CN115322693A - Adhesive composition, adhesive and adhesive sheet - Google Patents

Adhesive composition, adhesive and adhesive sheet Download PDF

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Publication number
CN115322693A
CN115322693A CN202211046246.3A CN202211046246A CN115322693A CN 115322693 A CN115322693 A CN 115322693A CN 202211046246 A CN202211046246 A CN 202211046246A CN 115322693 A CN115322693 A CN 115322693A
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Prior art keywords
adhesive
meth
acrylate
monomer
mass
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大桥仁
高桥洋一
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Lintec Corp
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Lintec Corp
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Application filed by Lintec Corp filed Critical Lintec Corp
Priority to CN202211046246.3A priority Critical patent/CN115322693A/en
Publication of CN115322693A publication Critical patent/CN115322693A/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
    • C08G18/6225—Polymers of esters of acrylic or methacrylic acid
    • C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/625—Polymers of alpha-beta ethylenically unsaturated carboxylic acids; hydrolyzed polymers of esters of these acids
    • C08G18/6254—Polymers of alpha-beta ethylenically unsaturated carboxylic acids and of esters of these acids containing hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
    • C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
    • C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
    • C08G18/8022—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203 with polyols having at least three hydroxy groups
    • C08G18/8029—Masked aromatic polyisocyanates
    • 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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • 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
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3472—Five-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
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3495—Six-membered rings condensed with carbocyclic rings
    • 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
    • C09J11/04—Non-macromolecular additives inorganic
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/124—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)

Abstract

The invention provides an adhesive composition, an adhesive and an adhesive sheet, wherein the adhesive composition is used for forming the adhesive used for contacting with a metal member, and comprises the following components: a (meth) acrylate polymer (A) which contains, as a monomer unit constituting the polymer, more than 15% by mass and 30% by mass or less of a monomer having a hydroxyl group and does not contain a monomer having a carboxyl group; and a benzotriazole-based rust inhibitor (B). The adhesive composition can inhibit corrosion of a metal member in contact therewith, and is excellent in resistance to wet-heat whitening.

Description

Adhesive composition, adhesive and adhesive sheet
The present invention is a divisional application of chinese patent application having an application number of 201480077497.5, an application date of 2014, 3 and 28, entitled "adhesive composition, adhesive, and adhesive sheet".
Technical Field
The present invention relates to an adhesive and an adhesive sheet used in contact with a metal member, particularly a metal mesh of a touch panel, and an adhesive composition constituting the adhesive.
Background
In recent years, in various mobile electronic devices such as smartphones and tablet computers, the use of touch panels as displays has been increasing. As the touch panel, there are a resistive film system, a capacitive system, and the like, but in a mobile electronic device such as a mobile phone, the capacitive system is mainly used.
Electrodes of small touch panels used in smart phones and the like are mostly formed of transparent conductive films made of tin-doped indium oxide (ITO). However, since it is difficult to reduce the resistance value of ITO to 10 Ω/□ or less, signal degradation occurs when ITO is used for a large-sized electrode pattern, and it is difficult to increase the size of the touch panel.
Therefore, copper having a resistance value of 10 Ω/□ or less has attracted attention as an electrode material for a touch panel, and various copper electrodes have been studied. However, since copper is more easily corroded than ITO, if an adhesive used for an ITO electrode is used directly for a copper electrode, the copper electrode is corroded. Thus, an adhesive that does not corrode copper electrodes is required.
However, the touch panel is sometimes exposed to high temperature and high humidity conditions, and is required to have durability that can be used without any problem even under such conditions. However, in the conventional touch panel, when the touch panel is returned to normal temperature and normal humidity after high-temperature and high-humidity conditions, the problem of whitening of the adhesive layer (wet heat whitening) is likely to occur.
Patent document 1 discloses an adhesive for adhering to an electromagnetic wave shielding film, which contains a near-infrared ray absorbing dye for imparting a near-infrared ray absorbing effect and a benzotriazole compound for preventing deterioration of the near-infrared ray absorbing dye.
Documents of the prior art
Patent document
Patent document 1: japanese patent No. 4818236
Disclosure of Invention
Technical problems to be solved by the invention
However, the adhesive of patent document 1 is used for an optical filter of a plasma display panel, and cannot be applied to a touch panel of different applications. For example, when the adhesive is applied to a touch panel, the above-described problem of whitening due to heat and humidity occurs.
The present invention has been made in view of the above circumstances, and an object thereof is to provide an adhesive composition, an adhesive and an adhesive sheet which can suppress corrosion of a metal member in contact therewith and are excellent in resistance to wet-heat whitening.
Means for solving the problems
In order to achieve the above object, the present invention provides an adhesive composition for constituting an adhesive used in contact with a metal member, comprising: a (meth) acrylate polymer (A) containing a monomer having a hydroxyl group in an amount of more than 15% by mass and not more than 30% by mass as a monomer unit constituting the polymer, and containing no monomer having a carboxyl group; and a benzotriazole-based rust inhibitor (B) (invention 1).
The (meth) acrylate polymer (a) in the adhesive composition of the invention (invention 1) contains a hydroxyl group-containing monomer in the above-mentioned amount as a monomer unit constituting the polymer, and the adhesive obtained therefrom is excellent in wet-heat whitening resistance. On the other hand, if a predetermined amount of hydrophilic groups such as hydroxyl groups are present in the adhesive as described above, water is easily absorbed into the adhesive, and metal members in contact with the adhesive are easily corroded. However, the adhesive composition of the invention (invention 1) contains the benzotriazole-based rust inhibitor (B), and thus can suppress corrosion of a metal member in contact therewith. In addition, since the (meth) acrylate polymer (a) in the adhesive composition (invention 1) does not contain a carboxyl group-containing monomer, corrosion of a metal member due to a carboxyl group (acid) can be prevented.
In the above invention (invention 1), the benzotriazole-based rust inhibitor (B) preferably contains at least one selected from the group consisting of 1H-benzotriazole, 1H-tolyltriazole, 1- [ N, N-bis (2-ethylhexyl) aminomethyl ] benzotriazole and 1- [ N, N-bis (2-ethylhexyl) aminomethyl ] methylbenzotriazole (invention 2).
