CN104250524B - Adhesive composition, adhesive and adhesive sheet - Google Patents

Adhesive composition, adhesive and adhesive sheet Download PDF

Info

Publication number
CN104250524B
CN104250524B CN201410301348.4A CN201410301348A CN104250524B CN 104250524 B CN104250524 B CN 104250524B CN 201410301348 A CN201410301348 A CN 201410301348A CN 104250524 B CN104250524 B CN 104250524B
Authority
CN
China
Prior art keywords
adhesive
meth
acrylate
monomer
mass
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201410301348.4A
Other languages
Chinese (zh)
Other versions
CN104250524A (en
Inventor
又野仁
荒井隆行
所司悟
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lintec Corp
Original Assignee
Lintec Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Lintec Corp filed Critical Lintec Corp
Publication of CN104250524A publication Critical patent/CN104250524A/en
Application granted granted Critical
Publication of CN104250524B publication Critical patent/CN104250524B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
    • C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • 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
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • 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
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention provides an adhesive composition, an adhesive and an adhesive sheet which do not bring adverse effect to an adherend such as a transparent conductive film and have excellent durability. In order to solve the above problems, an adhesive composition is provided which comprises (meth) acrylate polymer (a), isocyanate-based crosslinking agent (B), silane coupling agent (C) having mercapto group, and active energy ray-curable component (D), wherein the (meth) acrylate polymer (a) has a weight average molecular weight of 100 to 250 ten thousand, and contains, as monomer units constituting the polymer, a monomer having hydroxyl group, a monomer having aromatic ring, and a monomer having carboxyl group; the (meth) acrylate polymer (A) contains, as monomer units constituting the polymer, 1 to 5 mass% of a monomer having a hydroxyl group, 5 to 30 mass% of a monomer having an aromatic ring, and 0.1 to 0.8 mass% of a monomer having a carboxyl group.

