomer (A),
the isocyanate compound is a trimethylolpropane adduct of toluene diisocyanate,
the gel fraction of the adhesive layer after crosslinking is more than 40% and less than 75%, the thickness of the adhesive layer is 1-25 μm, the adhesive force of the adhesive layer with the thickness of 25 μm is 1.5-6.0N/25 mm,
the aging treatment is already performed before the adhesive film on which the adhesive layer is formed is bonded to the adherend, and after the adhesive film on which the adhesive layer is formed is bonded to the adherend, the aging treatment is not necessary.
2. The adhesive layer of claim 1,
the hydroxyl group-containing copolymerizable vinyl monomer (B) in the adhesive composition is at least one selected from the group consisting of 8-hydroxyoctyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate.
3. The adhesive layer of claim 1 or 2,
the adhesive layer has an adhesive strength of 1.5 to 10N/25mm at 70 ℃ for 10 days after being bonded to an adherend.
4. An adhesive film comprising the adhesive layer according to any one of claims 1 to 3 formed on one surface of a release film, and having a structure of release film/adhesive layer/release film.
5. An adhesive film comprising a substrate and an adhesive layer according to any one of claims 1 to 3 laminated on one surface of the substrate.
6. An adhesive film for bonding a polarizing plate and a display panel, which comprises the adhesive film according to claim 4.
7. A polarizing plate having an adhesive layer, which comprises the adhesive film according to claim 4.
8. A polarizing plate with an adhesive layer, which comprises the adhesive film according to claim 4 and a retardation film having a retardation of λ/4 or λ/2 as a constituent material.
9. An optical film having an adhesive layer, wherein the adhesive layer according to any one of claims 1 to 3 is laminated on at least one surface of the optical film.
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