In the above inventions (inventions 1 and 2), it is more preferable that the (meth) acrylate polymer (a) contains, as a monomer unit constituting the polymer, a hard monomer having a glass transition temperature of 70 ℃ or higher as a homopolymer (invention 3).
In the above inventions (inventions 1 to 3), it is more preferable that the (meth) acrylate polymer (a) contains 2-ethylhexyl (meth) acrylate as a monomer unit constituting the polymer (invention 4).
In the above inventions (inventions 1 to 4), it is more preferable that the adhesive composition further contains a crosslinking agent (C) (invention 5).
The second aspect of the present invention provides an adhesive obtained by crosslinking the adhesive composition (invention 1 to 5) (invention 6).
In the above invention (invention 6), a dielectric constant at 1.0MHz is more preferably 2.0 to 8.0 (invention 7).
Third, the present invention provides an adhesive sheet comprising: two release sheets; and an adhesive layer sandwiched between the two release sheets so as to be in contact with the release surfaces of the release sheets, wherein the adhesive layer is composed of the adhesive (inventions 6 and 7) (invention 8).
In the above invention (invention 8), the adhesive layer is preferably disposed on the touch panel so as to be in contact with the metal mesh (invention 9).
Effects of the invention
According to the adhesive composition, the adhesive and the adhesive sheet of the present invention, corrosion of a metal member in contact therewith can be suppressed, and the adhesive composition, the adhesive and the adhesive sheet are excellent in wet-heat whitening resistance.
Drawings
Fig. 1 is a sectional view of an adhesive sheet according to an embodiment of the present invention.
Fig. 2 is a cross-sectional view showing one configuration example of the touch panel.
Detailed Description
Hereinafter, embodiments of the present invention will be described.
[ adhesive composition ]
The adhesive composition of the present embodiment (hereinafter referred to as "adhesive composition P") is an adhesive composition for constituting an adhesive used in contact with a metal member. As the metal member, a copper mesh as an electrode in a capacitive touch panel can be exemplified more preferably, but the metal member is not limited thereto.
The adhesive composition P contains: a (meth) acrylate polymer (A) containing a monomer having a hydroxyl group (hydroxyl group-containing monomer) in an amount of more than 15% by mass and not more than 30% by mass as a monomer unit constituting the polymer, and not containing a monomer having a carboxyl group (carboxyl group-containing monomer); and a benzotriazole-based rust inhibitor (B), preferably further containing a crosslinking agent (C). In the present specification, the term (meth) acrylate refers to both acrylate and methacrylate. Other similar terms are also the same. Also, the term "copolymer" is also included in the term "polymer".
The (meth) acrylate polymer (a) in the adhesive composition P contains the hydroxyl group-containing monomer in the above-mentioned amount as a monomer unit constituting the polymer, and the obtained adhesive is inhibited from whitening when it returns to normal temperature and humidity after being subjected to high temperature and high humidity conditions (for example, 240 hours under conditions of 85 ℃, 85% rh), that is, is excellent in wet heat and humidity resistance whitening. When the hydroxyl group-containing monomer is contained in the above amount as the monomer unit in the (meth) acrylate polymer (a), a predetermined amount of hydroxyl groups remains in the obtained adhesive. When a predetermined amount of such a hydrophilic group is present in the adhesive, the adhesive has good compatibility with moisture impregnated into the adhesive under high-temperature and high-humidity conditions even when the adhesive is left under high-temperature and high-humidity conditions, and as a result, whitening of the adhesive is suppressed.
However, as described above, if a predetermined amount of hydrophilic groups is present in the adhesive, the adhesive tends to absorb water, and metal members in contact with the adhesive tend to corrode. However, the adhesive composition P of the present embodiment contains the benzotriazole-based rust inhibitor (B), and thus can suppress corrosion of metal members in contact therewith.
Further, the reactivity of the crosslinking agent (C) and the (meth) acrylate polymer (a) described later tends to be lowered by the presence of the benzotriazole-based rust inhibitor (B), but when the hydroxyl group-containing monomer is contained in the above amount as a monomer unit in the (meth) acrylate polymer (a), the reaction of the crosslinking agent (C) and the (meth) acrylate polymer (a) can be favorably carried out.
On the other hand, since the (meth) acrylate polymer (a) in the adhesive composition P does not contain a carboxyl group-containing monomer, corrosion of a metal member due to a carboxyl group (acid) can also be prevented.
(1) (meth) acrylate ester Polymer (A)
Examples of the hydroxyl group-containing monomer which is a monomer unit constituting the (meth) acrylic acid ester polymer (A) 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 is more preferable from the viewpoint of reactivity with a hydroxyl group and a crosslinking agent (C) and copolymerizability with other monomers in the obtained (meth) acrylate polymer (a). These may be used alone or in combination of two or more.
As described above, the (meth) acrylate polymer (a) contains more than 15 mass% and 30 mass% or less of a hydroxyl group-containing monomer as a monomer unit constituting the polymer. If the content of the hydroxyl group-containing monomer as a monomer unit in the (meth) acrylate polymer (a) is 15% by mass or less, the adhesive agent layer is inferior in wet heat whitening resistance. On the other hand, if the content of the hydroxyl group-containing monomer exceeds 30 mass%, the amount of moisture absorbed into the adhesive becomes too large and the metal member is easily corroded even if the benzotriazole-based rust inhibitor (B) is contained.
From this viewpoint, the hydroxyl group-containing monomer is preferably contained in the (meth) acrylate polymer (a) in an amount of 16 to 25% by mass, and particularly preferably 18 to 20% by mass, as a monomer unit constituting the polymer.