Description

Adhesive composition, adhesive and adhesive sheet
Technical Field
The present invention relates to an adhesive composition, an adhesive (a material for curing the adhesive composition), and an adhesive sheet, and particularly relates to an adhesive composition, an adhesive, and an adhesive sheet suitable for use as an optical member such as a polarizing plate.
Background
In recent years, a touch panel that serves both as a display device and an input device has been widely used in various electronic devices. The touch panel is mainly classified into a resistive type, a capacitive type, an optical type and an ultrasonic type, the resistive type touch panel includes an analog resistive type and a matrix resistive type, and the capacitive type touch panel includes a surface type and a projection type.
Recently, a projected capacitive touch panel is often used as a touch panel of a mobile electronic device such as a smart phone or a tablet terminal. As a projection-type capacitive touch panel of the mobile electronic device, for example, a touch panel in which a liquid crystal display device (LCD), an adhesive layer, a transparent conductive film (tin-doped indium oxide: ITO), a glass substrate, a transparent conductive film (ITO), and a protective layer such as tempered glass are laminated in this order from bottom to top has been proposed.
As an optical member constituting the liquid crystal display device, a liquid crystal cell is generally used. In general, a liquid crystal cell is a cell in which alignment layers of two transparent electrode substrates on which the alignment layers are formed are disposed so as to form a predetermined space therebetween via a spacer sheet (スペーサ), and the periphery of the liquid crystal cell is sealed, and a liquid crystal material is sandwiched between the two transparent electrode substrates. Generally, polarizers are bonded to the outer sides of two transparent electrode substrates in a liquid crystal cell with an adhesive.
Here, in the configuration in which the polarizing plate of the liquid crystal display device is bonded to the transparent conductive film (ITO) via the adhesive layer as described above, the adhesive is in direct contact with the ITO. Therefore, there is a problem that ITO is corroded or the resistance value of ITO is changed due to an adhesive containing a large amount of carboxyl groups as an acid component.
As an optical adhesive, for example, an adhesive shown in patent document 1 is known. The adhesive comprises a copolymer (wherein the copolymer contains a hydroxyl group but does not contain a carboxyl group and has a weight-average molecular weight of 70 to 120 ten thousand) composed of 50 to 90 mass% of an alkyl ester monomer having 4 to 12 carbon atoms of (meth) acrylic acid, 3 to 10 mass% of an alicyclic alkyl ester monomer of (meth) acrylic acid, 0.1 to 1.0 mass% of a hydroxyalkyl ester monomer of (meth) acrylic acid, and 3 to 10 mass% of an alkyl ester monomer having 1 to 3 carbon atoms of (meth) acrylic acid (total 100 mass%), a crosslinking agent (0.02 to 1 part by mass per 100 parts by mass of the copolymer), and a crosslinking assistant (0.5 to 5.0 parts by mass per 100 parts by mass of the copolymer). Since this adhesive does not contain a carboxyl group as an acid component, the above problem is less likely to occur.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2012-001647
Disclosure of Invention
Technical problem to be solved
On the other hand, with the recent thinning of mobile electronic devices, the polarizing plate as a constituent member also starts to be thinned. Specifically, a polarizing plate having a reduced thickness of a protective film holding polyvinyl alcohol as polarizers on both sides is used. In the polarizing plate, the protective film has poor ability to prevent the polarizer from thermal shrinkage, and therefore the thermal shrinkage tends to be larger than before. As a material of the protective film, an optically functional film which easily generates outgas such as cycloolefin polymer (COP) is used instead of cellulose triacetate. Therefore, the adhesives used for these applications are required to have higher reliability (durability) than ever before.
However, when the adhesive of patent document 1 is used for the polarizing plate as described above, the durability is insufficient, and the adhesive may float or peel under high temperature conditions or wet heat conditions.
The present invention has been made in view of such a situation, and an object thereof is to provide an adhesive composition, an adhesive, and an adhesive sheet which do not adversely affect an adherend such as a transparent conductive film and which are excellent in durability.
(II) technical scheme
In order to achieve the above object, the present invention provides an adhesive composition comprising a (meth) acrylate polymer (a) having a weight average molecular weight of 100 to 250 ten thousand, a monomer having a hydroxyl group, a monomer having an aromatic ring, and a monomer having a carboxyl group as monomer units constituting the polymer; the (meth) acrylate polymer (a) contains, as monomer units constituting the polymer, 1 to 5 mass% of the monomer having a hydroxyl group, 5 to 30 mass% of the monomer having an aromatic ring, and 0.1 to 0.8 mass% of the monomer having a carboxyl group (invention 1).
The adhesive obtained by crosslinking the adhesive composition according to the invention (invention 1) has excellent durability because the (meth) acrylate polymer (a) contains predetermined amounts of the monomer having a hydroxyl group, the monomer having an aromatic ring, and the monomer having a carboxyl group as monomer units constituting the polymer, and the silane coupling agent (C) having a mercapto group exerts an excellent coupling effect, and the active energy ray-curable component (D) is cured and entangled with the crosslinked product of the (meth) acrylate polymer (a). In addition, since the amount of carboxyl groups contained in the (meth) acrylate polymer (a) is suppressed to a low level, defects of an adherend such as a transparent conductive film due to an acid can be suppressed.
In the above invention (invention 1), the isocyanate-based crosslinking agent (B) is preferably trimethylolpropane-modified tolylene diisocyanate (invention 2).
In the above-mentioned invention (invention 1, invention 2), the content of the isocyanate-based crosslinking agent (B) in the adhesive composition is preferably 0.01 to 1 part by mass relative to 100 parts by mass of the (meth) acrylate polymer (a) (invention 3).
In the above-mentioned inventions (inventions 1 to 3), the content of the silane coupling agent (C) in the adhesive composition is preferably 0.01 to 0.5 parts by mass relative to 100 parts by mass of the (meth) acrylate polymer (a) (invention 4).
In the above inventions (inventions 1 to 4), the aromatic ring-containing monomer is preferably 2-phenylethyl (meth) acrylate (invention 5).
In the above inventions (inventions 1 to 5), the active energy ray-curable component (D) is preferably a polyfunctional acrylate monomer having a molecular weight of less than 1000 (invention 6).
In the invention (invention 6) above, the polyfunctional acrylate monomer preferably has a cyclic structure (invention 7).
In the above-mentioned inventions (inventions 1 to 7), the content of the active energy ray-curable component (D) in the adhesive composition is preferably 1 to 50 parts by mass relative to 100 parts by mass of the (meth) acrylate polymer (a) (invention 8).
Secondly, the present invention provides an adhesive obtained by curing the adhesive composition (invention 1 to invention 8) by irradiation with an active energy ray (invention 9).
In the above invention (invention 9), the gel fraction is preferably 55% to 85% (invention 10).
In the above inventions (inventions 9 and 10), the storage modulus at 23 ℃ is preferably 0.15 to 0.3MPa, and the storage modulus at 80 ℃ is preferably 0.05 to 0.2MPa (invention 11).
The third aspect of the present invention provides an adhesive sheet comprising a base material and an adhesive layer, wherein the adhesive layer contains the adhesive (aspects 9 to 11) (aspect 12).
In the above invention (invention 12), the base material is preferably an optical member (invention 13).
In the above invention (invention 13), the optical member is preferably a polarizing plate (invention 14).
The fourth aspect of the present invention provides an adhesive sheet comprising two release sheets and an adhesive layer sandwiched between the release sheets so as to be in contact with release surfaces of the two release sheets, wherein the adhesive layer contains the adhesive (aspects 9 to 11) (aspect 15).
In the above-described inventions (inventions 12 to 15), when the laminate of the adhesive layer and the transparent conductive film is subjected to a moist heat acceleration test in which the laminate is exposed to an atmosphere of 65 ℃ and 95% RH for 500 hours, the rate of increase in the resistance value of the transparent conductive film calculated by the following equation is preferably 15% or less (invention 16).
A resistance value increase rate (%) { (R-R)0)/R0}×100
(in the formula, R0The resistance value is the initial resistance value before the moist heat acceleration test, and R is the resistance value after the moist heat acceleration test. )
(III) advantageous effects
The adhesive composition, the adhesive and the adhesive sheet according to the present invention have excellent durability without adversely affecting an adherend such as a transparent conductive film.
Drawings
Fig. 1 is a sectional view of an adhesive sheet according to embodiment 1 of the present invention.
Fig. 2 is a sectional view of an adhesive sheet according to embodiment 2 of the present invention.
Fig. 3 is a sectional view of the resistance value measurement sample produced in test example 3.
Fig. 4 is a perspective view illustrating a test method of test example 3.
Detailed Description
Hereinafter, embodiments of the present invention will be described.
[ adhesive composition ]
The adhesive composition according to the present embodiment (hereinafter referred to as "adhesive composition P") contains a (meth) acrylate polymer (a) having a weight average molecular weight of 100 to 250 ten thousand, a monomer having a hydroxyl group (hydroxyl group-containing monomer), a monomer having an aromatic ring (aromatic ring-containing monomer), and a monomer having a carboxyl group (carboxyl group-containing monomer) as monomer units constituting the polymer, preferably further contains a photopolymerization initiator (E), an isocyanate-based crosslinking agent (B), a silane coupling agent having a mercapto group (C), and an active energy ray-curable component (D). The (meth) acrylate polymer (A) contains 1 to 5% by mass of a hydroxyl group-containing monomer, 5 to 30% by mass of an aromatic ring-containing monomer, and 0.1 to 0.8% by mass of a carboxyl group-containing monomer as a monomer unit constituting the polymer. In the present specification, the term (meth) acrylate refers to both acrylates and methacrylates. Other similar terms are also used. In addition, the term "copolymer" is also included in the term "polymer".
In the adhesive composition P, the (meth) acrylate polymer (a) contains a hydroxyl group-containing monomer, an aromatic ring-containing monomer and a carboxyl group-containing monomer in predetermined amounts as monomer units constituting the polymer, and the adhesive obtained by curing the adhesive composition P has both cohesive force and stress relaxation properties, and is excellent in durability.
Further, when the adhesive composition P is cured, the mercapto group of the silane coupling agent (C) easily forms a thiourethane bond with the isocyanate group of the isocyanate-based crosslinking agent (B), and the other isocyanate group of the isocyanate-based crosslinking agent (B) reacts with the hydroxyl group of the (meth) acrylate polymer (a) to crosslink the (meth) acrylate polymer (a) and form a 1 st three-dimensional network structure. Further, it is presumed that the alkoxysilyl group of the silane coupling agent (C) is suspended from the (meth) acrylate polymer (a) at an appropriate distance from the (meth) acrylate polymer (a). This exerts an excellent coupling effect. On the other hand, the plurality of active energy ray-curable components (D) are bonded to each other to form a 2 nd three-dimensional network structure. It is presumed that the 1 st three-dimensional network structure and the 2 nd three-dimensional network structure are intertwined with each other to form an integral three-dimensional network structure (hereinafter, this structure is referred to as "structure X"). By this structure X and the coupling effect, the obtained adhesive is excellent in adhesion durability also under high temperature conditions or under wet heat conditions.
In addition, in the adhesive composition P, since the content of the carboxyl group-containing monomer contained as a monomer unit in the (meth) acrylate polymer (a) is suppressed to a low level, it is possible to suppress the problems caused by an acid to be applied to the obtained adhesive, for example, in the case of a transparent conductive film, a metal film, or the like, these problems caused by an acid can be suppressed. In particular, when the object to be attached is a transparent conductive film, corrosion of the transparent conductive film and change in the resistance value of the transparent conductive film can be suppressed.
(1) (meth) acrylate ester Polymer (A)
