CN106916555B - Adhesive, adhesive sheet using same, polarizing plate adhesive sheet, and liquid crystal cell member - Google Patents

Adhesive, adhesive sheet using same, polarizing plate adhesive sheet, and liquid crystal cell member Download PDF

Info

Publication number
CN106916555B
CN106916555B CN201611052481.6A CN201611052481A CN106916555B CN 106916555 B CN106916555 B CN 106916555B CN 201611052481 A CN201611052481 A CN 201611052481A CN 106916555 B CN106916555 B CN 106916555B
Authority
CN
China
Prior art keywords
adhesive
group
compound
weight
meth
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
CN201611052481.6A
Other languages
Chinese (zh)
Other versions
CN106916555A (en
Inventor
福田克哲
小林孝行
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.)
Toyochem Co Ltd
Artience Co Ltd
Original Assignee
Toyo Ink SC Holdings Co Ltd
Toyochem Co Ltd
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 Toyo Ink SC Holdings Co Ltd, Toyochem Co Ltd filed Critical Toyo Ink SC Holdings Co Ltd
Publication of CN106916555A publication Critical patent/CN106916555A/en
Application granted granted Critical
Publication of CN106916555B publication Critical patent/CN106916555B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • 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
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/21—Urea; Derivatives thereof, e.g. biuret
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • 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
    • 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
    • C09J7/21—Paper; Textile fabrics
    • 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
    • C09J7/22—Plastics; Metallised plastics
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133528—Polarisers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1515—Three-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/205—Compounds containing groups, e.g. carbamates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5435—Silicon-containing compounds containing oxygen containing oxygen in a ring
    • 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
    • C09J2433/00—Presence of (meth)acrylic polymer

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Polarising Elements (AREA)

Abstract

The present invention relates to an adhesive, an adhesive sheet using the same, a polarizing plate adhesive sheet, and a liquid crystal cell member, which have excellent releasability and are less likely to cause lifting or peeling from an adherend after exposure to a high-temperature environment or a high-temperature and high-humidity environment. The adhesive comprises an acrylic copolymer (A), a crosslinking agent (B), a silane coupling agent (C) and a compound (D) having an epoxy group or an epoxycyclohexyl group, wherein the copolymer (A) is a copolymer containing at least a carboxyl group-containing monomer (a-1) unit and a hydroxyl group-containing monomer (a-2) unit, and the compound (D) is represented by the following formula [ I ]]Or formula [ II]The compounds represented.
Figure DDA0001160670000000011
In the formula, p, q and r are integers, p is more than or equal to 1 and less than or equal to 30, q is more than or equal to 5 and less than or equal to 50, r is more than or equal to 5 and less than or equal to 50, and q + r is more than or equal to 10 and less than or equal to 100; x1～X4Is alkyl, X5Is a divalent organic residue having 1 to 10 carbon atoms, and Y represents an epoxy group or an epoxycyclohexyl group.