The (meth) acrylate polymer (a) does not contain a carboxyl group-containing monomer as a monomer unit constituting the polymer. Here, "a monomer having no carboxyl group" means a monomer having no carboxyl group in practice, and the carboxyl group-containing monomer is allowed to be contained to such an extent that corrosion of the metal member due to the carboxyl group does not occur, except for not containing the carboxyl group-containing monomer at all. Specifically, the (meth) acrylate polymer (a) may contain the carboxyl group-containing monomer in an amount of 0.1 mass% or less, preferably 0.01 mass% or less, as a monomer unit.
In the (meth) acrylate polymer (a), an alkyl (meth) acrylate having 1 to 20 carbon atoms and containing an alkyl group is preferable as a monomer unit constituting the polymer. Thus, the obtained adhesive can exhibit preferable adhesiveness. In addition, a hard monomer described later is removed from the alkyl (meth) acrylate.
Examples of the alkyl (meth) acrylate in which the alkyl group has 1 to 20 carbon atoms include methyl 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, tetradecyl (meth) acrylate, hexadecyl (meth) acrylate, and octadecyl (meth) acrylate. Among these, from the viewpoint of further improving the adhesion, a (meth) acrylate having an alkyl group with 1 to 8 carbon atoms is preferable, n-butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate are particularly preferable, and 2-ethylhexyl (meth) acrylate is further preferable. According to the 2-ethylhexyl (meth) acrylate, the dielectric constant of the obtained adhesive can be reduced, and false activation of the touch panel can be suppressed. These may be used alone or in combination of two or more.
In the (meth) acrylate polymer (a), the monomer unit constituting the polymer is preferably an alkyl (meth) acrylate having 1 to 20 carbon atoms and containing an alkyl group in an amount of 30 to 85% by mass, particularly preferably 40 to 75% by mass, and further preferably 50 to 65% by mass.
In the (meth) acrylate polymer (a), it is preferable that a hard monomer having a glass transition temperature (Tg) of 70 ℃ or higher as a homopolymer is contained as a monomer unit constituting the polymer. By containing the hard monomer as a monomer unit constituting the (meth) acrylate polymer (a), the cohesive force of the obtained adhesive is improved, and the durability is excellent. In particular, when 2-ethylhexyl (meth) acrylate is used as a monomer unit constituting the (meth) acrylate polymer (a), cohesive force tends to decrease, and therefore the above hard monomer is preferably used. The glass transition temperature (Tg) of the homopolymer of the hard monomer is preferably 75 to 200 ℃ and particularly preferably 80 to 180 ℃.
Examples of the hard monomer include methyl methacrylate (Tg 105 ℃ C.), isobornyl acrylate (Tg 94 ℃ C.), isobornyl methacrylate (Tg 180 ℃ C.), acryloyl morpholine (Tg 145 ℃ C.), adamantyl acrylate (Tg 115 ℃ C.), adamantyl methacrylate (Tg 141 ℃ C.), dimethylacrylamide (Tg 89 ℃ C.), and acrylamide (Tg 165 ℃ C.). These may be used alone or in combination of two or more.
Among the above hard monomers, methyl methacrylate, isobornyl acrylate and acryloylmorpholine are more preferable, and methyl methacrylate is particularly preferable, from the viewpoint of preventing adverse effects on other properties such as tackiness and transparency and further exhibiting the performance of the hard monomers.
In the (meth) acrylate polymer (a), the hard monomer is preferably contained in an amount of 10 to 45 mass%, particularly preferably 15 to 30 mass%, as a monomer unit constituting the polymer. By containing the hard monomer in an amount of 10% by mass or more, the effect of improving the durability based on the monomer unit can be expected. On the other hand, by setting the content of the hard monomer to 45 mass% or less, relative shortage of the other monomer units in the (meth) acrylate polymer (a) is prevented, and the obtained adhesive can be made excellent in adhesiveness and resistance to wet heat whitening.
The (meth) acrylate polymer (a) may contain other monomers as a monomer unit constituting the polymer, if necessary. As the other monomer, a monomer having no reactive functional group is preferable in order not to impair the effect of the hydroxyl group-containing monomer. Examples of the other monomer include alkoxyalkyl (meth) acrylates such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate, (meth) acrylic acid esters having an aliphatic ring such as cyclohexyl (meth) acrylate, (meth) acrylic acid esters having a non-crosslinkable tertiary amino group such as N, N-dimethylaminoethyl (meth) acrylate and N, N-dimethylaminopropyl (meth) acrylate, vinyl acetate, styrene, and the like. These may be used alone or in combination of two or more.
The polymerization form 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 30 to 100 ten thousand, preferably 40 to 90 ten thousand, and particularly preferably 50 to 70 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.
The (meth) acrylate polymer (a) as the main adhesive agent of the adhesive composition P has a weight average molecular weight of 30 ten thousand or more, and the obtained adhesive has improved durability, and the (meth) acrylate polymer (a) has a weight average molecular weight of 100 ten thousand or less, so that the coating property of the adhesive composition P is improved.
In the adhesive composition P, one kind of the (meth) acrylate polymer (a) may be used alone, or two or more kinds may be used in combination.
(2) Benzotriazole type rust inhibitor (B)
Examples of the benzotriazole-based rust inhibitor (B) include 1H-benzotriazole, 1H-tolyltriazole, 1- [ N, N-bis (2-ethylhexyl) aminomethyl ] benzotriazole, 1- [ N, N-bis (2-ethylhexyl) aminomethyl ] methylbenzotriazole, carboxybenzotriazole, 2,2' - [ [ (methyl-1H-benzotriazol-1-yl) methyl ] imino ] diethanol, and the like. Among them, 1H-benzotriazole, 1H-tolyltriazole, 1- [ N, N-bis (2-ethylhexyl) aminomethyl ] benzotriazole and 1- [ N, N-bis (2-ethylhexyl) aminomethyl ] methylbenzotriazole are preferable. According to the above, corrosion of the metal member in contact therewith can be effectively suppressed. The benzotriazole-based rust inhibitor (B) may be used alone or in combination of two or more.