The (meth) acrylate polymer (A) is preferably an alkyl (meth) acrylate having 1 to 20 carbon atoms and containing an alkyl group, in addition to the hydroxyl group-containing monomer, aromatic ring-containing monomer, and carboxyl group-containing monomer, as a monomer unit constituting the polymer, and is particularly preferably contained as a main component. Further, other monomers may be contained as necessary.
The (meth) acrylate polymer (A) can exhibit excellent adhesion by containing an alkyl (meth) acrylate having 1 to 20 carbon atoms in the alkyl group as a monomer unit constituting the polymer. Examples of the alkyl (meth) acrylate having an alkyl group with 1 to 20 carbon atoms include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-decyl (meth) acrylate, n-dodecyl (meth) acrylate, myristyl (meth) acrylate, palmityl (meth) acrylate, and stearyl (meth) acrylate. Among these, from the viewpoint of further improving the adhesiveness, a (meth) acrylate in which the alkyl group has 1 to 8 carbon atoms is preferable, and methyl (meth) acrylate and n-butyl (meth) acrylate are particularly preferable. These may be used alone or in combination of two or more.
The (meth) acrylate polymer (a) preferably contains, as a monomer unit constituting the polymer, 50 to 93.9 mass% of an alkyl (meth) acrylate ester having an alkyl group with 1 to 20 carbon atoms, particularly preferably 64.2 to 93 mass%, and more preferably 80 to 90 mass%. In addition, if the alkyl (meth) acrylate is contained in an amount of 50% by mass or more, excellent adhesiveness can be imparted to the (meth) acrylate polymer (a). By containing 93.9 mass% or less of the alkyl (meth) acrylate, other monomer components can be introduced into the (meth) acrylate polymer (a) in a preferred amount.
The (meth) acrylate polymer (a) contains a hydroxyl group-containing monomer as a monomer unit constituting the polymer. The hydroxyl group is highly reactive with the isocyanate group of the isocyanate-based crosslinking agent (B), and the (meth) acrylate polymer (a) is crosslinked by the isocyanate-based crosslinking agent (B) through the reaction thereof. The crosslinked structure provides an adhesive having excellent durability.
Examples of the hydroxyl group-containing monomer include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. Among them, 2-hydroxyethyl (meth) acrylate or 4-hydroxybutyl (meth) acrylate is preferable from the viewpoint of reactivity with the isocyanate-based crosslinking agent (B). These may be used alone or in combination of two or more.
The (meth) acrylate polymer (a) contains 1 to 5 mass%, preferably 2 to 4 mass%, of a hydroxyl group-containing monomer as a monomer unit constituting the polymer. When the content of the hydroxyl group-containing monomer is within the above range, the crosslinked structure formed becomes good, and the resulting adhesive has excellent durability. If the content of the hydroxyl group-containing monomer is less than 1% by mass, the crosslinking point is too small, the cohesive force is reduced, and the resulting adhesive cannot exhibit excellent durability. On the other hand, if the content of the hydroxyl group-containing monomer exceeds 5 mass%, the crosslinking points become too large, the resulting adhesive becomes not soft, and the stress relaxation property is lowered, whereby the adhesive cannot cope with shrinkage of the substrate, and the durability is deteriorated.
The (meth) acrylate polymer (a) contains an aromatic ring-containing monomer as a monomer unit constituting the polymer. Thus, the (meth) acrylate polymer (a) has an appropriate hardness, and the obtained adhesive is easy to have both an adhesive force and stress relaxation properties, and is excellent in durability.
Examples of the aromatic ring-containing monomer include phenyl (meth) acrylate, 2-phenylethyl (meth) acrylate, benzyl (meth) acrylate, naphthyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxybutyl (meth) acrylate, ethoxylated o-phenylphenol acrylate, phenoxydiethylene glycol (meth) acrylate, ethylene oxide-modified cresol (meth) acrylate, Ethylene Oxide (EO) -modified nonylphenol (meth) acrylate, and the like, and among them, 2-phenylethyl (meth) acrylate is preferable from the viewpoint of improving cohesive force. These may be used alone or in combination of two or more.
The (meth) acrylate polymer (a) contains 5 to 30 mass%, preferably 7 to 25 mass%, and particularly preferably 10 to 20 mass% of an aromatic ring-containing monomer as a monomer unit constituting the polymer. When the content of the aromatic ring-containing monomer is within the above range, the obtained adhesive has excellent stress relaxation property and excellent durability. If the content of the aromatic ring-containing monomer is less than 5% by mass, the durability of the resulting adhesive is deteriorated. On the other hand, if the content of the aromatic ring-containing monomer exceeds 30 mass%, the amount of other components to be blended decreases, and the durability of the resulting adhesive deteriorates.
The (meth) acrylate polymer (a) contains a carboxyl group-containing monomer as a monomer unit constituting the polymer. The carboxyl group can promote the crosslinking reaction between the hydroxyl group in the (meth) acrylate polymer (A) and the isocyanate crosslinking agent (B), and the carboxyl group itself also undergoes the crosslinking reaction with the isocyanate crosslinking agent (B). Thus, the obtained adhesive has an appropriate degree of crosslinking, and the degree of crosslinking is equalized among the (meth) acrylate polymers (a), thereby having excellent durability.
The (meth) acrylate polymer (a) contains a carboxyl group-containing monomer in an amount of 0.1 to 0.8 mass%, preferably 0.1 to 0.5 mass%, and particularly preferably 0.1 to 0.3 mass%, as a monomer unit constituting the polymer. When the carboxyl group-containing monomer is in the above range, the resulting adhesive has excellent durability. If the content of the carboxyl group-containing monomer is less than 0.1 mass%, the durability of the resulting adhesive is deteriorated. On the other hand, if the content of the carboxyl group-containing monomer exceeds 0.8 mass%, the transparent conductive film or the like is corroded and the resistance value of the transparent conductive film is largely changed when the adhesive to be obtained is a transparent conductive film or the like.
As the other monomer, a monomer containing no functional group reactive with the isocyanate-based crosslinking agent (B) is preferable, even if it does not inhibit the reaction between the hydroxyl group of the hydroxyl-containing monomer and the carboxyl group of the carboxyl-containing monomer with the isocyanate-based crosslinking agent (B). Examples of such other monomers include alkoxyalkyl (meth) acrylates such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate; non-crosslinkable acrylamides such as acrylamide and methacrylamide; non-crosslinkable (meth) acrylic acid esters having a tertiary amino group such as N, N-dimethylaminoethyl (meth) acrylate and N, N-dimethylaminopropyl (meth) acrylate; vinyl acetate, and the like. These may be used alone or in combination of two or more.
The polymerization mode of the (meth) acrylate polymer (a) may be a random copolymer or a block copolymer.
The weight average molecular weight of the (meth) acrylate polymer (a) is 100 to 250 ten thousand, preferably 140 to 220 ten thousand, and particularly preferably 180 to 200 ten thousand. The weight average molecular weight in the present specification is a value in terms of polystyrene measured by a Gel Permeation Chromatography (GPC) method.
If the weight average molecular weight of the (meth) acrylate polymer (a) is less than 100 ten thousand, the durability of the resulting adhesive is deteriorated. When the weight average molecular weight of the (meth) acrylate polymer (A) exceeds 250 ten thousand, the processability of the resulting adhesive is deteriorated.
In the adhesive composition P, the (meth) acrylate polymer (a) may be used alone or in combination of two or more. The adhesive composition P may further contain a (meth) acrylate polymer containing no hydroxyl group-containing monomer, aromatic ring-containing monomer, or carboxyl group-containing monomer as a constituent monomer unit.
(2) Isocyanate crosslinking agent (B)
The isocyanate-based crosslinking agent (B) has an advantage of excellent reactivity with a hydroxyl group of the (meth) acrylate polymer (a) and reactivity with a mercapto group of the silane coupling agent (C).
The isocyanate-based crosslinking agent (B) is a crosslinking agent containing at least a polyisocyanate compound. Examples of the polyisocyanate compound include aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate; alicyclic polyisocyanates such as isophorone diisocyanate and hydrogenated diphenylmethane diisocyanate; and biuret and isocyanurate compounds thereof, and further includes adduct compounds with reactants containing low molecular active hydrogen compounds such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, castor oil, etc., among which trimethylolpropane-modified aromatic polyisocyanate is preferable, and trimethylolpropane-modified tolylene diisocyanate is particularly preferable from the viewpoint of durability and processability in the case of using the resulting product for a polarizing plate. The isocyanate-based crosslinking agent (B) may be used alone or in combination of two or more.
The content of the isocyanate-based crosslinking agent (B) in the adhesive composition P is preferably 0.01 to 1 part by mass, particularly preferably 0.05 to 0.5 part by mass, and more preferably 0.1 to 0.3 part by mass, based on 100 parts by mass of the (meth) acrylate polymer (a). When the content of the isocyanate-based crosslinking agent (B) is in the above range, a crosslinked structure having excellent stress relaxation property and durability can be formed in the obtained adhesive.
(3) Silane coupling agent (C)
The silane coupling agent (C) in the present embodiment has a mercapto group. The mercapto group is easily reacted with the isocyanate group of the isocyanate-based crosslinking agent (B). As described above, in the adhesive for curing the adhesive composition P, it is presumed that the alkoxysilyl group of the silane coupling agent (C) is suspended on the (meth) acrylate polymer (a) with an appropriate distance from the (meth) acrylate polymer (a), that is, with a distance between a plurality of isocyanate groups in the isocyanate-based crosslinking agent (B). As described above, the alkoxysilyl group is present at an appropriate distance from the (crosslinked) (meth) acrylate polymer (a), and an excellent coupling effect can be exhibited, whereby the obtained adhesive is excellent in adhesiveness and excellent in adhesion durability even under high-temperature conditions and moist-heat conditions. This effect is particularly remarkable when the target to which the adhesive is applied is an inorganic material such as glass or metal.
The silane coupling agent (C) is an organosilicon compound having at least one mercapto group and at least one alkoxysilyl group in the molecule, and is preferably one having good compatibility with the adhesive component and light transmittance, for example, substantially transparent.
Specific examples of the silane coupling agent (C) include mercapto group-containing low-molecular-weight silane coupling agents such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and 3-mercaptopropyldimethoxymethylsilane; and mercapto group-containing oligomer type silane coupling agents such as cocondensates of mercapto group-containing silane compounds such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and 3-mercaptopropyldimethoxymethylsilane with alkyl group-containing silane compounds such as methyltriethoxysilane, ethyltriethoxysilane, methyltrimethoxysilane, and ethyltrimethoxysilane. Among these, a mercapto group-containing oligomer type silane coupling agent is preferable from the viewpoint of improving durability, and particularly, a cocondensate of a mercapto group-containing silane compound and an alkyl group-containing silane compound is preferable, and a cocondensate of 3-mercaptopropyltrimethoxysilane and methyltriethoxysilane is more preferable. These may be used alone or in combination of two or more.
The content of the silane coupling agent (C) in the adhesive composition P is preferably 0.01 to 0.5 parts by mass, and particularly preferably 0.1 to 0.4 parts by mass, based on 100 parts by mass of the (meth) acrylate polymer (a). If the content of the silane coupling agent (C) is less than 0.01 part by mass, the effect of the silane coupling agent (C) may be difficult to obtain. On the other hand, if the content of the silane coupling agent (C) exceeds 0.5 parts by mass, the reaction between the isocyanate-based crosslinking agent (B) and the (meth) acrylate polymer (a) may be inhibited.
(4) Active energy ray-curable component (D)
The active energy ray-curable component (D) is not particularly limited as long as it is a component that is cured by irradiation with an active energy ray so as not to impair the effects of the present invention, and may be any of a monomer, an oligomer, or a polymer, or a mixture of these. Among them, preferred are polyfunctional acrylate monomers having a molecular weight of less than 1000, which are excellent in compatibility with the (meth) acrylate polymer (a) and the like.