Description

Adhesive, adhesive sheet using same, polarizing plate adhesive sheet, and liquid crystal cell member
Technical Field
The invention relates to an adhesive, an adhesive sheet, a polarizing plate adhesive sheet and a liquid crystal unit member. More specifically, the present invention relates to an adhesive, an adhesive sheet, a polarizing plate adhesive sheet, and a liquid crystal cell member which can be suitably used for members such as plastic and glass.
Background
Display devices such as liquid crystal displays used in various devices such as home appliances and business electric appliances including computers, electronic clocks, mobile phones, and televisions are becoming larger in size, and particularly, liquid crystal televisions and plasma televisions are becoming larger in size. In recent years, touch panel type liquid crystal displays typified by smartphones and tablet computers have rapidly spread, and a large market expansion is expected in the future. On the other hand, liquid crystal displays are also used for vehicle-mounted devices such as car navigation systems, and are required to have durability that can be used in severe vehicle environments such as high-temperature and high-humidity environments. In addition, in a liquid crystal display, a polarizing plate, a retardation plate, or the like having various optical functions is used, and these members are attached to an adherend such as a liquid crystal cell using glass or transparent plastic via an adhesive.
The polarizing plate is generally a laminate in which a polyvinyl alcohol film is sandwiched between a triacetyl cellulose film and a cycloolefin film. Further, since these films have different mechanical properties and have different dimensional change rates during heating, the laminate often undergoes warpage when left in a high-temperature environment.
Here, for example, when a member for a liquid crystal cell, which is a polarizing plate, an adhesive layer, or glass (glass is a surface member of a liquid crystal cell), is placed in a high-temperature environment, the following problems may occur: warpage due to the dimensional change rate between the constituent members of the polarizing plate occurs, bubbles (foaming) occur at the adhesion interface between the adhesive layer and the glass, or the polarizing plate floats from the glass and peels off. Further, the warpage causes the stress distribution of the liquid crystal cell member to be uneven, and the stress is concentrated on the peripheral end portion of the liquid crystal cell member, resulting in a problem of a so-called "light leakage phenomenon" in which light leaks from the four corners or the peripheral end portion of the liquid crystal cell member. The problem also occurs in a high-temperature and high-humidity environment.
On the other hand, in the production process of a liquid crystal display or the like, when a polarizing plate is bonded to an optical component such as a liquid crystal cell, the polarizing plate is peeled off after a certain time has elapsed after bonding, and the expensive liquid crystal cell is reused. Therefore, the following characteristics (reworkability) are required for the adhesive: after a certain time has elapsed after the attachment, the polarizing plate can be peeled off from the liquid crystal cell.
In order to solve these problems, patent document 1 discloses the following technique: the acrylic copolymer containing aromatic ring-containing monomers improves stress relaxation and prevents light leakage. However, the adhesive using an aromatic ring-containing monomer disclosed in patent document 1 has a problem that white spots are generated and optical characteristics are deteriorated in light leakage evaluation.
Patent document 2 discloses the following technique: in order to impart removability, a low-molecular-weight acrylic polymer having a high acid value and a weight-average molecular weight of 0.2 to 10 ten thousand is blended with a high-molecular-weight acrylic polymer having a weight-average molecular weight of 50 ten thousand or more. However, the adhesive described in patent document 2 has a problem that drying conditions of the adhesive are limited.
On the other hand, patent document 3 discloses the following technique: by using a block polymer using two or more monomers, durability or adhesive properties under heating or humidifying conditions are improved. However, the adhesive described in patent document 3 has a problem that the transmittance under heating or humidifying conditions is lowered.
Further, patent document 4 discloses the following technique: a water-dispersed adhesive comprising an acrylic copolymer having a glass transition temperature of-55 ℃ or higher and less than 0 ℃ and an acrylic copolymer having a glass transition temperature of 0 ℃ or higher and 180 ℃ or lower, which is less likely to cause depolarization and is imparted with reworkability and recyclability. However, the adhesive described in patent document 4 has the following problems: due to various additives used in the adhesive, the reworkability after attachment is insufficient over a long period of time.
Further, patent document 5 discloses the following technique: the mutually permeable network structure is constructed in a cured state by using an acrylic copolymer containing a hydroxyl group and an alkylene oxide group and a polyfunctional isocyanate-based curing agent, thereby suppressing the floating and peeling under a high-temperature and high-humidity environment. However, the adhesive described in patent document 5 has the following problems: when the epoxy resin composition is left in a high-temperature and high-humidity environment for a long period of time, decomposition of the epoxy alkyl group occurs, and floating and peeling occur.
Further, patent document 6 discloses the following technique: the acrylic copolymer containing hydroxyl groups and carboxyl groups, the mercapto group-containing silane compound, and the alcohol inhibit the adhesive sheet from lifting and peeling when the sheet is left in a high-temperature, high-humidity environment for a long period of time. However, the adhesive disclosed in patent document 6 has the following problems: since a silane compound having high volatility is used, the silane compound volatilizes when the adhesive is applied and dried, and a sufficient amount of the silane compound does not remain in the adhesive layer after application, and therefore, the peeling off by floating occurs.
[ Prior art documents ]
[ patent document ]
[ patent document 1] Japanese patent laid-open No. 2007-1699329
[ patent document 2] Japanese patent application laid-open No. 2010-100710
[ patent document 3] Japanese patent laid-open publication No. 2013-82772
[ patent document 4] Japanese patent laid-open No. 2014-1365
[ patent document 5] Japanese patent laid-open No. 2014-055299
[ patent document 6] Japanese patent laid-open No. 2004-059711
Disclosure of Invention
[ problems to be solved by the invention ]
The present invention has been made to solve the above problems, and an object of the present invention is to provide an adhesive which has excellent releasability when used in an adhesive sheet and is less likely to float or peel off from an adherend after being exposed to a high-temperature environment or a high-temperature and high-humidity environment, and an adhesive sheet using the same. Further, it is an object to provide an adhesive which has a good adhesive force and does not contaminate an adherend such as glass, which is extremely low in evaluation of light leakage when used for fixing a polarizing plate and which can maintain high transparency even when exposed to a high-temperature and high-humidity environment, and an adhesive sheet using the same.
[ means for solving problems ]
The invention relates to an adhesive, which comprises an acrylic copolymer (A), a cross-linking agent (B), a silane coupling agent (C) and a compound (D) having at least one epoxy group or epoxy cyclohexyl group in the molecule,
the adhesive is characterized in that: the acrylic copolymer (A) is a copolymer containing at least a carboxyl group-containing monomer (a-1) unit and a hydroxyl group-containing monomer (a-2) unit as monomer units constituting the copolymer,
the crosslinking agent (B) contains an isocyanate compound, and
the compound (D) having at least one epoxy group or epoxycyclohexyl group in the molecule is a compound represented by the following formula [ I ] or formula [ II ],
[ solution 1]
Figure BDA0001160669990000041
(wherein p, q and r are integers representing a repeating unit, p is 1. ltoreq. p.ltoreq.30, q is 5. ltoreq. q.ltoreq.50, r is 5. ltoreq. r.ltoreq.50, q + r is 10. ltoreq. r.ltoreq.100; X1～X4Each independently represents an alkyl group, X5Represents a divalent organic residue having 1 to 10 carbon atoms, and Y represents an epoxy group or an epoxycyclohexyl group).
An embodiment of the present invention relates to the adhesive, wherein the adhesive contains 0.05 to 2 parts by weight of a compound (D) having at least one epoxy group or epoxycyclohexyl group in a molecule, based on 100 parts by weight of the acrylic copolymer (a).
In addition, an embodiment of the present invention relates to the adhesive, wherein the crosslinking agent (B) is an isocyanate-based compound.
In addition, an embodiment of the present invention relates to the adhesive, wherein the silane coupling agent (C) is a silane coupling agent having an ethoxy group.
Further, an embodiment of the present invention relates to the adhesive, wherein the crosslinking agent (B) is contained in an amount of 0.5 to 20 parts by weight based on 100 parts by weight of the acrylic copolymer (a).
In addition, an embodiment of the present invention relates to an adhesive sheet including a base material and an adhesive layer including the adhesive.
In addition, the embodiment of the invention relates to a polarizing plate adhesive sheet, which comprises a polarizing plate and an adhesive layer containing the adhesive.
In addition, an embodiment of the present invention relates to a liquid crystal cell member including a glass plate, an adhesive layer including the adhesive, and an optical member.
[ Effect of the invention ]
The present invention can provide an adhesive which is excellent in removability, and after exposure to a high-temperature environment or a high-temperature and high-humidity environment, for example, is less likely to float or peel off from an adherend on glass, plastic, or the like, and can be used as an adhesive sheet which is less likely to cause light leakage.