The content of the benzotriazole-based rust inhibitor (B) in the adhesive composition P is preferably 0.01 to 2.0 parts by mass, particularly preferably 0.05 to 1.0 part by mass, and further preferably 0.1 to 0.5 part by mass, based on 100 parts by mass of the (meth) acrylate polymer (a). When the content of the benzotriazole-based rust inhibitor (B) is 0.01 part by mass or more, the corrosion inhibiting effect of the metal member can be sufficiently obtained. When the content of the benzotriazole-based rust inhibitor (B) is 2.0 parts by mass or less, the adhesiveness is not adversely affected.
(3) Crosslinking agent (C)
The adhesive composition P preferably contains a crosslinking agent (C). When the crosslinking agent (C) is contained in the adhesive composition P, the (meth) acrylate copolymer (a) is crosslinked to form a three-dimensional network structure, thereby improving the cohesive force of the obtained adhesive.
The crosslinking agent (C) may be reacted with a reactive group (hydroxyl group of the hydroxyl group-containing monomer as a monomer unit) of the (meth) acrylate copolymer (a), and examples thereof include isocyanate-based crosslinking agents, epoxy-based crosslinking agents, amine-based crosslinking agents, melamine-based crosslinking agents, aziridine-based crosslinking agents, hydrazine-based crosslinking agents, aldehyde-based crosslinking agents, oxazoline-based crosslinking agents, metal alkoxide-based crosslinking agents, metal chelate-based crosslinking agents, metal salt-based crosslinking agents, and ammonium salt-based crosslinking agents. Among these, an isocyanate-based crosslinking agent having excellent reactivity with the hydroxyl group of the (meth) acrylate polymer (a) is preferably used. The crosslinking agent (C) may be used singly or in combination of two or more.
The isocyanate-based crosslinking agent contains 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 include adducts of low molecular active hydrogen-containing compounds such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane and castor oil. Among them, trimethylolpropane-modified aromatic polyisocyanates are preferable from the viewpoint of reactivity with hydroxyl groups, and trimethylolpropane-modified tolylene diisocyanate is particularly preferable.
The content of the crosslinking agent (C) in the adhesive composition P is preferably 0.001 to 10 parts by mass, particularly preferably 0.01 to 5 parts by mass, and more preferably 0.02 to 1 part by mass, based on 100 parts by mass of the (meth) acrylate polymer (a).
When the content of the crosslinking agent (C) is within the above range, the cohesive force of the adhesive obtained is more preferable, and the durability of the adhesive is improved.
(4) Various additives
Various additives generally used as acrylic adhesives, for example, silane coupling agents, antistatic agents, tackifiers, antioxidants, ultraviolet absorbers, light stabilizers, softeners, fillers, refractive index modifiers, and the like can be added to the adhesive composition P as needed.
In particular, from the viewpoint of improving durability, it is preferable to add a silane coupling agent as an additive to the adhesive composition P. The silane coupling agent is preferably an organosilicon compound having at least 1 alkoxysilyl group in the molecule, and has good compatibility with the (meth) acrylate polymer (a). When the adhesive sheet 1 is used for optical applications, a silane coupling agent having light transmittance is preferable.
Examples of the silane coupling agent (C) include polymerizable unsaturated group-containing silicon compounds such as vinyltrimethoxysilane, vinyltriethoxysilane and methacryloxypropyltrimethoxysilane, silicon compounds having an epoxy structure such as 3-glycidoxypropyltrimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, mercapto group-containing silicon compounds such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane and 3-mercaptopropyldimethoxymethylsilane, amino group-containing silicon compounds such as 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane and 3-isocyanatopropyltriethoxysilane, and condensates of at least one of these compounds with an alkyl group-containing silicon compound such as methyltriethoxysilane, ethyltriethoxysilane, methyltrimethoxysilane and ethyltrimethoxysilane. These may be used alone or in combination of two or more.
The amount of the silane coupling agent added is preferably 0.01 to 1.0 part by mass, and particularly preferably 0.05 to 0.5 part by mass, based on 100 parts by mass of the (meth) acrylate polymer (a).
(5) Preparation of adhesive composition
The adhesive composition P can be prepared by preparing the (meth) acrylate polymer (a), mixing the obtained (meth) acrylate polymer (a) and the benzotriazole-based rust inhibitor (B), and adding the crosslinking agent (C) and additives as needed.
The (meth) acrylate polymer (a) can be prepared by polymerizing a mixture of monomer units constituting the polymer by a general radical polymerization method. If necessary, the (meth) acrylate polymer (a) can be polymerized by solution polymerization or the like using a polymerization initiator. Examples of the polymerization solvent include ethyl acetate, n-butyl acetate, n-isobutyl acetate, toluene, acetone, hexane, methyl ethyl ketone, and the like, and two or more kinds thereof may be used in combination.
The polymerization initiator may, for example, be an azo compound or an organic peroxide, or two or more kinds thereof may be used in combination. Examples of the azo compounds include 2,2' -azobisisobutyronitrile, 2,2' -azobis (2-methylbutyronitrile), 1,1' -azobis (cyclohexane-1-carboxynitrile), 2,2' -azobis (2,4-dimethylvaleronitrile), 2,2' -azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2' -azobis (2-methylpropionate), 4,4' -azobis (4-cyanopentanoic acid), 2,2' -azobis (2-hydroxymethylpropionitrile), and 2,2' -azobis [2- (2-imidazolin-2-yl) propane ].
Examples of the organic peroxide include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, bis (2-ethoxyethyl) peroxydicarbonate, t-butyl peroxyneodecanoate, t-butyl peroxypivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropyl peroxide, and diacetyl peroxide.
In the polymerization step, the weight average molecular weight of the obtained polymer can be adjusted by adding a chain transfer agent such as 2-mercaptoethanol.
After the (meth) acrylate polymer (a) is obtained, the benzotriazole-based rust inhibitor (B) is added to the solution of the (meth) acrylate polymer (a), and if necessary, the crosslinking agent (C), the additive, and the diluting solvent are added and sufficiently mixed to obtain the adhesive composition P (coating solution) diluted with the solvent.