Examples of the polyfunctional acrylate monomer having a molecular weight of less than 1000 include 2-functional types such as 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, neopentyl glycol adipate di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, dicyclopentyl di (meth) acrylate, caprolactone-modified dicyclopentenyl di (meth) acrylate, ethylene oxide-modified phosphoric acid di (meth) acrylate, di (acryloyloxyethyl) isocyanurate, and allylated cyclohexyl di (meth) acrylate; 3-functional types such as trimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid-modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide-modified trimethylolpropane tri (meth) acrylate, and tris (acryloyloxyethyl) isocyanurate; 4-functional types such as diglycerin tetra (meth) acrylate and pentaerythritol tetra (meth) acrylate; 5-functional types such as propionic acid-modified dipentaerythritol penta (meth) acrylate; and 6-functional types such as dipentaerythritol hexa (meth) acrylate and caprolactone-modified dipentaerythritol hexa (meth) acrylate. These may be used alone or in combination of two or more.
Among the above-mentioned polyfunctional acrylate monomers, those having a cyclic structure in the skeleton are preferable because they are more excellent in durability. The cyclic structure may be a carbocyclic structure, a heterocyclic structure, a monocyclic structure, or a polycyclic structure. Examples of the polyfunctional acrylate monomer include those having an isocyanurate structure such as bis (acryloyloxyethyl) isocyanurate and tris (acryloyloxyethyl) isocyanurate, dimethylol dicyclopentane diacrylate, ethylene oxide-modified hexahydrophthalic acid diacrylate, tricyclodecane dimethanol acrylate, and adamantane diacrylate.
As the active energy ray-curable component (D), an active energy ray-curable acrylate oligomer can also be used. The acrylic oligomer preferably has a weight average molecular weight of 50,000 or less. Examples of the acrylate oligomer include polyester acrylates, epoxy acrylates, urethane acrylates, polyether acrylates, polybutadiene acrylates, and silicone acrylates.
Here, the polyester acrylate oligomer can be obtained, for example, by esterifying the hydroxyl groups of a polyester oligomer having hydroxyl groups at both ends, which is obtained by polycondensation of a polycarboxylic acid and a polyhydric alcohol, with (meth) acrylic acid; alternatively, the hydroxyl group at the end of an oligomer obtained by adding an alkylene oxide to a polycarboxylic acid may be esterified with (meth) acrylic acid. The epoxy acrylate oligomer can be obtained by, for example, reacting (meth) acrylic acid with an oxirane ring of a bisphenol epoxy resin or a novolak epoxy resin having a relatively low molecular weight and esterifying the resulting product. In addition, a carboxyl-modified epoxy acrylate oligomer obtained by partially modifying the epoxy acrylate oligomer with a dicarboxylic acid anhydride may be used. The urethane acrylate oligomer can be obtained, for example, by esterifying a urethane oligomer obtained by reacting a polyether polyol or a polyester polyol with a polyisocyanate with (meth) acrylic acid. The polyol acrylate oligomer can be obtained by esterifying the hydroxyl group of a polyether polyol with (meth) acrylic acid.
The weight average molecular weight of the acrylate oligomer is preferably 50,000 or less, particularly preferably 500 to 50,000, and more preferably 3,000 to 40,000. These acrylate oligomers may be used alone or in combination of two or more.
In addition, as the active energy ray-curable component (D), an adduct acrylate polymer in which a group having a (meth) acryloyl group is introduced into a side chain may be used. Such an addition acrylate polymer can be obtained by using a copolymer of a (meth) acrylate and a monomer having a crosslinkable functional group in the molecule, and reacting a compound having a (meth) acryloyl group and a group reactive with the crosslinkable functional group with a part of the crosslinkable functional group of the copolymer.
The (meth) acrylate is preferably an alkyl (meth) acrylate having 1 to 20 carbon atoms and containing an alkyl group, and examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, myristyl (meth) acrylate, palmityl (meth) acrylate, and stearyl (meth) acrylate. These may be used alone or in combination of two or more.
The monomer having a crosslinkable functional group in a molecule preferably contains at least one functional group selected from a hydroxyl group, a carboxyl group, an amino group and an amide group as a functional group. Examples of the monomer include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate; acrylamides such as acrylamide, methacrylamide, N-methylacrylamide, N-methylmethacrylamide, N-methylolacrylamide, and N-methylolmethacrylamide; monoalkylaminoalkyl (meth) acrylates such as monomethylaminoethyl (meth) acrylate, monoethylaminoethyl (meth) acrylate, monomethylaminopropyl (meth) acrylate, and monoethylaminopropyl (meth) acrylate; ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, and citraconic acid. These monomers may be used alone or in combination of two or more.
Examples of the compound having a group that reacts with a (meth) acryloyl group and a crosslinkable functional group include, preferred examples thereof include 2-methacryloyloxyethyl isocyanate, 2- (0- [ 1' -methylpropylamino ] carboxyamino) ethyl methacrylate, 2- [ (3, 5-dimethylpyrazole) carbonylamino ] ethyl methacrylate, 1- (bisacryloxymethyl) ethyl isocyanate, 2-acryloyloxyethyl succinate, 2-acryloyloxyethyl hexahydrophthalimide, omega-carboxy-polycaprolactone monoacrylate, monohydroxyethyl phthalate acrylate and 2-hydroxy-3-phenoxypropyl acrylate. These compounds may be used alone, or two or more of them may be used in combination.
The weight average molecular weight of the addition acrylic ester polymer is preferably about 30 to 200 ten thousand, and particularly preferably 50 to 85 ten thousand.
The active energy ray-curable component (D) may be used by selecting one from the above-mentioned polyfunctional acrylate monomers, acrylate oligomers and addition acrylic polymers, or may be used by combining two or more kinds thereof, or may be used by combining other active energy ray-curable components.
The content of the active energy ray-curable component (D) in the adhesive composition P is preferably 1 to 50 parts by mass, particularly preferably 2 to 20 parts by mass, and further preferably 3 to 10 parts by mass, based on 100 parts by mass of the (meth) acrylate polymer (a). It is presumed that the structure X can be formed well with an adhesive obtained from the adhesive composition P containing the active energy ray-curable component (D) within the above range. In particular, it is presumed that by setting the content of the active energy ray-curable component (D) to 3 to 10 parts by mass, the structure X can achieve both flexibility and cohesive force at a high level, and can be an adhesive having particularly excellent durability.
(5) Photopolymerization initiator (E)
When ultraviolet rays are used as the active energy rays to be irradiated to the adhesive composition P, the adhesive composition P preferably further contains a photopolymerization initiator (E). By containing the photopolymerization initiator (E) in this manner, the active energy ray-curable component (D) can be efficiently cured, and the polymerization curing time and the irradiation dose of the active energy ray can be reduced.
Examples of the photopolymerization initiator (E) include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2-dimethoxy-2-phenylacetophenone, 2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholin-propan-1-one, 4- (2-hydroxyethoxy) phenyl-2- (hydroxy-2-propyl) ketone, and the like, Benzophenone, p-phenylbenzophenone, 4' -diethylaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2, 4-dimethylthioxanthone, 2, 4-diethylthioxanthone, benzyldimethylketal, acetophenone dimethylketal, p-dimethylaminobenzoate, oligo [ 2-hydroxy-2-methyl-1 [4- (1-methylvinyl) phenyl ] acetone ], 2,4, 6-trimethylbenzoyl-diphenyl-phosphine oxide, and the like. These may be used alone or in combination of two or more.
The photopolymerization initiator (E) is preferably used in an amount in the range of 2 to 15 parts by mass, and particularly preferably 5 to 12 parts by mass, based on 100 parts by mass of the active energy ray-curable component (D).
(6) Various additives
The adhesive composition P may contain, as necessary, various additives commonly used in acrylic adhesives, for example, antistatic agents, tackifiers, antioxidants, ultraviolet absorbers, light stabilizers, softeners, fillers, and refractive index adjusting agents.
Specific examples of the antistatic agent include N-butyl-4-methylpyridinium hexafluorophosphate, N-hexyl-4-methylpyridinium hexafluorophosphate, N-butyl-2-hexylpyridinium perchlorate, potassium bis (fluorosulfonylimide) (KFSI), potassium bis (trifluoromethanesulfonylimide) (KTFSI), lithium bis (fluorosulfonylimide) (LiFSI), lithium bis (trifluoromethanesulfoniylimide) (LiTFSI), N-butyl-2-hexylpyridinium bis (trifluoromethanesulfonyl) imide, and the like. These antistatic agents may be used alone or in combination of two or more.
[ method for producing adhesive composition ]
The adhesive composition P can be produced by producing the (meth) acrylate polymer (a), mixing the obtained (meth) acrylate polymer (a) with the isocyanate-based crosslinking agent (B), the silane coupling agent (C), and the active energy ray-curable component (D), and adding the photopolymerization initiator (E), additives, and the like at an optional stage as needed.
The (meth) acrylate polymer (a) can be produced by polymerizing a mixture of monomer units constituting the polymer by a general radical polymerization method. The polymerization of the (meth) acrylate polymer (a) can be carried out by a solution polymerization method or the like using a polymerization initiator as needed. Examples of the polymerization solvent include ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, acetone, hexane, and methyl ethyl ketone, and two or more kinds thereof may be used simultaneously.
The polymerization initiator includes azo compounds, organic peroxides, and the like, and two or more kinds thereof may be used simultaneously. Examples of the azo compound include 2,2 ' -azobisisobutyronitrile, 2 ' -azobis (2-methylbutyronitrile), 1 ' -azobis (cyclohexane 1-carbonitrile), 2 ' -azobis (2, 4-dimethylvaleronitrile), 2 ' -azobis (2, 4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2 ' -azobis (2-methylpropionate), 4 ' -azobis (4-cyanovaleric acid), 2 ' -azobis (2-hydroxymethylpropionitrile), and 2,2 ' -azobis [ 2- (2-imidazolin-2-yl) propane ].
Examples of the organic peroxide include benzoyl peroxide, tert-butyl peroxybenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, bis (2-ethoxyethyl) peroxydicarbonate, tert-butyl peroxyneodecanoate, tert-butyl peroxypivalate, (3,5, 5-trimethylhexanoyl) peroxide, dipropyl peroxide, and diacetyl peroxide.
In the polymerization step, a chain transfer agent such as 2-mercaptoethanol is added to adjust the weight average molecular weight of the obtained polymer.
After the (meth) acrylate polymer (a) is obtained, an isocyanate-based crosslinking agent (B), a silane coupling agent (C), an active energy ray-curable component (D), and if necessary, a photopolymerization initiator (E), a diluting solvent, additives, and the like are added to a solution of the (meth) acrylate polymer (a) and sufficiently mixed to obtain an adhesive composition P (coating solution) diluted with a solvent.
Examples of the diluting solvent used for diluting the adhesive composition P to obtain a coating solution include aliphatic hydrocarbons such as hexane, heptane and cyclohexane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as dichloromethane and dichloroethane; alcohols such as methanol, ethanol, propanol, butanol, and 1-methoxy-2-propanol; ketones such as acetone, methyl ethyl ketone, 2-pentanone, isophorone, and cyclohexanone; esters of ethyl acetate, butyl acetate, and the like; and cellosolve solvents such as ethyl cellosolve.
The concentration and viscosity of the coating solution prepared in this manner are not particularly limited as long as the coating solution can be applied, and may be appropriately selected depending on the case. For example, the concentration of the adhesive composition P may be diluted to 10 to 40 mass%. In addition, when obtaining a coating solution, the addition of a diluting solvent or the like is not an essential condition, and the diluting solvent may not be added as long as the adhesive composition P has a viscosity capable of being coated. In this case, the adhesive composition P is a coating solution in which the polymerization solvent of the (meth) acrylate polymer (a) is directly used as a dilution solvent.
[ Adhesives ]
The adhesive according to the present embodiment is preferably obtained by applying and drying the adhesive composition P to a desired object, and then curing the adhesive composition P by irradiation with an active energy ray. After these treatments, a curing period of about 1 to 2 weeks may be set at normal temperature (e.g., 23 ℃ C., 50% RH) as necessary. When the curing period is required, an adhesive (layer) is formed after the curing period; when the curing period is not required, the adhesive (layer) is formed after the irradiation of the active energy ray.
The drying of the adhesive composition P may be performed by air drying, but is generally performed by heat treatment (preferably, hot air drying). When the heat treatment is performed, the heating temperature is preferably 50 to 150 ℃, and particularly preferably 70 to 120 ℃. The heating time is preferably 10 seconds to 10 minutes, and particularly preferably 50 seconds to 2 minutes.
As the active energy ray, ultraviolet rays, electron beams, or the like are generally used. The dose of the active energy ray varies depending on the kind of the energy ray, and for example, when ultraviolet rays are used, the dose is preferably 50mJ/cm2～1000mJ/cm2Particularly preferably 100mJ/cm2～500mJ/cm2. When an electron beam is used, it is preferably about 10 to 1000 krad.