Detailed Description
The present invention will be described in detail below. In the present specification, the term (meth) acrylate refers to a generic term for acrylate and methacrylate. The epoxycyclohexyl group is a group represented by the following formula [ III ].
[ solution 2]
Figure BDA0001160669990000051
The adhesive of the present invention comprises: the acrylic copolymer (a), the crosslinking agent (B), the silane coupling agent (C), and the compound (D) having at least one epoxy group or epoxycyclohexyl group in the molecule (hereinafter sometimes referred to simply as the compound (D)).
< acrylic copolymer (A) >
The acrylic copolymer (a) in the present specification is a copolymer containing at least a carboxyl group-containing monomer (a-1) unit and a hydroxyl group-containing monomer (a-2) unit as monomer units constituting the copolymer, and can be obtained by copolymerizing a monomer mixture containing at least a carboxyl group-containing monomer (a-1) and a hydroxyl group-containing monomer (a-2).
The carboxyl group-containing monomer (a-1) is a monomer having a carboxyl group (hereinafter, may be abbreviated as monomer (a-1)). The monomer (a-1) not only forms a polymer network by a crosslinking reaction with a crosslinking agent, but also forms a hydrogen bond with the surface of an adherend, thereby contributing to suppression of floating and peeling, and suppression of light leakage. The monomer (a-1) is preferably a carboxyl group-containing monomer having no hydroxyl group.
Specific examples of the monomer (a-1) include: (meth) acrylic acid, p-carboxybenzyl acrylate, beta-carboxyethyl acrylate, maleic acid, monoethylmaleic acid, itaconic acid, citraconic acid, fumaric acid, and the like. These monomers may be used alone or in combination of two or more.
The monomer (a-1) is preferably contained in the acrylic copolymer in an amount of 0.1 to 20% by weight, more preferably 0.5 to 10% by weight, as a monomer unit constituting the copolymer. When the content is 0.1 wt% or more, the cohesive force is further improved. Further, when the content is 20 wt% or less, the cohesion and the stress relaxation property are easily combined.
The hydroxyl group-containing monomer (a-2) is a monomer having a hydroxyl group (hereinafter, may be abbreviated as monomer (a-2)). The monomer (a-2) forms a polymer network by a crosslinking reaction with a crosslinking agent, thereby contributing to suppression of floating and peeling, suppression of light leakage. The monomer (a-2) is preferably a hydroxyl group-containing monomer having no carboxyl group.
Specific examples of the monomer (a-2) 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, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, and 8-hydroxyoctyl (meth) acrylate, and diol mono (meth) acrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and 1, 4-cyclohexanedimethanol mono (meth) acrylate, and caprolactone-modified (meth) acrylates. These monomers may be used alone or in combination of two or more.
The monomer (a-2) is preferably contained in the acrylic copolymer in an amount of 0.05 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, as a monomer unit constituting the copolymer. When the content is 0.05 parts by weight or more, the cohesive force is further improved. When the content is 10 wt% or less, the composition is likely to have both cohesive force and stress relaxation properties.
Examples of the monomer unit constituting the acrylic copolymer (a) other than the above monomers that can be used include alkyl (meth) acrylates and other vinyl monomers. Examples of the alkyl (meth) acrylate 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, tetradecyl (meth) acrylate, hexadecyl (meth) acrylate, octadecyl (meth) acrylate, and the like. Among these monomers, butyl (meth) acrylate is preferable in terms of easily obtaining good adhesive properties. These monomers may be used alone or in combination of two or more.
The alkyl (meth) acrylate is preferably contained in the acrylic copolymer in an amount of 70 to 99.85% by weight, more preferably 85 to 99.85% by weight, as a monomer unit constituting the copolymer. When the content is 70% by weight or more, the cohesive force is further improved. Further, when the content is 99.85 wt% or less, the cohesion and the stress relaxation are easily combined.
Examples of the other vinyl monomers include: the monomer having an amide bond, the monomer having an epoxy group, the monomer having an amino group, the monomer having an alkylene oxide unit, vinyl acetate, vinyl crotonate, styrene, acrylonitrile, and the like are not particularly limited as long as they can be copolymerized.
Examples of the amide bond-containing monomer include: (meth) acrylamide compounds such as (meth) acrylamide, N-methacrylamide, N-isopropylacrylamide, N-dimethylacrylamide, N-diethylacrylamide, N-dimethylaminopropyl (meth) acrylamide, diacetone acrylamide, N- (hydroxymethyl) acrylamide, and N- (butoxymethyl) acrylamide, heterocyclic ring-containing compounds such as N-vinylpyrrolidone, N-vinylcaprolactam, and acryloylmorpholine, and N-vinylformamide, N-vinylacetamide, and N-vinyl-N-methylacetamide.
Examples of the epoxy group-containing monomer include: glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 3, 4-epoxycyclohexylmethyl (meth) acrylate, 6-methyl-3, 4-epoxycyclohexylmethyl (meth) acrylate, and the like.
Examples of the amino group-containing monomer include: monoalkylamino (meth) acrylates such as monomethylaminoethyl (meth) acrylate, monoethylaminoethyl (meth) acrylate, monomethylaminopropyl (meth) acrylate, and monoethylaminopropyl (meth) acrylate.
The monomer having an alkylene oxide unit preferably has an ethylene oxide, propylene oxide or the like unit. Specific examples thereof include: 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-phenoxyethyl acrylate, methoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, ethoxypolypropylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, phenoxypolypropylene glycol (meth) acrylate, and the like.
Other vinyl monomers these monomers may be used alone or in combination of two or more. The other vinyl monomer is preferably contained in the acrylic copolymer in an amount of 80 to 99.9 wt%, more preferably 85 to 99.5 wt%, as a monomer unit constituting the copolymer. When the content is 80% by weight or more, the cohesive force is further improved. When the content is 99.9 wt% or less, both cohesion and stress relaxation are easily achieved.
The weight average molecular weight of the acrylic copolymer (A) is preferably from 50 to 200 ten thousand, more preferably from 70 to 180 ten thousand. In the range of 50 to 200 ten thousand, the cohesive force and the like are further improved, and therefore, the floating and peeling can be further suppressed, and the stress relaxation property is further improved. The acrylic polymer (A) preferably has a molecular weight distribution (Mw/Mn) representing the ratio of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn)) of 2 to 20. Within the above range, the floating and peeling are less likely to occur, and the adhesive force is further improved. The weight average molecular weight and the number average molecular weight are values in terms of polystyrene measured by a Gel Permeation Chromatography (GPC) method. Details of the measurement by GPC are described in examples.
The acrylic copolymer (a) can be obtained by polymerizing a monomer mixture. The polymerization may be a known polymerization method such as solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization, etc., and solution polymerization is preferable. The solvent used for the solution polymerization is preferably acetone, methyl acetate, ethyl acetate, toluene, xylene, anisole, methyl ethyl ketone, cyclohexanone, or the like. The polymerization temperature is preferably 60 to 120 ℃ and the polymerization time is preferably 5 to 12 hours.
The polymerization initiator is preferably a radical polymerization initiator. The radical polymerization initiator is not particularly limited as long as it is a compound capable of generating radicals at a polymerization temperature, and known compounds such as peroxides and azo compounds can be used.
Examples of peroxides include: dialkyl peroxides such as di-tert-butyl peroxide, dicumyl peroxide, tert-butylcumyl peroxide, α' -bis (tert-butylperoxy-m-isopropyl) benzene, and 2, 5-di (tert-butylperoxy) hexyne-3;
peroxyesters such as t-butyl peroxybenzoate, t-butyl peroxyacetate, and 2, 5-dimethyl-2, 5-di (benzoylperoxy) hexane;
ketone peroxides such as cyclohexanone peroxide, 3, 5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, etc.;
peroxyketals such as 2, 2-bis (4, 4-di-tert-butylperoxycyclohexyl) propane, 1-bis (tert-butylperoxy) 3, 3, 5-trimethylcyclohexane, 1-bis (tert-butylperoxy) cyclohexane, and n-butyl-4, 4-bis (tert-butylperoxy) valerate;
hydroperoxides such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, and 2, 5-dimethylcyclohexane-2, 5-dihydroperoxide;
diacyl peroxides such as benzoyl peroxide, decanoyl peroxide, lauroyl peroxide, and 2, 4-dichlorobenzoyl peroxide;
organic peroxides such as peroxydicarbonates such as bis (t-butylcyclohexyl) peroxydicarbonate, and mixtures of these compounds.
Azo compounds can be used, for example: 2, 2 ' -azobisbutyronitrile such as 2, 2 ' -azobisisobutyronitrile (abbreviated as AIBN) and 2, 2 ' -azobis (2-methylbutyronitrile);
2, 2 ' -azobisvaleronitriles such as 2, 2 ' -azobis (4-methoxy-2, 4-dimethylvaleronitrile) and 2, 2 ' -azobis (2, 4-dimethylvaleronitrile);
2, 2 '-azobispropionitrile such as 2, 2' -azobis (2-hydroxymethylpropionitrile);
1, 1 '-azobis-1-alkanenitriles such as 1, 1' -azobis (cyclohexane-1-carbonitrile), and the like.
The polymerization initiator may be used alone or in combination of two or more. The polymerization initiator is preferably used in an amount of 0.01 to 10 parts by weight, more preferably 0.1 to 2 parts by weight, based on 100 parts by weight of the monomer mixture.
< crosslinking agent (B) >
Next, the crosslinking agent (B) will be described. The crosslinking agent forms a resin network by undergoing a crosslinking reaction with the acrylic polymer, and the following effects are obtained: suppressing floating and peeling, suppressing light leakage, and maintaining high transparency even when exposed to a high-temperature and high-humidity environment.