Examples of the diluting solvent include aliphatic hydrocarbons such as hexane, heptane and cyclohexane, aromatic hydrocarbons such as toluene and xylene, chlorinated hydrocarbons such as methylene chloride and ethylene chloride, 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 such as ethyl acetate and butyl acetate, 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 can be appropriately selected according to the situation. For example, the concentration of the adhesive composition P is 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 if the adhesive composition P has a coatable viscosity or the like, the diluting solvent may not be added. 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.
[ adhesive agent ]
The pressure-sensitive adhesive of the present embodiment is obtained by crosslinking the pressure-sensitive adhesive composition P. The crosslinking of the adhesive composition P can be performed by heat treatment. Further, the drying treatment when volatilizing the diluent solvent or the like of the adhesive composition P may be performed as the heating treatment.
When the heat treatment is performed, the heating temperature is preferably 50 to 150 ℃, particularly preferably 70 to 120 ℃. The heating time is preferably 30 seconds to 10 minutes, and particularly preferably 50 seconds to 2 minutes. After the heat treatment, the curing period may be set to normal temperature (e.g., 23 ℃ C., 50% RH) for about 1 to 2 weeks, if necessary. When the curing period is required, the adhesive is formed after the curing period has elapsed, and when the curing period is not required, the adhesive layer is formed after the heat treatment is finished.
The adhesive obtained by crosslinking the adhesive composition P can inhibit corrosion of a metal member in contact therewith by the benzotriazole-based rust inhibitor (B), and exhibits excellent resistance to wet-heat whitening by the hydroxyl group of the (meth) acrylate polymer (a).
The adhesive of the present embodiment preferably has a dielectric constant at 1.0MHz of 2.0 to 8.0, particularly preferably 2.0 to 7.0, and further preferably 2.0 to 6.0. The dielectric constant of the adhesive is 2.0 to 8.0, whereby erroneous activation of the touch panel by the adhesive can be effectively suppressed. The method for measuring the dielectric constant of the adhesive is shown in the test examples described below.
[ adhesive sheet ]
As shown in fig. 1, the adhesive sheet 1 of the present embodiment 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. However, the release sheets 12a and 12b are not essential components of the adhesive sheet 1, and are released and removed when the adhesive sheet 1 is used. 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.
(1) Adhesive layer
The adhesive layer 11 is composed of an adhesive obtained by crosslinking the above-mentioned adhesive composition P. The thickness (value measured according to JIS K7130) of the adhesive layer 11 is preferably 10 to 300. Mu.m, particularly preferably 25 to 250. Mu.m, and further preferably 50 to 100. Mu.m. When the thickness of the adhesive agent layer 11 is 10 μm or more, excellent adhesive force can be sufficiently exhibited, and when the thickness of the adhesive agent layer 11 is 300 μm or less, workability becomes good. When the thickness of the adhesive layer 11 is 25 to 100 μm, it is suitable for optical applications, particularly for touch panels. The adhesive layer 11 may be formed of a single layer or may be formed by stacking a plurality of layers.
(2) Release sheet
The release sheets 12a and 12b are not particularly limited, and a known plastic film may be used. For example, a polyethylene film, a polyacrylic 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) acrylate copolymer film, a polystyrene film, a polycarbonate film, a polyimide film, a fluororesin film, or the like can be used. Also, crosslinked films thereof may be used. Further, a laminated film thereof may be used.
The release surfaces (particularly, the surfaces in contact with the adhesive agent layer 11) of the release sheets 12a and 12b are preferably subjected to a release treatment. Examples of the release agent used in the release treatment include release agents such as alkyd, silicone, fluorine, unsaturated polyester, polyolefin, and wax. In addition, of the release sheets 12a and 12b, one release sheet is preferably a heavy release type release sheet having a large release force, and the other release sheet is preferably a light release type release sheet having a small release force.
The thickness of the release sheets 12a and 12b is not particularly limited, and is usually about 20 to 150 μm.
(3) Preparation of adhesive sheet
As one preparation example of the adhesive sheet 1, after the coating layer is formed by applying the coating liquid of the adhesive composition P to the release surface of one release sheet 12a (or 12 b), and performing heat treatment to crosslink the adhesive composition P, the release surface of the other release sheet 12b (or 12 a) is superposed on the coating layer. When the curing period is required, the curing period is set in advance, and when the curing period is not required, the coating layer directly becomes the adhesive layer 11. Thereby, the adhesive sheet 1 described above can be obtained. The conditions for the heat treatment and curing are as described above.
As another preparation example of the adhesive sheet 1, a coating solution of the adhesive composition P is applied to the release surface of one release sheet 12a, and heat treatment is performed to crosslink the adhesive composition P to form a coating layer, thereby obtaining a release sheet 12a with a coating layer. Then, the coating solution of the adhesive composition P is applied to the release surface of the other release sheet 12b, and heat treatment is performed to crosslink the adhesive composition P to form a coating layer, thereby obtaining a release sheet 12b with a coating layer. Then, the coated release sheet 12a and the coated release sheet 12b are bonded so that the two coated layers are in contact with each other. When the curing period is required, the curing period is set in advance, and when the curing period is not required, the coating layer stacked as described above directly serves as the adhesive layer 11. Thereby, the adhesive sheet 1 described above can be obtained. According to this production example, the production can be stably performed even when the adhesive layer 11 is thick.
Examples of the method of applying the coating liquid of the adhesive composition P include a bar coating method, a blade coating method, a roll coating method, a blade coating method, a die coating method, and a gravure coating method.
(4) Haze value
The haze value (value measured according to JIS K7136: 2000) of the adhesive layer 11 in the present embodiment is preferably 1.0% or less, particularly preferably 0.8% or less, and further preferably 0.6% or less. When the haze value is 1.0% or less, the transparency is extremely high, and the coating composition is suitable for optical applications. The haze value of the adhesive layer 11 is particularly preferably within the above range even after the evaluation test of the wet heat whitening resistance described later.