By the above heat treatment (and curing), the (meth) acrylic ester polymer (a) is crosslinked by the isocyanate-based crosslinking agent (B) to form a 1 st three-dimensional network structure. Further, the mercapto group of the silane coupling agent (C) is likely to react with the isocyanate group of the isocyanate-based crosslinking agent (B), and it is presumed that the alkoxysilyl group of the silane coupling agent (C) is present at an appropriate distance from the (meth) acrylate polymer (a) and further from the three-dimensional network structure by the isocyanate-based crosslinking agent (B), and an excellent coupling effect is exhibited. On the other hand, the active energy ray-curable components (D) are bonded to each other by irradiation with an active energy ray to form a 2 nd three-dimensional network structure. It is presumed that the 2 nd three-dimensional network structure and the 1 st three-dimensional network structure are intertwined with each other to form the above-mentioned structure X. The adhesive having the structure X has appropriate adhesion and stress relaxation properties and has high cohesive force, and therefore has excellent durability.
The adhesive obtained by curing the adhesive composition P has an appropriate cohesive force due to the aromatic ring even when the 1 st three-dimensional network structure is in a relatively loose state. This improves stress relaxation property without reducing cohesive force, and therefore, the adhesive has high durability. Further, the excellent coupling effect obtained by the silane coupling agent (C) is excellent in adhesion to a glass surface or the like, and can exhibit excellent adhesion durability even under high temperature conditions or moist heat conditions. The adhesive can prevent/suppress the occurrence of floating, peeling, air bubbles, etc., even when left to stand for 250 hours under a high temperature condition of 85 ℃ or a wet heat condition of 60 ℃ and 90% RH, for example.
The gel fraction of the adhesive according to the present embodiment is preferably 55% to 85%, and particularly preferably 60% to 80%. If the gel fraction is less than 55%, the cohesive force of the adhesive is insufficient, and the durability and reworkability may be reduced. In particular, when the adhesive is used for a COP polarizing plate, sufficient adhesion durability may not be obtained at a high temperature. On the other hand, if the gel fraction exceeds 85%, the stress relaxation property becomes too low, and the durability may be reduced.
The storage modulus (G') at 23 ℃ of the adhesive of the present embodiment is preferably 0.15 to 0.3MPa, particularly preferably 0.18 to 0.28MPa, from the viewpoint of durability, and more preferably 0.20 to 0.26MPa, from the viewpoint of further improving the haze value. The storage modulus (G') at 80 ℃ is preferably 0.05MPa to 0.2MPa, particularly preferably 0.08MPa to 0.18MPa, from the viewpoint of durability, and more preferably 0.1MPa to 0.14MPa from the viewpoint of further improving the haze value. The storage modulus (G') is a value measured by the torsional shear method described later.
[ adhesive sheet ]
As shown in fig. 1, the adhesive sheet 1A according to embodiment 1 is composed of a release sheet 12, an adhesive layer 11 laminated on the release surface of the release sheet 12, and a base material 13 laminated on the adhesive layer 11, in this order from bottom to top.
As shown in fig. 2, the adhesive sheet 1B according to embodiment 2 is composed of two release sheets 12a and 12B and an adhesive layer 11 sandwiched between the two release sheets 12a and 12B so as to be in contact with the release surfaces of the two release sheets 12a and 12B. The release surface of the release sheet in the present specification means a surface having releasability in the release sheet, and includes any one of a surface subjected to a release treatment and a surface showing releasability even if the release treatment is not performed.
In both adhesive sheets 1A and 1B, adhesive layer 11 contains an adhesive obtained by curing adhesive composition P.
The thickness of the adhesive layer 11 is suitably determined depending on the purpose of use of the adhesive sheets 1A and 1B, but is usually in the range of 5 μm to 100 μm, preferably 10 μm to 60 μm, and for example, in the case of using as an optical member, particularly as an adhesive layer for a polarizing plate, preferably 10 μm to 50 μm, particularly preferably 15 μm to 30 μm.
The substrate 13 is not particularly limited, and any substrate used as a substrate sheet of a general adhesive sheet can be used. Examples of the optical member include woven or nonwoven fabrics using fibers such as rayon, acrylic, and polyester; synthetic paper; high quality paper, glassine paper, paper containing impregnated paper, coated paper, etc.; metal foils of aluminum, copper, and the like; foams such as polyurethane foams and polyethylene foams; polyester films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; cellulose films such as polyurethane films, polyethylene films, polypropylene films, and triacetylcellulose; plastic films such as polyvinyl chloride films, polyvinylidene chloride films, polyvinyl alcohol films, ethylene-vinyl acetate copolymer films, polystyrene films, polycarbonate films, acrylic resin films, norbornene resin films, cycloolefin resin films; a laminate of two or more of these. The plastic film may be a uniaxially stretched film or a biaxially stretched film.
Examples of the optical member include a polarizer (polarizing film), a polarizer, a retardation plate (retardation film), a viewing angle compensation film, a brightness enhancement film, a contrast enhancement film, a liquid crystal polymer film, a diffusion film, and a transflective film. Among them, a polarizing plate (polarizing film) is likely to shrink and has a large dimensional change, and therefore, is suitable as a base material for forming the adhesive (the adhesive layer 11) of the present embodiment from the viewpoint of the requirement for durability. In particular, a polycycloolefin film or a polarizing plate (COP polarizing plate) provided with the same is suitable as a base material for forming the adhesive (the adhesive layer 11) of the present embodiment in view of the requirement of adhesiveness and adhesion durability, because it is easy to shrink and has a large dimensional change, a large contact angle, and low adhesion.
The thickness of the substrate 13 varies depending on the type thereof, and in the case of an optical member, for example, it is usually 10 to 500 μm, preferably 50 to 300 μm, and particularly preferably 80 to 150 μm.
Examples of the release sheets 12, 12a, and 12b include a polyethylene film, a polypropylene film, a polybutylene film, a polybutadiene film, a polymethylpentene film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyethylene terephthalate film, a polyethylene naphthalate film, a polybutylene terephthalate film, a polyurethane film, an ethylene vinyl acetate film, an ionomer resin film, an ethylene- (meth) acrylic acid copolymer film, an ethylene- (meth) acrylic acid ester copolymer film, a polystyrene film, a polycarbonate film, a polyimide film, and a fluororesin film. In addition, these crosslinked films can also be used. Further, a laminated film of these may be used.
The release surface of the release sheet (particularly, the surface in contact with the adhesive layer 11) is preferably subjected to a release treatment. Examples of the release agent used for the release treatment include alkyd based, silicone based, fluorine based, unsaturated polyester based, polyolefin based, and wax based release agents.
The thickness of the release sheets 12, 12a, 12b is not particularly limited, and is usually about 20 μm to 150 μm.
To produce the adhesive sheet 1A, a solution (coating solution) containing the adhesive composition P is applied to the release surface of the release sheet 12 and dried to form a coating film of the adhesive composition P, and then the substrate 13 is laminated on the coating film. Then, the coating film is irradiated with active energy rays through the release sheet 12. The coating film becomes adhesive layer 11 as it is when a curing period is not required, and becomes adhesive layer 11 after the curing period is passed when a curing period is required. The drying and curing conditions are as described above.
In order to produce the adhesive sheet 1B, a coating solution containing the adhesive composition is applied to the release surface of one release sheet 12a (or 12B) and dried to form a coating film of the adhesive composition P, and then the release surface of the other release sheet 12B (or 12a) is superimposed on the coating film. Then, the coating film is irradiated with active energy rays through the release sheet 12a (or 12 b). The coating film becomes adhesive layer 11 as it is when a curing period is not required, and becomes adhesive layer 11 after the curing period is passed when a curing period is required.
Examples of the method of applying the coating solution include a bar coating method, a blade coating method, a roll coating method, a plate coating method, a die coating method, and a gravure coating method.
The haze value (value measured according to JIS K7136: 2000) of the adhesive layer 11 in the adhesive sheets 1A and 1B is preferably 1.0% or less, particularly preferably 0.9% or less, and more preferably 0.8% or less. When the haze value is 1.0% or less, the transparency is extremely high, and the coating composition is suitably used for optical applications.
Here, for example, in order to manufacture a liquid crystal display device including a liquid crystal cell and a polarizing plate, the polarizing plate is used as the base 13 of the adhesive sheet 1A, the release sheet 12 of the adhesive sheet 1A is peeled off, and the exposed adhesive layer 11 is bonded to the liquid crystal cell.
For example, in order to manufacture a liquid crystal display device in which a retardation plate is disposed between a liquid crystal cell and a polarizer, one release sheet 12a (or 12B) of the adhesive sheet 1B is first peeled off, and the adhesive layer 11 exposed from the adhesive sheet 1B is bonded to the retardation plate. Then, the release sheet 12 of the adhesive sheet 1A using a polarizing plate as the base 13 is peeled off, and the adhesive layer 11 exposed from the adhesive sheet 1A is bonded to the retardation plate. Further, the other release sheet 12B (or 12a) is peeled from the adhesive layer 11 of the adhesive sheet B, and the adhesive layer 11 exposed from the adhesive sheet B is bonded to the liquid crystal cell.
Since adhesive sheets 1A and 1B have excellent durability of adhesive layer 11, the occurrence of floating, peeling, air bubbles, and the like with substrate 13 or an adherend can be prevented/suppressed even under high-temperature conditions or moist-heat conditions. In particular, even when the substrate 13 is a COP polarizing plate, the adhesive layer 11 can absorb and relax the stress that may be generated by the deformation of the COP polarizing plate, thereby exhibiting excellent durability.
The adhesive sheets 1A and 1B according to the present embodiment also preferably have a transparent conductive film as an adherend. In the (meth) acrylate polymer (a) in the adhesive composition P, the amount of the carboxyl group-containing monomer contained as a monomer unit is small as described above, and therefore, the adverse effect of the acid component on the transparent conductive film can be suppressed. Specifically, corrosion of the transparent conductive film or change in the resistance value of the transparent conductive film can be suppressed.
Examples of the transparent conductive film include metals such as platinum, gold, silver, and copper; oxides such as tin oxide, indium oxide, cadmium oxide, zinc oxide, and zinc oxide; tin-doped indium oxide (ITO), zinc oxide-doped indium oxide, fluorine-doped indium oxide, antimony-doped tin oxide, fluorine-doped tin oxide, aluminum-doped zinc oxide, and the like; a transparent conductive film made of a non-oxide compound such as chalcogenide, lanthanum hexaboride, titanium nitride, or titanium carbide.
Specifically, when a laminate obtained by bonding the adhesive layer 11 and the transparent conductive film using the adhesive sheet 1A or the adhesive sheet 1B according to the present embodiment is subjected to a moist heat acceleration test in which the laminate is exposed to an atmosphere of 65 ℃ and 95% RH for 500 hours, the increase rate of the resistance value of the transparent conductive film calculated by the following equation is preferably 15% or less, and particularly preferably 10% or less.
A resistance value increase rate (%) { (R-R)0)/R0}×100
(in the formula, R0The resistance value is the initial resistance value (Ω) before the moist heat acceleration test, and R is the resistance value (Ω) after the moist heat acceleration test. )
The method for measuring the increase rate of the resistance value of the transparent conductive film will be described in detail later.
The adhesive sheet 1A using a polarizing plate as the base 13 (hereinafter, referred to as "polarizing plate with adhesive layer") has an adhesive strength to alkali-free glass of preferably 0.1N/25mm to 20N/25mm, particularly preferably 0.5N/25mm to 10N/25mm, and more preferably 1N/25mm to 5N/25 mm. When the adhesive strength is within the above range, the adhesive can be prevented from floating or peeling from an adherend such as a glass plate. The term "adhesion" as used herein basically means a bond formed by a method based on JIS Z0237: 2009, the adhesion force measured by the 180 ° peel method, the adhesion force obtained by cutting a measurement sample into a width of 25mm and a length of 100mm, pressing the measurement sample against an adherend at 0.5MPa and 50 ℃ for 20 minutes, leaving the sample under normal pressure, 23 ℃ and 50% RH for 24 hours, and then measuring at a peel speed of 300 mm/min.