Examples of the crosslinking agent (B) include: isocyanate-based compounds, epoxy compounds, aziridine compounds, acid anhydride group-containing compounds, carbodiimide compounds, N-methylol group-containing compounds, metal chelate compounds, and the like. Among these compounds, an isocyanate compound is preferably essential. Wherein the crosslinking agent (B) is other than the silane coupling agent (C) and the compound (D) having at least one epoxy group or epoxycyclohexyl group in the molecule.
Specifically, the isocyanate compound is an isocyanate monomer having 2 or more isocyanate groups, and specifically, it is preferable that: isocyanate monomers such as aromatic polyisocyanate, aliphatic polyisocyanate, aromatic aliphatic polyisocyanate and alicyclic polyisocyanate, and biuret, urethane and adduct.
Examples of the aromatic polyisocyanate include: 1, 3-phenylene diisocyanate, 4 ' -diphenyl diisocyanate, 1, 4-phenylene diisocyanate, 4 ' -diphenylmethane diisocyanate, 2, 4-tolylene diisocyanate, 2, 6-tolylene diisocyanate, 4 ' -toluidine diisocyanate, 2, 4, 6-triisocyanate toluene, 1, 3, 5-triisocyanate benzene, dianisidine diisocyanate, 4 ' -diphenyl ether diisocyanate, 4 ', 4 "-triphenylmethane triisocyanate, and the like.
Examples of the aliphatic polyisocyanate include: trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (also known as HMDI), pentamethylene diisocyanate, 1, 2-propylene diisocyanate, 2, 3-butylene diisocyanate, 1, 3-butylene diisocyanate, dodecamethylene diisocyanate, 2, 4, 4-trimethylhexamethylene diisocyanate, and the like.
Examples of the aromatic aliphatic polyisocyanate include: omega, omega '-diisocyanate-1, 3-dimethylbenzene, omega' -diisocyanate-1, 4-diethylbenzene, 1, 4-tetramethylxylylene diisocyanate, 1, 3-tetramethylxylylene diisocyanate, and the like.
Examples of the alicyclic polyisocyanate include: 3-isocyanatomethyl-3, 5, 5-trimethylcyclohexyl isocyanate (also known as IPDI, isophorone diisocyanate), 1, 3-cyclopentane diisocyanate, 1, 3-cyclohexane diisocyanate, 1, 4-cyclohexane diisocyanate, methyl-2, 6-cyclohexane diisocyanate, 4' -methylenebis (cyclohexyl isocyanate), 1, 4-bis (isocyanatomethyl) cyclohexane, and the like.
The biuret refers to a self-condensed product having a biuret bond obtained by self-condensing an isocyanate monomer. Specifically, for example, biuret products of hexamethylene diisocyanate are mentioned.
The uretate compound is a trimer of an isocyanate monomer, and examples thereof include: a trimer of hexamethylene diisocyanate, a trimer of isophorone diisocyanate, a trimer of toluene diisocyanate, and the like.
The adduct is a difunctional or higher isocyanate compound obtained by reacting an isocyanate monomer with a difunctional or higher active hydrogen-containing low molecular weight compound, and examples thereof include: a compound obtained by reacting trimethylolpropane with hexamethylene diisocyanate, a compound obtained by reacting trimethylolpropane with toluene diisocyanate, a compound obtained by reacting trimethylolpropane with xylylene diisocyanate, a compound obtained by reacting trimethylolpropane with isophorone diisocyanate, a compound obtained by reacting 1, 6-hexanediol with hexamethylene diisocyanate, and the like.
Examples of the difunctional or higher active hydrogen-containing low-molecular-weight compound include: ethylene glycol, propylene glycol, diethylene glycol, butanediol, 1, 6-hexanediol, 3-methyl-1, 5-pentanediol, 3 '-dimethylolheptane, 2-methyl-1, 8-octanediol, 3' -dimethylolheptane, 2-butyl-2-ethyl-1, 3-propanediol, polyoxyethylene glycol (ethylene oxide having a molar number of addition of 10 or less), polyoxypropylene glycol (propylene oxide having a molar number of addition of 10 or less), 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 8-octanediol, 1, 9-nonanediol, neopentyl glycol, butylethylpentanediol, 2-ethyl-1, 3-hexanediol, cyclohexanediol, cyclohexanedimethanol, aliphatic or alicyclic diols such as tricyclodecanedimethanol, cyclopentadienol and dimer diol;
aromatic glycols such as 1, 3-bis (2-hydroxyethoxy) benzene, 1, 2-bis (2-hydroxyethoxy) benzene, 1, 4-bis (2-hydroxyethoxy) benzene, 4 '-methylenediphenol, 4' - (2-norbornylene) diphenol, 4 '-dihydroxybiphenol, o-dihydroxybenzene, m-dihydroxybenzene, p-dihydroxybenzene, 4' -isopropylidenephenol, bisphenols such as bisphenol a and bisphenol F to which an alkylene oxide such as ethylene oxide or propylene oxide is added;
1, 1, 1-trimethylolpropane, 1, 1, 1-trimethylolbutane, 1, 1, 1-trimethylolpropane, 1, 1, 1-trimethylolpentane, 1, 1, 1-trimethylolhexane, 1, 1, 1-trimethylolheptane, 1, 1, 1-trimethyloloctane, 1, 1, 1-trimethylolnonane, 1, 1, 1-trimethyloldecane, 1, 1, 1-trimethylolundecane, 1, 1, 1-trimethyloldodecane, 1, 1, 1-trimethyloltridecane, 1, 1, 1-trimethyloltetradecane, 1, 1, 1-trimethylolpropane pentadecane, 1, 1, 1-trimethylolhexadecane, 1, 1, 1-trimethylolheptadecane, 1, 1, 1-trimethyloloctadecane, 1, 1, 1-trimethylolnonadecane, Trimethylolbranched alkanes such as 1, 1, 1-trimethylol-sec-butane, 1, 1, 1-trimethylol-tert-pentane, 1, 1, 1-trimethylol-tert-nonane, 1, 1, 1-trimethylol-tert-tridecane, 1, 1, 1-trimethylol-tert-heptadecane, 1, 1, 1-trimethylol-2-methyl-hexane, 1, 1, 1-trimethylol-3-methyl-hexane, 1, 1, 1-trimethylol-2-ethyl-hexane, 1, 1, 1-trimethylol-3-ethyl-hexane, 1, 1, 1-trimethylol-isoheptane, trimethylolbutene, trimethylol heptene, trimethylol pentene, trimethylol hexene, and the like, Trifunctional polyols such as trimethylolheptene, trimethyloloctene, trimethyloldecene, trimethyloldodecene, trimethyloltridecene, trimethylolpentadecene, trimethylolhexadecene, trimethylolheptadecene, trimethyloloctadecene, 1, 2, 6-butanetriol, 1, 2, 4-butanetriol and glycerol;
tetrafunctional or higher polyhydric alcohols such as pentaerythritol, dipentaerythritol, sorbitol, and xylitol;
aliphatic polyamines such as ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, hexylenediamine, heptylenediamine, octylenediamine, nonylenediamine, diaminodicyclohexylmethane, 3-aminomethyl-3, 5, 5-trimethylcyclohexylamine, 1, 3-bis (aminomethyl) cyclohexane, triethylenetetramine, diethylenetriamine, and triaminopropane;
aromatic polyamines such as phenylenediamine, toluenediamine, diaminodiphenylmethane, and diaminodiphenylether;
polythiols such as ethanedithiol, propanedithiol, butanedithiol, pentanethiol, hexanedithiol, heptanethiol, octanethiol, nonanedithiol, dimercaptodicyclohexylmethane, 3-mercaptomethyl-3, 5, 5-trimethylcyclohexylthiol, 1, 3-bis (mercaptomethyl) cyclohexane, 1, 4-bis (3-mercaptobutyryloxy) butane and pentaerythritol tetrakis (3-mercaptobutyrate). These polyfunctional active hydrogen-containing low-molecular compounds may be used alone or in combination of two or more.
The isocyanate-based curing agent is preferably a trifunctional isocyanate compound, and more preferably an adduct of an isocyanate monomer and a trifunctional active hydrogen-containing low-molecular-weight compound, from the viewpoint of forming a sufficient crosslinked structure. Specifically, it is preferable that: trimethylolpropane adduct of hexamethylene diisocyanate, trimethylolpropane adduct of toluene diisocyanate, trimethylolpropane adduct of isophorone diisocyanate, uric acid ester body of isophorone diisocyanate, trimethylolpropane adduct of xylylene diisocyanate, and particularly preferably: and aromatic aliphatic polyisocyanate compounds such as trimethylolpropane adduct of tolylene diisocyanate and trimethylolpropane adduct of xylylene diisocyanate. These polyisocyanate compounds may be used alone or in combination of two or more.
Examples of the epoxy compound include: bisphenol a-epichlorohydrin type epoxy resins, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerol triglycidyl ether, 1, 6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, diglycidylaniline, N ' -tetraglycidyl-m-xylylenediamine, 1, 3-bis (N, N ' -diglycidylaminomethyl) cyclohexane, N ' -tetraglycidylaminophenylmethane, and the like.
Examples of aziridine compounds include: n, N ' -diphenylmethane-4, 4 ' -bis (1-aziridinecarbonyl), N ' -toluene-2, 4-bis (1-aziridinecarbonyl), bis-isophthaloyl-1- (2-methylaziridine), tris-1-aziridinylphosphine oxide, N ' -hexamethylene-1, 6-bis (1-aziridinecarbonyl), 2 ' -bishydroxymethylbutanol-tris [3- (1-aziridinyl) propionate ], trimethylolpropane tris- β -aziridinylpropionate, tetramethylolmethane tris- β -aziridinylpropionate, tris-2, 4, 6- (1-aziridinyl) -1, 3, 5-triazine, 4' -bis (ethyleneiminocarbonylamino) diphenylmethane, and the like.
Carbodiimide compounds are listed as follows: a high molecular weight polycarbodiimide produced by subjecting a diisocyanate compound to a decarboxylation (decarboxylation) condensation reaction in the presence of a carbodiimidization catalyst. Examples of such high molecular weight polycarbodiimides include the Carbodilite series of Nisshinbo textile Co. Among them, Carbodilite (Carbodilite) V-01, 03, 05, 07, and 09 are preferable because they are excellent in compatibility with organic solvents.
The acid anhydride group-containing compound is a compound having 2 or more carboxylic anhydride groups, and is not particularly limited, and is preferably: tetracarboxylic dianhydride, tricarboxylic anhydride, hexacarboxylic dianhydride, maleic anhydride copolymerized resin, etc. In addition, polycarboxylic acids, polycarboxylic acid esters, polycarboxylic acid half-esters, and the like which can become anhydrides through dehydration reaction in the reaction are included in the "anhydride group-containing compound" of the present invention.
Examples of tetracarboxylic dianhydrides include: pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, oxydiphthalic dianhydride, diphenyl sulfone tetracarboxylic dianhydride, diphenyl sulfide tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, perylene tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, and the like.
Examples of the metal chelate compound include: polyvalent metals such as aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium, and zirconium, and complexes of acetylacetone or ethyl acetoacetate. Specific examples thereof include: aluminum ethyl acetoacetate diisopropoxide, aluminum triacetylacetonate, aluminum bis-ethyl acetoacetate monoacetylacetonate, and aluminum alkyl acetoacetate diisopropoxide.
These crosslinking agents may be used alone or in combination of two or more. Among these crosslinking agents, polyisocyanate compounds are preferable from the viewpoint of having both of substrate adhesion and removability.
The crosslinking agent (B) is preferably contained in an amount of 0.1 to 25 parts by weight, more preferably 0.5 to 20 parts by weight, based on 100 parts by weight of the acrylic copolymer. When the amount is within the above range, both the cohesive force and the stress relaxation property are easily achieved.