(5) Use of adhesive sheet
By using the adhesive sheet 1, for example, a capacitive touch panel 2 shown in fig. 2 can be prepared. The touch panel 2 includes: a display body module 3; a first thin film sensor 5a laminated on the display body module 3 via an adhesive layer 4; a second thin film sensor 5b laminated on the first thin film sensor 5a via an adhesive layer 11; the cover material 6 is laminated on the second thin film sensor 5b via the adhesive layer 11.
The adhesive layer 11 in the touch panel 2 is the adhesive layer 11 of the adhesive sheet 1.
Examples of the display module 3 include a Liquid Crystal Display (LCD) module, a Light Emitting Diode (LED) module, an organic electroluminescence (organic EL) module, and electronic paper.
The adhesive layer 4 may be formed by the adhesive layer 11 of the adhesive sheet 1, or may be formed by another adhesive or adhesive sheet. In the latter case, the adhesive constituting the adhesive layer 4 may, for example, be an acrylic adhesive, a rubber adhesive, a silicone adhesive, a urethane adhesive, a polyester adhesive, a polyvinyl ether adhesive, or the like, and among them, an acrylic adhesive is preferred.
The first thin film sensor 5a and the second thin film sensor 5b in the present embodiment each include a base thin film 51 and an electrode 52 formed on the base thin film 51 and made of a metal mesh. The base film 51 is not particularly limited, and for example, a polyethylene terephthalate film, an acrylic film, a polycarbonate film, or the like can be used.
Examples of the metal mesh constituting the electrode 52 include copper and silver, and copper is particularly preferable. According to copper, the resistance value can be reduced to 10 Ω/□ or less, and the touch panel can be increased in size. However, copper is more susceptible to corrosion than noble metals such as platinum, gold, and silver, or than transparent conductive materials such as tin-doped indium oxide (ITO). However, according to the adhesive layer 11 formed of the adhesive composition P, corrosion of the electrode 52 made of a copper mesh can be suppressed.
The electrodes 52 of the first thin-film sensor 5a and the electrodes 52 of the second thin-film sensor 5b are usually formed as a circuit pattern in the X-axis direction, and the other is formed as a circuit pattern in the Y-axis direction.
In fig. 2, the electrode 52 of the second thin film sensor 5b in the present embodiment is located above the second thin film sensor 5 b. On the other hand, in fig. 2, the electrode 52 of the first thin-film sensor 5a is located above the first thin-film sensor 5a, but the present invention is not limited thereto, and may be located below the first thin-film sensor 5 a.
The covering material 6 is generally a glass plate or a plastic plate as a main body. The glass plate is not particularly limited, and examples thereof include chemically strengthened glass, alkali-free glass, quartz glass, soda-lime glass, barium-strontium-containing glass, aluminosilicate glass acid, lead glass, borosilicate glass, barium borosilicate glass, and the like. The plastic plate is not particularly limited, and examples thereof include an acrylic plate made of polymethyl methacrylate or the like, and a polycarbonate plate.
Further, functional layers such as a hard coat layer, an antireflection layer, and an antiglare layer may be provided on one surface or both surfaces of the glass plate or the plastic plate, and optical components such as a hard coat film, an antireflection film, and an antiglare film may be laminated.
In the present embodiment, the covering material 6 has a step on the surface on the adhesive layer 11 side, specifically, a step formed by the presence or absence of the printed layer 7. The printed layer 7 is generally formed in a frame shape on the adhesive layer 11 side of the covering material 6.
The material constituting the printed layer 7 is not particularly limited, and a known material for printing can be used. The thickness of the printed layer 7, that is, the step height is preferably 3 to 45 μm, more preferably 5 to 35 μm, particularly preferably 7 to 25 μm, and further preferably 7 to 15 μm.
The thickness (height of the step) of the print layer 7 is preferably 3 to 30%, particularly preferably 3.2 to 20%, and further preferably 3.5 to 15% of the thickness of the adhesive layer 11. This makes it easy for the adhesive layer 11 to follow the level difference caused by the printed layer 7, and can suppress the occurrence of lifting, bubbles, and the like near the level difference.
An example of the method for manufacturing the touch panel 2 will be described below.
As the adhesive sheet 1, a first adhesive sheet 1 and a second adhesive sheet 1 are prepared. One release sheet 12a is peeled off from the first adhesive sheet 1, and the exposed adhesive layer 11 (first adhesive layer 11) is bonded to the second thin-film sensor 5b so as to be in contact with the electrode 52 of the second thin-film sensor 5 b. Then, one release sheet 12a is peeled off from the second adhesive sheet 1, and the exposed adhesive layer 11 (second adhesive layer) is bonded to the first thin-film sensor 5a so as to be in contact with the electrode 52 of the first thin-film sensor 5 a.
The other release sheet 12b of the second adhesive sheets is peeled off, and the exposed second adhesive layer 11 and the surface of the second thin-film sensor 5b opposite to the side on which the first adhesive layer 11 is laminated (the exposed surface of the base film 51 of the second thin-film sensor 5 b) are bonded so as to be in contact with each other. Thus, a laminate in which the release sheet 12b, the first adhesive layer 11, the second thin-film sensor 5b, the second adhesive layer 11, and the first thin-film sensor 5a are laminated in this order was obtained.
Next, the adhesive layer 4 provided on the release sheet is bonded to the surface of the laminate on the first thin-film sensor 5a side (exposed surface of the base film 51 of the first thin-film sensor 5 a). Next, the release sheet 12b is peeled off from the laminate, and the covering material 6 is bonded to the exposed first adhesive layer 11 so that the printed layer 7 side of the covering material 6 is in contact with the adhesive layer 11. Thus, a structure was obtained in which the covering material 6, the first adhesive layer 11, the second thin-film sensor 5b, the second adhesive layer 11, the first thin-film sensor 5a, the adhesive layer 4, and the release sheet were laminated in this order.
Finally, the release sheet is peeled off from the above-described constituent body, and the constituent body is bonded to the display module 3 so that the exposed adhesive layer 4 comes into contact with the display module 3. Thereby, the touch panel 2 shown in fig. 2 can be prepared.