The embodiments described above are described to facilitate understanding of the present invention, and are not described to limit the present invention. Therefore, each element disclosed in the above embodiments includes all design modifications and equivalents that fall within the technical scope of the present invention.
For example, the release sheet 12 of the adhesive sheet 1A may be omitted, and either one of the release sheets 12a and 12B of the adhesive sheet 1B may be omitted.
Examples
The present invention will be further specifically described below with reference to examples and the like, but the scope of the present invention is not limited to these examples and the like.
[ example 1 ]
Preparation of (meth) acrylate Polymer
76.9 parts by mass of n-butyl acrylate, 10 parts by mass of methyl acrylate, 10 parts by mass of 2-phenylethyl acrylate, 3 parts by mass of 2-hydroxyethyl acrylate and 0.1 part by mass of acrylic acid were copolymerized to prepare a (meth) acrylate polymer (A). The molecular weight of the (meth) acrylate polymer (A) was measured by the method described later, and the weight average molecular weight was 150 ten thousand.
2. Preparation of adhesive composition
100 parts by mass (solid content equivalent; the same applies hereinafter) of the (meth) acrylate polymer (A) obtained in the above step (1), 0.1 part by mass of trimethylolpropane-modified tolylene diisocyanate (trade name "CORONATE L" manufactured by Nippon polyurethane industries Co., Ltd.) as the isocyanate-based crosslinking agent (B), 0.3 part by mass of a cocondensate of 3-mercaptopropyltrimethoxysilane and methyltriethoxysilane (trade name "X-411-, 0.5 parts by mass of a photopolymerization initiator (E) prepared by mixing benzophenone and 1-hydroxycyclohexyl phenyl ketone in a ratio of 1: 1 (IRGACURE 500, manufactured by qianye specialty chemicals) were mixed and sufficiently stirred, and diluted with ethyl acetate to obtain a coating solution of the adhesive composition.
The formulation of the adhesive composition is shown in table 1. The abbreviations and the like shown in table 1 are described in detail below.
[ (meth) acrylate Polymer ]
BA: acrylic acid n-butyl ester
MA: acrylic acid methyl ester
PhEA: acrylic acid 2-phenyl ethyl ester
HEA: 2-hydroxyethyl acrylate
AA: acrylic acid
[ silane coupling agent ]
C1: cocondensate of 3-mercaptopropyltrimethoxysilane and methyltriethoxysilane (trade name "X-411-1810" manufactured by shin-Etsu chemical Co., Ltd.)
C2: 3- (2, 3-Oxypropoxy) propyltrimethoxysilane (trade name "KBM-403" manufactured by shin-Etsu Silicone Co., Ltd.)
3. Production of polarizing plate with adhesive layer
The obtained coating solution of the adhesive composition was applied to the release-treated surface of a release sheet (SP-PET3811 manufactured by Lindelco Ltd., thickness: 38 μm) obtained by releasing one surface of a polyethylene terephthalate film with a silicone-based release agent by a blade coater to a thickness of 20 μm after drying, and then subjected to a heat treatment at 90 ℃ for 1 minute to form a coating film of the adhesive composition.
Then, a COP polarizer having a thickness of 100 μm, which was obtained by protecting one surface of a polarizer made of a polyvinyl alcohol film with a triacetylcellulose film and the other surface with a cycloolefin polymer film, was laminated on the coating film so that the exposed surface of the coating film was in contact with the surface of the cycloolefin polymer film. Then, the coating film was irradiated with ultraviolet rays through a release sheet under the following conditions and cured at 23 ℃ and 50% RH for 7 days, thereby obtaining a polarizing plate with an adhesive layer.
< ultraviolet irradiation conditions >
An electrodeless lamp H BULB manufactured by FUSION
Illuminance 600mW/cm2Light quantity of 150mJ/cm2
The UV illuminance/photometer used was "UVPF-36" manufactured by EYE GRAPHICS Co "
[ examples 2 to 13, comparative examples 1 to 4 ]
A polarizing plate with an adhesive layer was produced in the same manner as in example 1, except that the kind and ratio of each monomer constituting the (meth) acrylate polymer (a), the weight average molecular weight of the (meth) acrylate polymer (a), the blending amount of the isocyanate-based crosslinking agent (B), the kind and blending amount of the silane coupling agent (C), the blending amount of the active energy ray-curable component (D), and the blending amount of the photopolymerization initiator (E) were changed as shown in table 1. In example 7, 1.8 parts by mass of an equimolar mixture of lithium bis (trifluoromethanesulfonylimide) and tetraethylene glycol dimethyl ether (trade name "sanbonol TGR" manufactured by photochemistry corporation) was added as an antistatic agent during preparation of the adhesive composition.
Here, the weight average molecular weight (Mw) is a weight average molecular weight in terms of polystyrene measured by Gel Permeation Chromatography (GPC) under the following conditions (GPC measurement).
< measurement Condition >
GPC measurement apparatus: HLC-8020 manufactured by TOSOH
GPC column (passage in the following order): manufactured by TOSOH Inc
TSK guard column HXL-H
TSK gel GMHXL(×2)
TSK gel G2000HXL
Determination of the solvent: tetrahydrofuran (THF)
Measurement temperature: 40 deg.C
[ test example 1 ] (measurement of gel fraction)
In place of the polarizing plate used for producing the polarizing plate with an adhesive layer in the examples or comparative examples, an adhesive sheet was produced by using a release sheet (SP-PET3801 manufactured by Linekec Co., Ltd., thickness: 38 μm) obtained by peeling one surface of a polyethylene terephthalate film with a silicone-based release agent. Specifically, the release sheets were laminated on the exposed coating film of the construct comprising the release sheet/coating film of the adhesive composition obtained in the production process of examples or comparative examples so that the release-treated surfaces were in contact with each other, and then aged at 23 ℃ and 50% RH for 7 days. Thus, an adhesive sheet having a structure of release sheet (SP-PET 3801)/adhesive layer (thickness: 20 μm)/release sheet (SP-PET3811) was produced.
The obtained adhesive sheet was prepared into a sample of 80mm × 80mm in size, the adhesive layer thereof was wrapped with a polyester mesh (mesh size 200), and the mass of the adhesive alone was weighed with a precision balance. The mass at this time was taken as M1.
Subsequently, the adhesive wrapped with the polyester mesh was immersed in ethyl acetate at room temperature (23 ℃) for 24 hours. Thereafter, the adhesive was taken out, air-dried at a temperature of 23 ℃ and a relative humidity of 50% for 24 hours, and further dried in an oven at 80 ℃ for 12 hours. The individual mass of the dried adhesive was weighed with a precision balance. The mass at this time was taken as M2. Gel fraction (%) is represented by (M2/M1). times.100. The results are shown in Table 2.
[ test example 2 ] (measurement of haze value)
As a measurement sample, an adhesive sheet similar to the adhesive sheet used for measuring the gel fraction was prepared. The adhesive layer (thickness: 20 μm) of this adhesive sheet was measured using a haze meter (NDH 2000, manufactured by japan electro-chromic industries, inc.) based on jis k 7136: 2000, haze value (%) was measured. The results are shown in Table 2.
[ test example 3 ] (measurement of the rate of increase in resistance value)
The adhesive layer-attached polarizing plates obtained in examples and comparative examples were measured for resistance value of the ITO film according to the following test method, and the rate of increase in resistance value was calculated.
As shown in fig. 3, a cross-sectional view of the resistance value measurement sample S is shown. A polyethylene terephthalate (PET) film 21 having an ITO film 22 provided on one surface 21a by sputtering was prepared, and the surface 21b of the PET film 21 on which the ITO film 22 was not provided was bonded to one surface 23a of the glass plate 23 with an adhesive tape 24 (trade name "TACKLINER TL-70" manufactured by lindecco).
Then, on the opposite surface 22a (hereinafter referred to as "one surface") of the ITO film 22 to the surface in contact with the PET film 21, a conductive resin material containing silver (trade name "FA-301 CA", dot touch panel circuit type, manufactured by rattan chemical corporation) was applied in a rectangular electrode shape of 20mm × 5mm, and then heated at 80 ℃ for 20 minutes to dry, thereby forming two electrodes 25 serving as resistance value measurement points. At this time, the positions of the two electrodes 25, 25 are adjusted so that the distance therebetween is slightly larger than 20 mm.
On the other hand, the adhesive layer-attached polarizing plate 1A ' obtained in example or comparative example was cut into a size of 20mm × 250mm, and the release sheet was peeled off (in this case, the adhesive layer-attached polarizing plate 1A ' was a laminate composed of a polarizing plate 13 ' and an adhesive layer 11). Then, the adhesive layer 11 of the adhesive layer-attached polarizing plate 1A' was attached to the one surface 22a of the ITO film 22 along the edges of the two electrodes 25 and 25 (just without coming into contact therewith), and a sample S for measuring the resistance value was prepared as shown in fig. 3.
Thereafter, as shown in FIG. 4, an initial resistance value R between the electrodes 25, 25 was measured by a digital multimeter (product name "3802-50" manufactured by Nichikoku corporation) 300(omega). The resistance value measuring sample S was left to stand at 60 ℃ and 90% RH for 500 hours, and then the resistance value R (omega) after the promotion of moist heat was measured. According to the obtained initial resistance value R0And a resistance value R after the promotion of moist heat, and the rate of increase in the resistance value of the resistance value measurement sample S was calculated by the following formula. The results are shown in Table 2.
A resistance value increase rate (%) { (R-R)0)/R0}×100
[ test example 4 ] (evaluation of durability)
The adhesive layer-attached polarizing plates obtained in examples and comparative examples were cut to prepare samples having dimensions of 200mm × 150 mm. The release sheet was peeled from the sample, and after the release sheet was stuck to an alkali-free glass (Eagle XG, manufactured by corning corporation) through the exposed adhesive layer, the sample was pressurized at 50 ℃ and 0.5MPa for 20 minutes in an autoclave manufactured by chestnut.
Thereafter, the glass was put into an environment under the following durability conditions, and after 250 hours, the presence or absence of lifting or peeling was checked using a 10-fold loupe. The evaluation criteria are as follows. The results are shown in Table 2.
◎ No floating or peeling was observed.
○, it was found that the film had a size of 0.5mm or less and floated or peeled.
△, the floating or peeling was observed to be larger than 0.5mm and not larger than 1.0 mm.
X: the floating or peeling of the size larger than 1.0mm was confirmed.
< endurance Condition >
Drying at 85 ℃
60 ℃ and relative humidity 90% RH
[ test example 5 ] (measurement of surface resistance value of adhesive layer)
The polarizing plate with an adhesive layer obtained in example 7 was cut into a size of 50mm × 50mm, and the obtained sample was left at 23 ℃ and 50% RH for 24 hours. Thereafter, the release sheet was peeled off, and the surface resistance value (Ω/sq) was measured on the exposed surface of the adhesive layer based on JIS K6911 using a resistivity meter (HIRESTA UP MCP-HT450, manufactured by Mitsubishi chemical analysis). The results are shown in Table 2.
In addition, the surface resistance value is preferably 3.0 × 1011Omega/sq or less, particularly preferably 1.0X 1011Omega/sq or less, more preferably 8.0X 1010Omega/sq or less. When the surface resistance value is not more than the above value, good antistatic property can be exhibited.
[ test example 6 ] (measurement of storage modulus)
As a measurement sample, an adhesive sheet similar to the adhesive sheet used for the gel fraction measurement was prepared. A cylindrical test piece having a diameter of 8 mm. times.3 mm was prepared by laminating the adhesive layer (thickness: 20 μm) of the adhesive sheet, and the storage modulus (G') was measured by the torsional shear method under the following conditions. The results are shown in Table 2.
The measurement device: dynamic viscoelasticity measuring apparatus "DYNAMICALLYZER RDAII", manufactured by Rheometric Co., Ltd "
Frequency: 1Hz
Temperature: 23 ℃ and 80 DEG C
TABLE 1
Figure BDA0000528817930000301
TABLE 2
Figure BDA0000528817930000302
As is clear from table 2, the adhesive of the adhesive layer obtained in the examples has excellent durability and the resistance value of the transparent conductive film as an adherend is not easily changed.
Industrial applicability of the invention
The adhesive and the adhesive sheet of the present invention are suitably used for bonding a transparent conductive film, particularly a transparent conductive film made of tin-doped indium oxide (ITO), to an optical member, particularly a polarizing plate.
Description of the reference numerals
1A, 1B … adhesive sheet
1A' … polarizing plate with adhesive layer
11 … adhesive layer
12. 12a, 12b … release sheet
13 … base material
13' … polarized light sheet
21 … PET film
21a, 21b … side
22 … ITO film
22a … face
23 … glass plate
23a … face
24 … adhesive tape
25 … electrode
30 … digital multimeter
S … sample for measuring resistance value