< silane coupling agent (C) >
The adhesive of the present invention contains a silane coupling agent. By using the silane coupling agent, floating or peeling in the case of exposure to a high-temperature environment or a high-temperature and high-humidity environment can be suppressed.
Examples of the silane coupling agent in the present specification include: (meth) acryloyloxy-containing alkoxysilane compounds such as 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 3- (meth) acryloyloxypropyltripropoxysilane, 3- (meth) acryloyloxypropyltributoxysilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane and 3- (meth) acryloyloxypropylmethyldiethoxysilane;
alkoxysilane compounds having a vinyl group such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltributoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, etc.;
alkoxysilane compounds having an amino group such as 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltripropoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldiethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane;
alkoxysilane compounds having a mercapto group such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltripropoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 3-mercaptopropylmethyldiethoxysilane;
alkoxysilane compounds having an epoxy group such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltripropoxysilane, 3-glycidoxypropyltributoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane;
tetraalkoxysilane compounds such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane and tetrabutoxysilane;
3-chloropropyltrimethoxysilane, N-hexyltrimethoxysilane, N-hexyltriethoxysilane, N-decyltrimethoxysilane, N-decyltriethoxysilane, styryltrimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, 3-triethoxysilyl-N- (1, 3-dimethylbutylidene) propylamine, 1, 3, 5-tris (3-trimethoxysilylpropyl) isocyanurate, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, hexamethyldisilazane, silicone resins having alkoxysilyl groups in the molecule, and the like.
The silane coupling agent may be used alone or in combination of two or more. Among these silane coupling agents, silane coupling agents having an ethoxy group are preferable from the viewpoint of having both substrate adhesion and removability. The silane coupling agent is used preferably in a range of 0.01 to 2 parts by weight, more preferably 0.05 to 1 part by weight, based on 100 parts by weight of the acrylic copolymer (a).
< Compound (D) having at least one epoxy group or epoxycyclohexyl group in the molecule >
The compound (D) having at least one epoxy group or epoxycyclohexyl group in the molecule in the present specification contributes to suppression of floating and peeling and suppression of light leakage by forming a covalent bond or a hydrogen bond with the surface of the substrate.
The compound (D) is a compound represented by the formula [ I ] or the formula [ II ], and p is an integer in the range of 1. ltoreq. p.ltoreq.30, preferably an integer in the range of 1. ltoreq. p.ltoreq.30, and more preferably an integer in the range of 5. ltoreq. p.ltoreq.20.
The formula [ II]In, X1～X4Each independently represents an alkyl group, and examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. Among them, methyl, ethyl, propyl, and butyl are preferable, and methyl is more preferable.
X5The divalent organic residue having 1 to 10 carbon atoms includes: examples of the alkylene group include a linear alkylene group such as a methylene group, a 1, 2-ethylene group, a 1, 3-propylene group, a 1, 4-butylene group, a 1, 5-pentylene group, a 1, 6-hexylene group, a 1, 7-heptylene group, a 1, 8-octylene group, a 1, 9-nonylene group, and a 1, 10-decylene group, and a branched alkylene group such as a 1, 1-ethylene group, a 1, 2-propylene group, a 1, 1-propylene group, a 1-methyl-1, 3-butylene group, a 2-methyl-1, 3-butylene group, a 1, 2-dimethyl-1, 2-butylene group, a 1, 1-butylene group, and an ethyl-1, 2-ethylene group. Among these alkylene groups, a linear alkylene group is preferable, and methylene, 1, 2-ethylene, 1, 3-propylene, and 1, 4-butylene are more preferable.
Y represents an epoxy group or an epoxycyclohexyl group. Among them, epoxycyclohexyl is more preferable.
q is an integer in the range of 5. ltoreq. q.ltoreq.50, preferably an integer in the range of 10. ltoreq. q.ltoreq.50, more preferably an integer in the range of 10. ltoreq. q.ltoreq.40.
r is an integer in the range of 5. ltoreq. r.ltoreq.50, preferably an integer in the range of 10. ltoreq. r.ltoreq.50, more preferably an integer in the range of 10. ltoreq. r.ltoreq.40.
q + r is an integer in the range of 10. ltoreq. q + r. ltoreq.100, preferably an integer in the range of 10. ltoreq. q + r. ltoreq.80, more preferably an integer in the range of 20. ltoreq. q + r. ltoreq.80.
Among the compounds (D), the compounds represented by the formula [ I ] include, specifically: danacol (Denacol) EX810, danacol (Denacol) EX811, danacol (Denacol) EX850, danacol (Denacol) EX851, danacol (Denacol) EX821, danacol (Denacol) EX830, danacol (Denacol) EX832, danacol (Denacol) EX841, danacol (Denacol) EX861 "manufactured by Nagase ChemteX limited company.
Among the compounds (D), the compounds represented by the formula [ II ] include, specifically: KR-516, X-41-1810, X-40-2651, X-40-9296, KR-513, KR-511 (all manufactured by shin-Etsu chemical industries, Ltd.), and the like.
The compound (D) is preferably contained in an amount of 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, and particularly preferably 0.05 to 2 parts by weight, based on 100 parts by weight of the acrylic copolymer (a). When the content is 0.01 parts by weight or more, sufficient adhesion to the substrate can be obtained. When the content is within the above range, both the substrate adhesion and the removability are easily achieved.
In the adhesive of the present invention, various resins, oils, softeners, dyes, pigments, antioxidants, ultraviolet absorbers, weather stabilizers, plasticizers, fillers, antioxidants, antistatic agents, and the like may be blended as optional components within a range not to impair the effects of the present invention.
The adhesive of the present invention is suitable as an adhesive for optical members, and can be very usefully used as: various plastic sheets, general labels, sheets, paints, elastic wall materials, coating waterproof materials, flooring materials, tackiness imparting agents, adhesives for laminated structures, sealants, Molding materials, coating agents for surface modification, adhesives (magnetic recording media, ink adhesives, casting adhesives, baked brick (brick) adhesives, graft materials, microcapsules, glass fiber sizing (glass fiber sizing), etc.), urethane foams (hard, semi-hard, soft), urethane Reaction Injection Molding (RIM), Ultraviolet (UV), Electron Beam (EB) hardening resins, high-solid paints (high solid paints), thermosetting elastomers, microcellular (microcellular), fiber processing agents, plasticizers, sound absorbing materials, damping materials, surfactants, gel coating agents, resins for artificial marble, and the like, Impact resistance imparting agents for artificial marbles, resins for inks, films (laminating adhesives, protective films, etc.), resins for laminated glass (laminated glass), reactive diluents, various molding materials, elastic fibers, artificial leathers, synthetic leathers, and other raw materials, and can also be used as various resin additives and raw materials therefor.
< adhesive sheet >
The adhesive sheet of the present invention comprises a substrate and an adhesive layer comprising the adhesive of the present invention. The adhesive sheet is obtained by, for example, applying an adhesive to a substrate and drying the adhesive to form an adhesive layer. The adhesive sheet is obtained by applying an adhesive to a releasable sheet, drying the adhesive to form an adhesive layer, and bonding substrates to each other. The adhesive layer may be provided on at least one surface of the base material. In the present invention, the sheet, the film and the tape are synonymous. In addition, it is a matter of course that a releasable sheet is attached to the surface of the adhesive layer which is not in contact with the substrate.
When applying the adhesive, a suitable liquid medium may be added, for example: hydrocarbon solvents such as toluene, xylene, hexane, and heptane; ester solvents such as ethyl acetate and butyl acetate; ketone solvents such as acetone and methyl ethyl ketone; halogenated hydrocarbon solvents such as dichloromethane and chloroform; the viscosity is adjusted by an ether solvent such as diethyl ether, methoxytoluene, or dioxane, and an organic solvent such as another hydrocarbon solvent. In addition, the adhesive may be heated to lower the viscosity. Among them, water, alcohol and the like are preferably avoided because they inhibit the crosslinking reaction between the acrylic copolymer (B) and the polyisocyanate compound.
Examples of the substrate include: cellophane, plastic, rubber, foam, cloth, rubber cloth (rubber cloth), resin impregnated cloth, glass plate, wood, and the like. The substrate may be a plate or a film. The base material is also preferably a structure in which a plurality of base materials are stacked or separated.
Examples of plastics include: polyolefin resins such as polyvinyl alcohol, triacetyl cellulose, polypropylene, polyethylene, polycycloolefin, and ethylene-vinyl acetate copolymer, polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, polycarbonate resins, polynorbornene resins, polyarylate resins (copolymerized resins of PAR: bisphenol a and phthalic acid), polyacrylic resins, polyphenylene sulfide resins, polystyrene resins, polyamide resins, polyimide resins, and epoxy resins (resins obtained by reacting an epoxy group-containing resin with polyamine or carboxylic anhydride).
In the present invention, the adhesive can be applied by a known method. Examples thereof include: meyer bar, applicator (applicator), brush, spray, roller, gravure coater, pattern coater, lip coater, comma wheel coater, knife coater, reverse coater, spin coater, and the like. The drying method is not particularly limited, and methods using hot air drying, infrared rays or a reduced pressure method can be exemplified. The drying conditions may be generally hot air heating at about 60 ℃ to 160 ℃.
The thickness of the adhesive layer is preferably 0.1 to 300. mu.m, more preferably 1 to 100. mu.m. When the thickness is less than 0.1. mu.m, sufficient adhesive force may not be obtained, and even when the thickness exceeds 300. mu.m, the properties such as adhesive force may not be further improved in many cases.
The adhesive sheet of the present invention can be suitably used for bonding optical members. That is, it is preferable to use an optical member on the substrate. Specific examples of the optical member include: a polarizing plate, a retardation film, an elliptically polarizing film, an antireflection film, a brightness improving film, and the like.
The adhesive sheet of the present invention using an optical member on a substrate is also preferably used as a liquid crystal cell member by being attached to a glass member of a liquid crystal cell. In the case where the optical member is a polarizing plate, the adhesive layer has good stress relaxation properties when placed in a high-temperature environment or a high-temperature and high-humidity environment, and thus light leakage due to warpage of the polarizing plate can be suppressed.
The adhesive sheet of the present invention can be preferably used for various electronic components such as liquid crystal displays, plasma displays, touch panels, electrode peripheral components, and glass components such as protective films, building materials, and window glasses for vehicles, but can also be used for plastics such as polyolefin, Acrylonitrile Butadiene Styrene (ABS), acrylic, cardboard, wood, plywood, stainless steel, aluminum, and the like.
[ examples ]
The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. In the examples, "part" means "part by weight", and "%" means "% by weight".
< Synthesis of acrylic copolymer (A) >
< Synthesis example 1>
In a reaction vessel (hereinafter, may be simply referred to as "reaction vessel") equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introduction tube, 99.4 parts of butyl acrylate, 0.5 parts of acrylic acid, 0.1 parts of 2-hydroxyethyl acrylate, 100 parts of ethyl acetate, and 0.025 parts of 2, 2' -Azobisisobutyronitrile (AIBN) were charged, and then the air in the reaction vessel was replaced with nitrogen. Then, the reaction mixture was heated to 80 ℃ under nitrogen atmosphere with stirring to start the reaction. Further, the reaction solution was reacted at a reflux temperature for 7 hours. After the reaction, the reaction mixture was cooled and diluted with ethyl acetate to obtain a copolymer solution having a nonvolatile content of 30% and a viscosity of 3000 mPas. Further, the weight average molecular weight (Mw) of the acrylic copolymer was measured by GPC, and as a result, the weight average molecular weight was 100 ten thousand. The obtained copolymer was designated as copolymer (A-1).
Synthesis examples 2 to 20
Acrylic copolymers (a-2) to (a-20) were synthesized in the same manner as in synthesis example 1, except that the raw materials and amounts shown in table 1 and table 2 were changed, respectively, instead of the raw materials used in synthesis example 1. The weight average molecular weight of each of the obtained acrylic copolymers is shown in tables 1 and 2.
< measurement of weight-average molecular weight (Mw) >
The weight average molecular weight (Mw) was measured using GPC "LC-GPC system" manufactured by shimadzu corporation, and determined based on a converted value of polystyrene as a standard substance. The measurement conditions are shown below.
Device name: manufactured by Shimadzu corporation, LC-GPC System, "Proamince"
Pipe column: GMHXL manufactured by 4 Tosoh corporation and HXL-H manufactured by 1 Tosoh corporation are connected in series.
Mobile phase solvent: tetrahydrofuran (THF)
Flow rate: 1.0mL/min
Temperature of the pipe column: 40 deg.C
(example 1)
An adhesive was obtained by blending the copolymer solution obtained in synthetic example 1 as the acrylic copolymer (a) (the amount of the acrylic copolymer (a-1) in the solution was 100 parts), 1 part of an adduct of toluene diisocyanate and trimethylolpropane as the crosslinking agent (B), 0.1 part of 3-glycidoxypropyltriethoxysilane as the silane coupling agent (C), 1 part of the compound (D-1) shown in table 5 as the compound (D), and further blending ethyl acetate in an amount such that the nonvolatile content became 20%.
The adhesive was applied to a 38 μm thick polyethylene terephthalate (Cerapel MF; manufactured by Toray Film processing Co., Ltd.) release sheet so that the dried thickness became 25 μm, and dried at 100 ℃ for 2 minutes to form an adhesive layer. Then, a laminate structure of a polarizing plate (HLC2-5618 manufactured by Santly (SANRITZ)) having a laminated structure in which a polyvinyl alcohol (PVA) polarizing element is sandwiched between triacetyl cellulose films (hereinafter referred to as "TAC films") on both surfaces thereof was laminated on the adhesive layer, and an adhesive sheet having a structure of so-called "release film/adhesive layer/TAC film/PVA/TAC film" was obtained. Then, the obtained adhesive sheet was aged at 35 ℃ and a relative humidity of 55% for 1 week to obtain a laminate.
(examples 2 to 34, comparative examples 1 to 10)
Adhesives were obtained in the same manner as in example 1, except that the materials and the amounts of blending shown in tables 3 and 4 were changed, respectively, instead of the materials used in example 1. Further, an adhesive sheet and a laminate were obtained in the same manner as in example 1.
The details of the compound (D) used are shown in table 5.
The obtained laminate was evaluated by the following method.
(1) Evaluation of Heat resistance and Wet Heat resistance
The obtained laminate was cut into a size of 160mm in width and 120mm in length. Subsequently, the peelable sheets were peeled off from the cut laminate, and attached to the alkali-free glass plate using a laminator. Then, the glass plate to which the laminate was attached was held in an autoclave at 50 ℃ under 5 atm for 20 minutes, and the respective members were closely adhered to each other, thereby obtaining a measurement sample. The heat resistance of the test sample was evaluated as resistance evaluation in a high-temperature environment. That is, the test specimen was left at 85 ℃ for 500 hours, and then the presence or absence of foaming, floating, and peeling was visually observed.
The test samples were evaluated for resistance to moist heat as resistance in a high-temperature and high-humidity environment. That is, the measurement sample was left at 60 ℃ and 95% relative humidity for 500 hours, and then the presence or absence of foaming, floating, and peeling was visually observed. The heat resistance and the moist heat resistance were evaluated based on the following criteria.
Very good: foaming, floating and peeling were not observed at all, and the results were good.
O: any of foaming, floating and peeling of 0.5mm or less was observed, but there was no problem in practical use.
X: foaming, floating and peeling were found on the whole surface, and the use was impossible.
(2) Evaluation of light leakage
The obtained laminate was cut into a size of 160mm in width and 120mm in length. Then, the peelable sheets were peeled off from the cut laminate, and 2 laminates were attached to both surfaces of the alkali-free glass plate using a laminator so that the absorption axes of the polarizing plates were orthogonal to each other, thereby obtaining a pressure-bonded product. Then, the pressure-bonded product was held in an autoclave at 50 ℃ under 5 atm for 20 minutes, and the respective members were closely adhered to each other, thereby obtaining a measurement sample. After the measurement sample was left at 85 ℃ for 500 hours, light leakage when light was transmitted through the polarizing plate was visually observed. The light leakage was evaluated based on the following criteria.
Very good: no white spots and good.
O: although white spots were observed in a very small portion, no total white spots were observed, and no practical problem was observed.
X: white spots exist on the whole surface, and the white spots cannot be used.
(3) Evaluation of Re-peelability
The obtained laminate was cut into a size of 160mm in width and 120mm in length. Subsequently, the peelable sheets were peeled off from the cut laminate, and attached to the alkali-free glass plate using a laminator. Then, the reaction mixture was held in an autoclave at 50 ℃ under 5 atm for 20 minutes to adhere the respective members to each other, thereby obtaining a measurement sample. After the measurement sample was left at 85 ℃ for 3 hours, a peel test in which the sample was pulled at a speed of 300mm/min in a direction of 180 ℃ was performed using a tensile tester ("Tensilon") manufactured by Ahonda (Orientec) under an environment of 23 ℃ and a relative humidity of 50%. Then, the haze of the glass surface after the peeling was visually observed, and the evaluation was performed based on the following criteria.
O: no residual gum and no blur were observed, and the results were good.
X: the residual glue and the blur were confirmed, and the method was not practical.
(4) Evaluation of adhesive force
The obtained laminate was cut into a size of 25mm in width and 100mm in length. Subsequently, the peelable sheets were peeled off from the cut laminate, and attached to the alkali-free glass plate using a laminator. Then, the reaction mixture was held in an autoclave at 50 ℃ under 5 atm for 20 minutes to adhere the respective members to each other, thereby obtaining a measurement sample. The measurement sample was left at 23 ℃ for 1 day, and then the adhesion (adhesion after 1 day of application) was measured under an environment of 23 ℃ and a relative humidity of 50% using a tensile tester ("Tensilon" manufactured by Ahond (Orientec)) under conditions of a peel speed of 300mm/min and a peel angle of 180 ℃. The measurement specimen was left at 23 ℃ for 14 days, and the adhesive force (adhesive force after 14 days of application) was measured in the same manner.
From the results in tables 6, 7 and 8, the adhesive of the present invention is excellent in durability, light leakage and removability under high temperature environment and high temperature and high humidity environment as shown in examples 1 to 34. On the other hand, all of comparative examples 1 to 10 could not satisfy the above characteristics.
Figure BDA0001160669990000211
Figure BDA0001160669990000221
Figure BDA0001160669990000231
Figure BDA0001160669990000241
Figure BDA0001160669990000251
Figure BDA0001160669990000261
[ Table 6]
Figure BDA0001160669990000271
[ Table 7]
Figure BDA0001160669990000281
[ Table 8]
Figure BDA0001160669990000282

Claims (8)

1. An adhesive comprising an acrylic copolymer (A), a crosslinking agent (B), a silane coupling agent (C), and a compound (D) having at least one epoxycyclohexyl group in the molecule, wherein:
the acrylic copolymer (A) is a copolymer containing at least a carboxyl group-containing monomer (a-1) unit and a hydroxyl group-containing monomer (a-2) unit as monomer units constituting the copolymer,
in the acrylic copolymer (A), the carboxyl group-containing monomer (a-1) unit is 0.5 to 20% by weight,
the crosslinking agent (B) contains an isocyanate-based compound, and
the compound (D) having at least one epoxycyclohexyl group in the molecule is a compound represented by the following formula [ II ],
Figure FDF0000010438600000011
wherein q and r are integers representing a repeating unit, q is not less than 5 and not more than 50, r is not less than 5 and not more than 50, and q + r is not less than 10 and not more than 100; x1～X4Each independently represents an alkyl group, X5Represents a divalent organic residue having 1 to 10 carbon atoms, and Y represents an epoxycyclohexyl group.
2. The adhesive of claim 1, wherein: the acrylic copolymer (A) contains 0.05 to 2 parts by weight of the compound (D) having at least one epoxycyclohexyl group in the molecule per 100 parts by weight of the acrylic copolymer (A).
3. Adhesive according to claim 1 or 2, characterized in that: the crosslinking agent (B) is an isocyanate compound.
4. Adhesive according to claim 1 or 2, characterized in that: the silane coupling agent (C) is a silane coupling agent having an ethoxy group.
5. Adhesive according to claim 1 or 2, characterized in that: the crosslinking agent (B) is contained in an amount of 0.5 to 20 parts by weight based on 100 parts by weight of the acrylic copolymer (A).
6. An adhesive sheet, comprising: a substrate, and an adhesive layer comprising the adhesive according to any one of claims 1 to 5.
7. A polarizing plate adhesive sheet, comprising: a polarizing plate, and an adhesive layer comprising the adhesive according to any one of claims 1 to 5.
8. A liquid crystal cell member comprising: a glass plate, an adhesive layer comprising the adhesive according to any one of claims 1 to 5, and an optical member.
CN201611052481.6A 2015-11-25 2016-11-24 Adhesive, adhesive sheet using same, polarizing plate adhesive sheet, and liquid crystal cell member Active CN106916555B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2015229257A JP6330792B2 (en) 2015-11-25 2015-11-25 Adhesive and adhesive sheet using the same
JP2015-229257 2015-11-25

Publications (2)

Publication Number Publication Date
CN106916555A CN106916555A (en) 2017-07-04
CN106916555B true CN106916555B (en) 2021-01-12

Family

ID=58816799

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201611052481.6A Active CN106916555B (en) 2015-11-25 2016-11-24 Adhesive, adhesive sheet using same, polarizing plate adhesive sheet, and liquid crystal cell member

Country Status (4)

Country Link
JP (1) JP6330792B2 (en)
KR (1) KR102571645B1 (en)
CN (1) CN106916555B (en)
TW (1) TWI707017B (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102477377B1 (en) * 2018-08-27 2022-12-15 주식회사 엘지화학 Pressure sensitive adhesive composition, optical laminate and display device
CN112210325B (en) * 2019-07-10 2023-11-17 日东电工（上海松江）有限公司 Adhesive composition
EP3885419A1 (en) * 2020-03-23 2021-09-29 3M Innovative Properties Company Pressure sensitive adhesive having low voc characteristics
CN118109147B (en) * 2024-02-28 2024-09-13 广州市昌鹏实业有限公司 Adhesive for polaroid

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102051146A (en) * 2009-10-27 2011-05-11 琳得科株式会社 Water-dispersed acrylic acid series sticker composition and adhesion sheet and preparation method thereof
JP2013224431A (en) * 2013-05-20 2013-10-31 Toyo Ink Sc Holdings Co Ltd Optical pressure-sensitive adhesive agent, and optical pressure-sensitive adhesive sheet
JP2014234419A (en) * 2013-05-31 2014-12-15 日本カーバイド工業株式会社 Adhesive composition for optical members and optical film

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4376492B2 (en) 2002-07-29 2009-12-02 日本カーバイド工業株式会社 Adhesive composition and adhesive sheet
JP2007169329A (en) 2005-12-19 2007-07-05 Saiden Chemical Industry Co Ltd Adhesive composition for optical use and adhesive sheet
KR101023842B1 (en) 2008-01-11 2011-03-22 주식회사 엘지화학 Pressure-sensitive adhesive compositions, polarizers and liquid crystal displays comprising the same
JP5591477B2 (en) * 2008-03-13 2014-09-17 日東電工株式会社 Optical member pressure-sensitive adhesive composition, optical member pressure-sensitive adhesive layer, pressure-sensitive adhesive optical member, transparent conductive laminate, touch panel, and image display device
JP5243182B2 (en) 2008-10-22 2013-07-24 日東電工株式会社 Optical member pressure-sensitive adhesive composition, optical member pressure-sensitive adhesive layer, pressure-sensitive adhesive optical member, and image display device
JP5436394B2 (en) * 2010-10-29 2014-03-05 チェイル インダストリーズ インコーポレイテッド Adhesive composition
JP5758261B2 (en) 2011-10-06 2015-08-05 日東電工株式会社 Optical pressure-sensitive adhesive, pressure-sensitive adhesive layer, optical film, and image display device
JP6093624B2 (en) 2012-05-24 2017-03-08 日東電工株式会社 Adhesive layer for optical film, optical film with adhesive layer, and image display device
JP6241816B2 (en) * 2013-03-29 2017-12-06 サイデン化学株式会社 Optical pressure-sensitive adhesive composition and method for producing optical pressure-sensitive adhesive composition
CN109554143A (en) * 2014-03-31 2019-04-02 日东电工株式会社 Pressure-sensitive adhesive for optical films composition, pressure-sensitive adhesive for optical films layer, optical film and image display device with adhesive phase
KR102513258B1 (en) * 2016-02-29 2023-03-23 토요잉크Sc홀딩스주식회사 Adhesive agent and adhesive sheet

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102051146A (en) * 2009-10-27 2011-05-11 琳得科株式会社 Water-dispersed acrylic acid series sticker composition and adhesion sheet and preparation method thereof
JP2013224431A (en) * 2013-05-20 2013-10-31 Toyo Ink Sc Holdings Co Ltd Optical pressure-sensitive adhesive agent, and optical pressure-sensitive adhesive sheet
JP2014234419A (en) * 2013-05-31 2014-12-15 日本カーバイド工業株式会社 Adhesive composition for optical members and optical film

Also Published As

Publication number Publication date
CN106916555A (en) 2017-07-04
JP6330792B2 (en) 2018-05-30
KR20170061070A (en) 2017-06-02
TW201718805A (en) 2017-06-01
JP2017095597A (en) 2017-06-01
TWI707017B (en) 2020-10-11
KR102571645B1 (en) 2023-08-25

Similar Documents

Publication Publication Date Title
JP6232723B2 (en) Adhesive and adhesive sheet using the same
CN107418480B (en) Adhesive, optical adhesive sheet, polarizing plate adhesive sheet, and liquid crystal cell member
CN107129778B (en) Adhesive, optical adhesive sheet, polarizing plate adhesive sheet, and liquid crystal cell member
JP6245032B2 (en) Adhesive and adhesive film using the same
JP2013127012A (en) Adhesive, adhesive sheet and display
JP6600954B2 (en) Re-peelable pressure-sensitive adhesive and pressure-sensitive adhesive sheet using the same
CN106916555B (en) Adhesive, adhesive sheet using same, polarizing plate adhesive sheet, and liquid crystal cell member
JP6631022B2 (en) Adhesive and adhesive sheet using the same
KR20180068322A (en) Adhesive composition for optical film, adhesive layer, optical member and image display device
JP6938974B2 (en) Adhesives and adhesive sheets
JP2019085479A (en) Optical adhesive and optical adhesive sheet
CN116802251A (en) Adhesive for flexible display, adhesive sheet, laminate, and flexible display
JP6679985B2 (en) Adhesive and adhesive sheet using the same
JP2014028983A (en) Adhesive, adhesive sheet and display
JP7331673B2 (en) Adhesive composition and adhesive sheet
KR101462412B1 (en) The adhesive, adhesive sheet and display
JP6330776B2 (en) Adhesive and adhesive sheet using the same
JP6213609B2 (en) Adhesive, adhesive sheet and display
JP2018135524A (en) Adhesive and adhesive sheet using the same
JP2018150536A (en) Adhesive and adhesive sheet prepared therewith

Legal Events

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