When the touch panel 2 is brought to normal temperature and normal humidity after being subjected to high temperature and high humidity conditions (for example, 240 hours under 85 ℃ and 85% rh), the adhesive agent layers 11 (the first adhesive agent layer 11 and the second adhesive agent layer 11) are excellent in wet heat whitening resistance, and therefore whitening is suppressed. Specifically, the haze value of the adhesive layer 11 can be maintained at 1.0% or less.
The embodiments described above are described for ease of understanding the present invention, and are not described for limiting the present invention. Therefore, each element disclosed in the above embodiments is intended to include all design modifications and equivalents that fall within the technical scope of the present invention.
For example, any of the release sheets 12a and 12b in the adhesive sheet 1 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]
1. Preparation of (meth) acrylate copolymers
The (meth) acrylate polymer (a) was prepared by copolymerizing 60 parts by mass of 2-ethylhexyl acrylate, 20 parts by mass of methyl methacrylate, and 20 parts by mass of 2-hydroxyethyl acrylate. The molecular weight of the (meth) acrylate polymer (a) was measured by the method described below, and the weight average molecular weight (Mw) was 60 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 step (1) above, 0.3 parts by mass of 1H-benzotriazole (JOHOKU CHEMICAL CO., LTD, product name "BT-120") as a benzotriazole-based rust inhibitor (B), 0.15 parts by mass of trimethylolpropane-modified tolylene diisocyanate (Nippon Polyurethane Co., ltd., product name "CORONATE L.") as a crosslinking agent (C), and 0.2 parts by mass of 3-glycidoxypropyltrimethoxysilane (Shin-Etsu CHEMICAL Co., ltd., product name "KBM-403") as a silane coupling agent were mixed and sufficiently stirred, and diluted with methyl ethyl ketone, to obtain a coating solution of an adhesive composition having a solid content of 25 mass%.
Here, the addition of the adhesive composition is shown in table 1. The abbreviations and the like described in table 1 are as follows.
[ (meth) acrylic ester Polymer (A) ]
2EHA: 2-ethylhexyl acrylate
MMA: methacrylic acid methyl ester
HEA: 2-Hydroxyethyl acrylate
BA: acrylic acid n-butyl ester
[ benzotriazole-based rust inhibitor (B) ]
Antirust agent B1: 1H-benzotriazole (JOHOKU CHEMICAL CO., LTD, product name "BT-120")
Antirust agent B2: 1H-tolyltriazole (product name "SEETEC TT-R" manufactured by SHIPRO KASEI KAISHA. LTD.)
Antirust agent B3:1- [ N, N-bis (2-ethylhexyl) aminomethyl ] benzotriazole (JOOOOKU CHEMICAL CO., LTD, product name "BT-LX")
Antirust agent B4:1- [ N, N-bis (2-ethylhexyl) aminomethyl ] methylbenzotriazole (JOHOKU CHEMICAL CO., LTD, product name "TT-LX")
3. Preparation of adhesive sheet
The obtained coating solution of the adhesive composition was applied to a release-treated surface of a heavy release type release sheet (manufactured by Lintec Corporation, product name "SP-PET382150" thickness: 38 μm) which was subjected to a release treatment on one surface of a polyethylene terephthalate film with a silicone-based release agent by a blade coater so that the thickness after drying became 50 μm, and then heat-treated at 90 ℃ for 1 minute, thereby forming a coating layer.
The light release type release sheet (product name "SP-PET382120" manufactured by LINTEC Corporation, thickness: 38 μm) was bonded to the coating layer so that the release-treated surface of the light release type release sheet was in contact with the coating layer, the release-treated surface being obtained by releasing one surface of the polyethylene terephthalate film with a silicone release agent. Thereafter, the film was cured at 23 ℃ and 50% RH for 7 days to prepare an adhesive sheet composed of a heavy-release type release sheet/an adhesive layer (thickness: 50 μm)/a light-release type release sheet.
[ examples 2 to 5 and comparative examples 1 to 2 ]
Adhesive sheets were prepared 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 (Mw) of the (meth) acrylate polymer (a), and the kind of the benzotriazole-based rust inhibitor (B) were changed as shown in table 1.
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 Corporation
GPC column (passage in the following order): manufactured by Tosoh Corporation
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] (evaluation of resistance to whitening by Damp Heat)
The adhesive layers of the adhesive sheets obtained in examples and comparative examples were sandwiched between two sheets of alkali-free glass (thickness: 1 mm) having a size of 70mm × 70mm, and the laminate was autoclaved at 50 ℃ under 0.5MPa for 30 minutes to obtain a sample.
The obtained samples were stored under moist heat conditions of 85 ℃ and 85% RH for 240 hours. Thereafter, the atmosphere was returned to 23 ℃ and 50% RH (normal temperature and normal humidity), and the haze value of the adhesive layer was measured. The haze value is within 30 minutes after returning to the normal temperature and normal humidity atmosphere described above in accordance with JIS K7136: the sample was measured using a haze meter (NIPPON DENSHOKU INDUSTRIES Co., ltd., product name "NDH-5000") 2000. The wet-heat whitening resistance was evaluated based on the measured haze value by the following criteria. The results are shown in Table 1.
O: haze value of 1.0% or less
X: the haze value is more than 1.0 percent
[ test example 2 ] (evaluation of corrosion inhibition)
(1) Production of copper mesh laminated film
A polyethylene terephthalate (PET) film (manufactured by TOYOBO co., ltd., product name "PET100a4100", thickness: 100 μm), a copper Foil (manufactured by Furukawa Circuit Foil co., ltd., product name "BW-S", thickness: 10 μm) on one surface of which blackening was performed, and a polyurethane adhesive (manufactured by Takeda Pharmaceutical Company limited., TAKELAC a310/TAKENATE A10/ethyl acetate =12/1/21 (mass ratio)) were prepared.
The surface of the copper foil opposite to the blackened surface was bonded to the PET film using the urethane adhesive to obtain a laminate composed of a PET film/adhesive layer/copper foil.
Casein was applied to the copper foil side (blackened side) of the obtained laminate, and dried to form a photosensitive resin layer. Then, the photosensitive resin layer is subjected to ultraviolet light close exposure through a mask having a pattern formed thereon, and developed with water. As the mask, a mask having a pattern with a line width of 10 μm and a pitch of 300 μm was used. Subsequently, after the curing treatment, the resist pattern was formed by baking at 100 ℃.
A laminated body having a resist pattern formed thereon was etched by spraying an iron chloride solution (Baume degree: 42, temperature: 30 ℃) from the resist pattern side, and then washed with water. Next, the resist pattern is stripped off with an alkaline solution, and then washed and dried. Thus, a copper mesh laminated film composed of a PET film, an adhesive layer, and a copper mesh was obtained.
(2) Evaluation of Corrosion inhibition
The light-release type release sheet was peeled from the adhesive sheets obtained in examples and comparative examples, and the exposed adhesive layer was attached to the copper mesh side of the copper mesh laminated film. Thereafter, a heavy-release type release sheet was peeled off from the adhesive layer, and a PET film (product name "PET a4100", manufactured by ltd., thickness: 100 μm) was attached to the exposed adhesive layer to obtain a laminate composed of a PET film/adhesive layer/copper mesh/adhesive layer/PET film, which was used as a sample.
The samples were stored for 250 hours under moist heat conditions of 85 ℃ and 85% RH. Thereafter, the presence or absence of corrosion of the copper mesh was visually confirmed, and the performance of corrosion inhibition was evaluated by the following criteria. The results are shown in Table 1.
O: the copper mesh is not corroded
X: corrosion of copper mesh
[ test example 3 ] (calculation of dielectric constant)
An adhesive layer having a thickness of 100 μm was formed on one surface of a polyethylene terephthalate film having a thickness of 50 μm in the same manner as in examples and comparative examples, and a polyethylene terephthalate film having a thickness of 50 μm was bonded to the adhesive layer, followed by cutting to 50mm × 50mm. The electrostatic capacitance (C1) of the laminate thus obtained was measured using an impedance analyzer ("HP-4194A" manufactured by Japan Hewlett-Packard Company). Then, two polyethylene terephthalate films having a thickness of 50 μm were stacked and cut into 50mm × 50mm, and the electrostatic capacitance (C2) was measured in the same manner. Then, C2 is subtracted from C1 to calculate the electrostatic capacitance (C3) of the adhesive. Based on the capacitance C3, the dielectric constant ε of the adhesive was calculated according to the following formula s . The results are shown in Table 1.
ε s ＝(C3×d)/(ε 0 ×S)
ε s : dielectric constant of adhesive
ε 0 : dielectric constant of vacuum (8.854 × 10) -12 )
C3: electrostatic capacity of adhesive
S: area of adhesive layer
d: thickness of adhesive layer
From the above results, the adhesive layer was evaluated as good when the dielectric constant ∈ s was 2.0 to 8.0, and as bad when it exceeded 8.0. The evaluation results are also shown in table 1.
[ Table 1]
Figure BDA0003822487580000221
As is clear from table 1, the adhesive sheets obtained in the examples are excellent in wet-heat whitening resistance and corrosion inhibition effect, and also sufficiently low in dielectric constant, and are good.
Industrial applicability
The adhesive composition, the adhesive and the adhesive sheet of the present invention can be suitably used for, for example, a capacitive touch panel using a copper mesh as an electrode.
Description of the reference numerals
1: an adhesive sheet; 11: an adhesive layer; 12a, 12b: peeling off the sheet; 2: a touch panel; 3: a display body module; 4: an adhesive layer; 5a: a first thin film sensor; 5b: a second thin film sensor; 51: a base film; 52: an electrode; 6: a covering material; 7: printing layer

Claims (6)

1. Use of an adhesive layer, characterized in that,
the adhesive layer is used in contact with a metal member,
the adhesive composition for forming the adhesive layer contains:
a (meth) acrylate polymer (A) containing more than 15% by mass and 30% by mass or less of a monomer having a hydroxyl group as a monomer unit constituting the polymer, 10 to 45% by mass of a hard monomer having a glass transition temperature of 70 ℃ or higher as a homopolymer, 2-ethylhexyl (meth) acrylate, and no monomer having a carboxyl group; and
a benzotriazole-based rust inhibitor (B).
2. Use of an adhesive layer according to claim 1,
the adhesive composition contains at least one selected from the group consisting of 1H-benzotriazole, 1H-tolyltriazole, 1- [ N, N-bis (2-ethylhexyl) aminomethyl ] benzotriazole and 1- [ N, N-bis (2-ethylhexyl) aminomethyl ] methylbenzotriazole as the benzotriazole-based rust inhibitor (B).
3. Use of an adhesive layer according to claim 1 or 2,
the adhesive composition further contains a crosslinking agent (C).
4. A structure comprising a metal member and an adhesive layer disposed in contact with the metal member, characterized in that,
the adhesive composition for forming the adhesive layer contains:
a (meth) acrylate polymer (A) containing more than 15% by mass and 30% by mass or less of a monomer having a hydroxyl group as a monomer unit constituting the polymer, 10 to 45% by mass of a hard monomer having a glass transition temperature of 70 ℃ or higher as a homopolymer, 2-ethylhexyl (meth) acrylate, and no monomer having a carboxyl group; and
a benzotriazole-based rust inhibitor (B).
5. The construct of claim 4,
the adhesive composition contains at least one selected from the group consisting of 1H-benzotriazole, 1H-tolyltriazole, 1- [ N, N-bis (2-ethylhexyl) aminomethyl ] benzotriazole and 1- [ N, N-bis (2-ethylhexyl) aminomethyl ] methylbenzotriazole as the benzotriazole-based rust inhibitor (B).
6. The construct according to claim 4 or 5,
the adhesive composition further contains a crosslinking agent (C).
CN202211046246.3A 2014-03-28 2014-03-28 Adhesive composition, adhesive and adhesive sheet Pending CN115322693A (en)

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