Claims (16)

1. An adhesive composition comprising:
the (meth) acrylate polymer (A) has a weight-average molecular weight of 100 to 250 ten thousand, and contains, as monomer units constituting the polymer, a monomer having a hydroxyl group, a monomer having an aromatic ring, a monomer having a carboxyl group,
Isocyanate crosslinking agents (B),
A silane coupling agent (C) having a mercapto group, and
an active energy ray-curable component (D);
the (meth) acrylate polymer (A) contains, as monomer units constituting the polymer, 1 to 5 mass% of the monomer having a hydroxyl group, 5 to 30 mass% of the monomer having an aromatic ring, and 0.1 to 0.5 mass% of the monomer having a carboxyl group.
2. The adhesive composition according to claim 1, wherein the isocyanate-based crosslinking agent (B) is trimethylolpropane-modified tolylene diisocyanate.
3. The adhesive composition according to claim 1, wherein the content of the isocyanate-based crosslinking agent (B) is 0.01 to 1 part by mass based on 100 parts by mass of the (meth) acrylate polymer (A).
4. The adhesive composition according to claim 1, wherein the content of the silane coupling agent (C) is 0.01 to 0.5 parts by mass based on 100 parts by mass of the (meth) acrylate polymer (A).
5. The adhesive composition according to claim 1, wherein the monomer having an aromatic ring is 2-phenylethyl (meth) acrylate.
6. The adhesive composition according to claim 1, wherein the active energy ray-curable component (D) is a polyfunctional acrylate monomer having a molecular weight of less than 1000.
7. The adhesive composition according to claim 6, wherein the polyfunctional acrylate monomer has a cyclic structure.
8. The adhesive composition according to claim 1, wherein the content of the active energy ray-curable component (D) is 1 to 50 parts by mass relative to 100 parts by mass of the (meth) acrylate polymer (A).
9. An adhesive obtained by curing the adhesive composition according to any one of claims 1 to 8 by irradiation with an active energy ray.
10. The adhesive according to claim 9, wherein the gel fraction is 55% to 85%.
11. The adhesive according to claim 9, wherein the storage modulus at 23 ℃ is 0.15 to 0.3MPa, and the storage modulus at 80 ℃ is 0.05 to 0.2 MPa.
12. An adhesive sheet characterized in that,
comprises a base material and an adhesive layer,
the adhesive layer contains the adhesive according to claim 9.
13. The adhesive sheet according to claim 12, wherein the substrate is an optical member.
14. The adhesive sheet according to claim 13, wherein the optical member is a polarizer.
15. An adhesive sheet is characterized by comprising:
two release sheets, and
an adhesive layer sandwiched between the two release sheets so as to be in contact with release surfaces of the two release sheets;
the adhesive layer contains the adhesive according to claim 9.
16. The adhesive sheet according to claim 12, wherein when the laminate of the adhesive layer and the transparent conductive film is subjected to a moist heat acceleration test in which the laminate is exposed to an atmosphere of 65 ℃ and 95% RH for 500 hours, the transparent conductive film has a resistance value increase rate of 15% or less as calculated by the following equation,
a resistance value increase rate (%) { (R-R)0)/R0}×100
In the formula, R0The resistance value is the initial resistance value before the moist heat acceleration test, and R is the resistance value after the moist heat acceleration test.
CN201410301348.4A 2013-06-28 2014-06-27 Adhesive composition, adhesive and adhesive sheet Active CN104250524B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2013-137538 2013-06-28
JP2013137538A JP6114648B2 (en) 2013-06-28 2013-06-28 Adhesive composition, adhesive and adhesive sheet

Publications (2)

Publication Number Publication Date
CN104250524A CN104250524A (en) 2014-12-31
CN104250524B true CN104250524B (en) 2020-02-21

Family

ID=52185788

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410301348.4A Active CN104250524B (en) 2013-06-28 2014-06-27 Adhesive composition, adhesive and adhesive sheet

Country Status (4)

Country Link
JP (1) JP6114648B2 (en)
KR (1) KR102281768B1 (en)
CN (1) CN104250524B (en)
TW (1) TWI636106B (en)

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI698665B (en) * 2015-03-03 2020-07-11 日商琳得科股份有限公司 Polarizing plate with adhesive layer
JP6463192B2 (en) * 2015-03-03 2019-01-30 リンテック株式会社 Optical film with adhesive layer
JP6438817B2 (en) * 2015-03-27 2018-12-19 リンテック株式会社 Adhesive composition, adhesive, adhesive sheet and optical film with adhesive layer
JP6554344B2 (en) * 2015-06-30 2019-07-31 リンテック株式会社 Adhesive sheet and display
KR101780547B1 (en) 2015-07-31 2017-09-22 삼성에스디아이 주식회사 Adhesive film for polarizing plate, polarizing plate comprising the same and optical display apparatus comprising the same
TWI562892B (en) * 2015-10-28 2016-12-21 Sumika Technology Co Ltd Touch display device
TWI642742B (en) 2015-11-24 2018-12-01 三星Ｓｄｉ股份有限公司 Adhesive film for polarizing plate, polarizing plate and optical display comprising the same
KR101908175B1 (en) * 2015-11-24 2018-10-15 삼성에스디아이 주식회사 Adhesive film for polarizing plate, polarizing plate and display deviece comprising the same
CN107163867B (en) * 2016-03-07 2021-10-26 日东电工株式会社 Optical adhesive sheet, polarizing film with adhesive layer, and liquid crystal display device
TW201825583A (en) * 2016-11-16 2018-07-16 日商東亞合成股份有限公司 Curable composition for producing resin sheet
JP7112828B2 (en) * 2016-12-16 2022-08-04 大王製紙株式会社 Adhesive sheet
KR102158871B1 (en) * 2017-07-04 2020-09-22 삼성에스디아이 주식회사 Adhesive composition for polarizing plate, adhesive film for polarizing plate prepared using the same, polarizing plate comprising the same and optical display apparatus comprising the same
CN109237434A (en) * 2018-09-29 2019-01-18 江苏锐阳照明电器设备有限公司 A kind of dust-proof coating of mining illuminating lamp tool
CN110387193A (en) * 2019-08-09 2019-10-29 苏州凡赛特材料科技有限公司 A kind of nano metal conductive film optics Adhesive composition and its glue film
KR102635555B1 (en) * 2021-06-18 2024-02-08 (주)이녹스첨단소재 Adhesive sheet for display and display comprising the same
CN113956423B (en) * 2021-08-19 2023-05-26 Oppo广东移动通信有限公司 Composition, polymer dispersed liquid crystal, film and electronic device
WO2023136052A1 (en) * 2022-01-12 2023-07-20 綜研化学株式会社 Pressure-sensitive adhesive composition for polarizing plate, and polarizing plate with pressure-sensitive adhesive layer
JP7327700B1 (en) 2023-04-05 2023-08-16 東洋インキＳｃホールディングス株式会社 Rolled conductive bonding sheet, wiring board with metal reinforcing plate, and electronic device

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101113314B (en) * 2006-07-26 2011-06-15 琳得科株式会社 Adhesive for laminating optical functional film, optical functional film with adhesive and method for manufacturing the same
CN102181244A (en) * 2009-12-29 2011-09-14 第一毛织株式会社 Adhesive binder, adhesive composition including the same, optical member, and a method for preparing adhesive binder layer

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3997270B2 (en) * 2005-11-21 2007-10-24 綜研化学株式会社 Optical film pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet, and optical member using the same
JP2007169329A (en) * 2005-12-19 2007-07-05 Saiden Chemical Industry Co Ltd Adhesive composition for optical use and adhesive sheet
JP5015648B2 (en) * 2007-04-11 2012-08-29 サイデン化学株式会社 Optical pressure-sensitive adhesive composition and optical functional film
JP5649276B2 (en) * 2007-12-25 2015-01-07 日本合成化学工業株式会社 Optical member pressure-sensitive adhesive and optical member
JP5379409B2 (en) * 2008-02-15 2013-12-25 日東電工株式会社 Adhesive composition for optical film, adhesive optical film, and image display device
JP2009221324A (en) * 2008-03-14 2009-10-01 Soken Chem & Eng Co Ltd Pressure-sensitive adhesive for optical member and protection film for optical member using the same
JP5616652B2 (en) 2010-02-24 2014-10-29 リンテック株式会社 Adhesive composition and adhesive sheet
JP5683229B2 (en) 2009-11-27 2015-03-11 日本合成化学工業株式会社 Adhesive, adhesive for optical member, optical member with adhesive layer, image display device, and adhesive composition
JP5729973B2 (en) * 2010-11-11 2015-06-03 日本合成化学工業株式会社 Acrylic adhesive, adhesive for optical members, optical member with adhesive layer, image display device
JP5552338B2 (en) * 2010-03-12 2014-07-16 リンテック株式会社 Adhesive composition, adhesive and adhesive sheet
KR20120001647A (en) 2010-06-28 2012-01-04 주식회사 누마스타세척기 Hand washing device
JP2012077299A (en) * 2010-09-10 2012-04-19 Nippon Synthetic Chem Ind Co Ltd:The Pressure-sensitive adhesive composition, pressure-sensitive adhesive, pressure-sensitive adhesive for optical member, optical member with pressure-sensitive adhesive layer, image display device
CN103168083B (en) * 2010-10-12 2015-11-25 日本合成化学工业株式会社 The optical component of Adhesive composition for optical component, optical component tackiness agent, band binder layer and image display device
KR101459124B1 (en) * 2011-12-07 2014-11-07 제일모직주식회사 Photo-curable adhesive composition and display device comprising the same

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101113314B (en) * 2006-07-26 2011-06-15 琳得科株式会社 Adhesive for laminating optical functional film, optical functional film with adhesive and method for manufacturing the same
CN102181244A (en) * 2009-12-29 2011-09-14 第一毛织株式会社 Adhesive binder, adhesive composition including the same, optical member, and a method for preparing adhesive binder layer

Also Published As

Publication number Publication date
KR102281768B1 (en) 2021-07-27
JP2015010192A (en) 2015-01-19
JP6114648B2 (en) 2017-04-12
TWI636106B (en) 2018-09-21
TW201504376A (en) 2015-02-01
KR20150002459A (en) 2015-01-07
CN104250524A (en) 2014-12-31

Similar Documents

Publication Publication Date Title
CN104250524B (en) Adhesive composition, adhesive and adhesive sheet
CN103980820B (en) Pressure-sensitive adhesive composition, pressure-sensitive adhesive, and pressure-sensitive adhesive sheet
KR102217567B1 (en) Laminate manufacturing method
CN110054997B (en) Active energy ray-curable adhesive sheet and laminate
KR102243211B1 (en) adhesion sheet and laminate
JP6196781B2 (en) Adhesive composition, adhesive and adhesive sheet
KR102314959B1 (en) adhesion composition, an adhesive and adhesion sheet
KR102278242B1 (en) adhesion composition, an adhesive and adhesion sheet
KR20150002460A (en) adhesion composition, an adhesive and adhesion sheet
WO2015155844A1 (en) Adhesive sheet and laminate
CN116515457A (en) Pressure-sensitive adhesive layer, method for producing same, pressure-sensitive adhesive sheet, optical film with pressure-sensitive adhesive layer, and image display device
JP6290466B2 (en) Adhesive sheet
JP2017115159A (en) Optical adhesive sheet
JP6502999B2 (en) Adhesive composition, adhesive and adhesive sheet
JP6756757B2 (en) Method of manufacturing a laminate
JP2018127625A (en) Active energy ray-curable adhesive sheet and laminate

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant