CN110662813A - Adhesive composition and adhesive film - Google Patents

Adhesive composition and adhesive film Download PDF

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Publication number
CN110662813A
CN110662813A CN201880033871.XA CN201880033871A CN110662813A CN 110662813 A CN110662813 A CN 110662813A CN 201880033871 A CN201880033871 A CN 201880033871A CN 110662813 A CN110662813 A CN 110662813A
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meth
adhesive composition
mass
copolymer
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CN201880033871.XA
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CN110662813B (en
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福永直人
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Otsuka Chemical Co Ltd
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Otsuka Chemical Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/26—Layered products comprising a layer of synthetic resin characterised by the use of special additives using curing agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)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
    • 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
    • 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
    • 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
    • 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
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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
    • C09J7/38—Pressure-sensitive adhesives [PSA]

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The technical problem is as follows: provided is an adhesive composition which can form an adhesive layer having a short curing period, low staining and suppressed re-peeling. The technical scheme is as follows: an adhesive composition comprising (A) a (meth) acrylic copolymer having a reactive functional group, wherein the (meth) acrylic copolymer is obtained by living radical polymerization, has a weight average molecular weight of 20 to 200 ten thousand, and has a molecular weight distribution (PDI) of less than 3.0, (B) an isocyanate-based crosslinking agent, and (C) a metal chelate compound.

Description

Adhesive composition and adhesive film
Technical Field
The present invention relates to an adhesive composition and an adhesive film.
Background
An optical film used for a liquid crystal display device, a liquid crystal display, a plasma display, an organic EL (electroluminescence) display, an image display device such as a touch panel, and the like is used by attaching a functional film having functions of surface protection (for example, protection from scratches, dust, contamination, and corrosion during transportation, storage, and processing), antiglare, antireflection, and scattering prevention (prevention of scattering of an adherend) to the surface.
The functional film is in the form of an adhesive film having an adhesive layer on one surface of a base film for attachment to an image display device, and a functional coating layer on the other surface as necessary. Before being attached to the surface of the image display device, the film is attached to the insulating film. In addition, an optical film used for a liquid crystal display device, such as a polarizing plate, a phase difference plate, or the like, is attached to a liquid crystal element using an adhesive.
The adhesive is a (meth) acrylic adhesive comprising a (meth) acrylate copolymer and a crosslinking agent, and is excellent in optical properties and easy in adhesive design. In addition, in order to obtain durability under a high-temperature and high-humidity environment, an isocyanate-based crosslinking agent is used as the crosslinking agent.
Here, the (meth) acrylic adhesive has the following problems: when the adhesive film is peeled from the adherend, contaminants from the adhesive layer remain on the adherend. This is considered to be caused by a low molecular weight component generated when the (meth) acrylate-based copolymer is produced. Further, such low molecular weight components also cause the following problems: when the adhesive is heated, the adhesive strength is excessively increased. If the adhesive agent is heated depending on the use environment of the article to which the adhesive film is attached, the adhesive force of the adhesive agent increases, and the adhesive agent is firmly fixed to the adherend and is difficult to be peeled off even after the use purpose of the adhesive film is completed. Further, even when the adhesive is peelable, the adhesive remains on the adherend and contaminates the adherend. Therefore, a (meth) acrylate copolymer having a small amount of low-molecular weight components has been desired.
In general, a (meth) acrylate copolymer is produced by a radical polymerization method, but it is difficult to obtain uniformity of the copolymer composition, and as a result, a low molecular weight component (oligomer) is often generated. Thus, patent document 1 proposes the use of a (meth) acrylate copolymer produced by a living radical polymerization method for an adhesive composition (see page 18, lines 5 to 10, 24 to 26 of patent document 1).
It is also known that when a (meth) acrylate copolymer obtained by a living radical polymerization method is used, delay in crosslinking and re-peeling over time occur (see comparative examples 1 and 5 in patent document 2). There are the following problems: the occurrence of delay in crosslinking results in a long curing period, and productivity of the adhesive film is deteriorated; the removability increases the storage stability of the adhesive film and the burden of handling during use. Therefore, patent document 2 proposes the use of a binder composition comprising: a (meth) acrylate copolymer obtained by a living radical polymerization method, an isocyanate crosslinking agent, and an organotin compound (see claim 1 of patent document 2)).
Documents of the prior art
Patent document
Patent document 1: international publication No. 2007/119884
Patent document 2: japanese patent laid-open No. 2014-31442
Disclosure of Invention
Technical problem to be solved by the invention
However, even the pressure-sensitive adhesive composition described in patent document 2 has insufficient effect of suppressing the occurrence of re-peeling, and there is still room for investigation. Further, although patent document 2 proposes the use of an organotin compound, a crosslinking accelerator which can replace the organotin compound is required from the viewpoint of the possibility of toxicity.
The present invention has been made in view of the above circumstances, and an object thereof is to provide a pressure-sensitive adhesive composition capable of forming a pressure-sensitive adhesive layer having a short curing period, low staining properties, and suppressed re-peeling.
Means for solving the problems
The pressure-sensitive adhesive composition of the present invention, which can solve the above-mentioned problems, is characterized by comprising (a) a (meth) acrylic copolymer having a reactive functional group, which is obtained by living radical polymerization, and has a weight average molecular weight of 20 to 200 ten thousand and a molecular weight distribution (PDI) of less than 3.0, (B) an isocyanate-based crosslinking agent, and (C) a metal chelate compound.
The pressure-sensitive adhesive composition of the present invention can provide a pressure-sensitive adhesive composition which can form a pressure-sensitive adhesive layer having a short curing period, low staining property and suppressed re-peeling even when a copolymer obtained by living radical polymerization is used by blending (C) a metal chelate compound.
The adhesive composition can be preferably used for optical purposes. The present invention also includes an adhesive film having a substrate film and an adhesive layer, wherein the adhesive layer is formed from the adhesive composition. The present invention also includes an image display device including the adhesive film.
Effects of the invention
The adhesive composition of the present invention has a short curing period when forming an adhesive layer. Further, the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention has low staining properties and is inhibited from being peeled off again from the separator.
Detailed Description
Next, an example of a preferred embodiment of the present invention will be described. The embodiments described below are merely examples. The present invention is not limited in any way by the following embodiments.
In the present invention, "(meth) acrylic group" means "at least one of an acrylic group and a methacrylic group". "(meth) acrylate" means "at least one of acrylate and methacrylate". "(meth) acryloyl" means "at least one of acryloyl and methacryloyl". "vinyl monomer" means a monomer having a carbon-carbon double bond in the molecule which can undergo radical polymerization. The "structural unit derived from a vinyl monomer" means a structural unit in which a carbon-carbon double bond capable of radical polymerization of a vinyl monomer is polymerized to form a carbon-carbon single bond. The term "structural unit derived from a (meth) acrylate" refers to a structural unit in which a carbon-carbon double bond capable of radical polymerization of a (meth) acrylate is polymerized to form a carbon-carbon single bond. The "structural unit derived from a (meth) acrylic acid based monomer" means a structural unit in which a carbon-carbon double bond capable of radical polymerization of a (meth) acrylic acid based monomer is polymerized to form a carbon-carbon single bond. The "structural unit derived from a vinyl monomer" means a structural unit in which a carbon-carbon double bond capable of radical polymerization of a vinyl monomer is polymerized to form a carbon-carbon single bond.
<1. adhesive composition >
The adhesive composition of the present invention contains (A) a (meth) acrylic copolymer having a reactive functional group, (B) an isocyanate-based crosslinking agent, and (C) a metal chelate compound. The (meth) acrylic copolymer (A) is obtained by living radical polymerization, and has a weight average molecular weight of 20 to 200 ten thousand and a molecular weight distribution (PDI) of less than 3.0.
The adhesive composition of the present invention can shorten the curing period in forming the adhesive layer by incorporating (C) a metal chelate compound. Further, the pressure-sensitive adhesive composition of the present invention can suppress re-peeling of a separator or an adherend even when a copolymer obtained by living radical polymerization is used by adding (C) a metal chelate compound.
Next, each constituent component and the like of the pressure-sensitive adhesive composition of the present invention will be described.
(A) a (meth) acrylic copolymer having a reactive functional group)
The (meth) acrylic copolymer (hereinafter, sometimes simply referred to as "copolymer (a)") having a reactive functional group (a) used in the present invention is a (meth) acrylic copolymer as follows: the weight average molecular weight of the product is 20-200 ten thousand, the molecular weight distribution (Mw/Mn) is less than 3.0, and the product has reactive functional groups.
The (meth) acrylic copolymer may be a copolymer mainly containing (50% by mass or more) a structural unit derived from a (meth) acrylic acid-based monomer, and may further contain a structural unit derived from a vinyl monomer other than the (meth) acrylic acid-based monomer. The content of the structural unit derived from the (meth) acrylic acid based monomer in the copolymer (a) is preferably 80% by mass or more, more preferably 90% by mass or more, based on 100% by mass of the entire copolymer. The copolymer (a) may be composed of only a structural unit derived from a (meth) acrylic acid based monomer.
The copolymer (A) is preferably a (meth) acrylate copolymer. The (meth) acrylate copolymer may be a copolymer containing a structural unit derived from a (meth) acrylate as a main component (50% by mass or more), and may further contain a structural unit derived from a vinyl monomer other than the (meth) acrylate. The (meth) acrylate refers to an ester compound formed from (meth) acrylic acid and a compound having a hydroxyl group. The content of the structural unit derived from the (meth) acrylate in the copolymer (a) is preferably 80% by mass or more, more preferably 90% by mass or more, based on 100% by mass of the entire copolymer. The copolymer (a) may be composed of only a structural unit derived from a (meth) acrylate ester.
The reactive functional group is a functional group that can react with an isocyanate group of an isocyanate-based crosslinking agent (B) described later. Examples of the reactive functional group include one or more selected from the group consisting of a hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, a phosphine group and an epoxy group, and a hydroxyl group and/or a carboxyl group is preferable.
The amount of the reactive functional group in 100g of the copolymer (A) is preferably not less than 0.5mmol/100g, more preferably not less than 5mmol/100g, still more preferably not less than 10mmol/100g, particularly preferably not less than 15mmol/100g, preferably not more than 150mmol/100g, more preferably not more than 100mmol/100g, still more preferably not more than 70mmol/100g, and particularly preferably not more than 50mmol/100 g. When the amount of the reactive functional group is 0.5mmol/100g or more, the adhesive composition has excellent durability, and when it is 150mmol/100g or less, the adhesive property to an adherend is excellent.
The copolymer (A) has a reactive functional group. That is, the copolymer (A) contains a structural unit (a-1) having a reactive functional group in its structure. The structural unit (a-1) having a reactive functional group may be only one kind, or may have two or more kinds. The reactive functional group may be present in any one of a structural unit derived from a (meth) acrylic acid based monomer (preferably a (meth) acrylate ester monomer) and a structural unit derived from a vinyl monomer other than a (meth) acrylic acid based monomer. That is, the structural unit (a-1) having a reactive functional group includes a structural unit derived from a (meth) acrylic acid based monomer (preferably, a (meth) acrylate monomer) having a reactive functional group, or a structural unit derived from a vinyl monomer having a reactive functional group other than the (meth) acrylic acid based monomer.
The content of the structural unit derived from the vinyl monomer having a reactive functional group (structural unit (a-1) having a reactive functional group) in the copolymer (a) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, further preferably 1% by mass or more, particularly preferably 3% by mass or more, preferably 20% by mass or less, more preferably 15% by mass or less, further preferably 10% by mass or less, and particularly preferably 8% by mass or less, based on 100% by mass of the entire copolymer. When the content of the structural unit (a-1) is within the above range, a pressure-sensitive adhesive composition having an excellent balance between adhesiveness to an adherend and durability can be obtained. The vinyl monomer having a reactive functional group includes a (meth) acrylic monomer having a reactive functional group and a vinyl monomer having a reactive functional group other than the (meth) acrylic monomer.
Examples of the (meth) acrylic acid based monomer include (b1) a (meth) acrylic acid based monomer having no reactive functional group and (b2) a (meth) acrylic acid based monomer having a reactive functional group. These monomers may be used alone or in combination of two or more. The (b1) a (meth) acrylic acid based monomer having no reactive functional group, preferably (b1-1) a (meth) acrylate monomer having no reactive functional group. The (meth) acrylic acid based monomer having a reactive functional group (b2) includes (b2-1) a (meth) acrylic acid ester monomer having a reactive functional group.
Examples of the (meth) acrylic acid based monomer having no reactive functional group (b1) include (meth) acrylates having a straight-chain alkyl group, (meth) acrylates having a branched-chain alkyl group, (meth) acrylates having an alkoxy group, (meth) acrylates having a polyethylene glycol structural unit, (meth) acrylates having an alicyclic hydrocarbon group, (meth) acrylates having an aromatic group, (meth) acrylates having an oxygen-containing heterocyclic group, (meth) acrylates having a tertiary amino group, and (meth) acrylamides. Among them, (meth) acrylates having a linear alkyl group, (meth) acrylates having a branched alkyl group, (meth) acrylates having an alicyclic hydrocarbon group, (meth) acrylates having an aromatic group, and (meth) acrylamides are preferable.
The (meth) acrylate having a straight-chain alkyl group is preferably a (meth) acrylate having a straight-chain alkyl group having 1 to 20 carbon atoms, and more preferably a (meth) acrylate having a straight-chain alkyl group having 1 to 10 carbon atoms. Examples of the (meth) acrylate having a straight-chain alkyl group include straight-chain alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, n-decyl (meth) acrylate, n-lauryl (meth) acrylate, and n-stearyl (meth) acrylate.
The (meth) acrylate having a branched alkyl group is preferably a (meth) acrylate having a branched alkyl group having 3 to 20 carbon atoms, and more preferably a (meth) acrylate having a branched alkyl group having 3 to 10 carbon atoms. Examples of the (meth) acrylate having a branched alkyl group include branched alkyl (meth) acrylates such as isopropyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isononyl (meth) acrylate, and isodecyl (meth) acrylate.
Examples of the (meth) acrylate having an alkoxy group include alkoxyalkyl (meth) acrylates such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate.
Examples of the (meth) acrylate having a polyethylene glycol structural unit include polyethylene glycol (having a polymerization degree of 1 to 10 (preferably 1 to 5)) methyl ether (meth) acrylate, polyethylene glycol (having a polymerization degree of 1 to 10 (preferably 1 to 5)) ethyl ether (meth) acrylate, polyethylene glycol (having a polymerization degree of 1 to 10 (preferably 1 to 5)) propyl ether (meth) acrylate, polypropylene glycol (having a polymerization degree of 1 to 10 (preferably 1 to 5)) methyl ether (meth) acrylate, polypropylene glycol (having a polymerization degree of 1 to 10 (preferably 1 to 5)) ethyl ether (meth) acrylate, polypropylene glycol (having a polymerization degree of 1 to 10 (preferably 1 to 5)) propyl ether (meth) acrylate, and the like.
Examples of the alicyclic hydrocarbon group include a saturated monocyclic hydrocarbon group, an unsaturated monocyclic hydrocarbon group, and a bridged cyclic hydrocarbon group. The (meth) acrylate having an alicyclic hydrocarbon group is preferably a compound in which an alicyclic hydrocarbon group is directly bonded to a (meth) acryloyloxy group. The (meth) acrylate having an alicyclic hydrocarbon group is preferably a (meth) acrylate having a saturated monocyclic hydrocarbon group, and more preferably a (meth) acrylate having a saturated monocyclic hydrocarbon group having 6 to 12 carbon atoms. Examples of the (meth) acrylate having an alicyclic hydrocarbon group include (meth) acrylates having a saturated monocyclic hydrocarbon group such as cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, and cyclododecyl (meth) acrylate; (meth) acrylates having a bridged hydrocarbon group such as bornyl (meth) acrylate, isobornyl (meth) acrylate, 1-adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, norbornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and dicyclopentenyl (meth) acrylate.
Examples of the (meth) acrylate having an alicyclic hydrocarbon group include (meth) acrylates having a cyclic alkyl group and (meth) acrylates having a polycyclic structure. The (meth) acrylate having a cyclic alkyl group is preferably a (meth) acrylate having a cyclic alkyl group having 6 to 12 carbon atoms. Examples of the cyclic alkyl group include cyclic alkyl groups having a monocyclic structure (for example, cycloalkyl groups), and may have a chain moiety. Examples of the (meth) acrylate having a cyclic alkyl group having a monocyclic structure include cyclic alkyl (meth) acrylates such as cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, and cyclododecyl (meth) acrylate.
The (meth) acrylate having a polycyclic structure is preferably a (meth) acrylate having a polycyclic structure with 6 to 12 carbon atoms. The polycyclic structure includes a cyclic alkyl group having a bridged ring structure (for example, an adamantyl group, a norbornyl group, an isobornyl group), and may have a chain moiety. Examples of the (meth) acrylic acid ester having a polycyclic structure include bornyl (meth) acrylate, isobornyl (meth) acrylate, 1-adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, norbornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, and dicyclopentenyloxyethyl (meth) acrylate.
The (meth) acrylate having an aromatic group is preferably a (meth) acrylate having an aromatic group having 6 to 12 carbon atoms. Examples of the aromatic group include aryl groups, and the like, and may have a chain portion such as an alkylaryl group, an aroyl group, an aryloxyalkyl group, and the like. Examples of the (meth) acrylate having an aromatic group include a compound in which an aryl group is directly bonded to a (meth) acryloyloxy group, a compound in which an aralkyl group is directly bonded to a (meth) acryloyloxy group, and a compound in which an alkylaryl group is directly bonded to a (meth) acryloyloxy group. The number of carbon atoms of the aryl group is preferably 6 to 12. The number of carbon atoms of the aralkyl group is preferably 6 to 12. The number of carbon atoms of the alkylaryl group is preferably 6 to 12. Examples of the (meth) acrylate having an aromatic group include benzyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl (meth) acrylate, and the like.
The (meth) acrylate having an oxygen-containing heterocyclic group is preferably an oxygen-containing heterocyclic group (meth) acrylate having a four-to six-membered ring. Examples of the (meth) acrylate having an oxygen-containing heterocyclic group include furfuryl (meth) acrylate, (3-ethyloxetan-3-yl) methyl (meth) acrylate, (2-methyl-2-ethyl-1, 3-dioxolan-4-yl) methyl (meth) acrylate, cyclic trimethylolpropane formal (meth) acrylate, 2- [ (2-tetrahydropyranyl) oxy ] ethyl (meth) acrylate, 1, 3-dioxane- (meth) acrylate and the like.
Examples of the (meth) acrylate having a tertiary amino group include 2- (dimethylamino) ethyl (meth) acrylate, and N, N-dimethylaminopropyl (meth) acrylate.
Examples of the (meth) acrylamide include N, N-dimethyl (meth) acrylamide, N-diethyl (meth) acrylamide, N-diisopropyl (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-tert-butyl (meth) acrylamide, N-octyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-propoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, diacetone acrylamide, and N- (meth) acryloylmorpholine. The (meth) acrylamide is a (meth) acrylic acid based monomer, but is not included in the (meth) acrylate ester monomer.
The (b2) reactive functional group-containing (meth) acrylic acid-based monomer includes a hydroxyl group-containing (meth) acrylic acid-based monomer (preferably a (meth) acrylate monomer), a carboxyl group-containing (meth) acrylic acid-based monomer (preferably a (meth) acrylate monomer), a sulfonic acid group-containing (meth) acrylic acid-based monomer (preferably a (meth) acrylate monomer), a phosphoric acid group-containing (meth) acrylic acid-based monomer (preferably a (meth) acrylate monomer), an epoxy group-containing (meth) acrylic acid-based monomer (preferably a (meth) acrylate monomer), and the like. Among them, a (meth) acrylic acid based monomer having a hydroxyl group and a (meth) acrylic acid based monomer having a carboxyl group are preferable.
Examples of the hydroxyl group-containing (meth) acrylic acid-based monomer include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, and 12-hydroxylauryl (meth) acrylate; hydroxyalkyl cycloalkyl (meth) acrylates such as (4-hydroxymethylcyclohexyl) methyl (meth) acrylate; caprolactone addition products of hydroxyalkyl (meth) acrylates, and the like. Among them, hydroxyalkyl (meth) acrylates are preferable, and (meth) acrylates having a hydroxyalkyl group having 1 to 5 carbon atoms are more preferable.
Examples of the (meth) acrylic acid based monomer having a carboxyl group include monomers obtained by reacting an acid anhydride such as maleic anhydride, succinic anhydride or phthalic anhydride with a (meth) acrylic ester having a hydroxyl group, such as carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinate, 2- (meth) acryloyloxyethyl maleate or 2- (meth) acryloyloxyethyl phthalate, and (meth) acrylic acid. Among them, (meth) acrylic acid is preferable.
Examples of the (meth) acrylic acid based monomer having a sulfonic acid group include ethyl (meth) acrylate sulfonate.
Examples of the (meth) acrylic acid based monomer having a phosphoric acid group include 2- (phosphonooxy) ethyl (meth) acrylate and the like.
Examples of the (meth) acrylate having an epoxy group include glycidyl (meth) acrylate and 3, 4-epoxycyclohexylmethyl (meth) acrylate.
Examples of the vinyl monomer other than the (meth) acrylic acid based monomer include (b3) a vinyl monomer having no reactive functional group other than the (meth) acrylic acid based monomer, and (b4) a vinyl monomer having a reactive functional group other than the (meth) acrylic acid based monomer. These monomers may be used alone or in combination of two or more.
Examples of the vinyl monomer having no reactive functional group other than the (b3) (meth) acrylic acid based monomer include aromatic vinyl monomers, heterocyclic ring-containing vinyl monomers, vinyl carboxylates, tertiary amine group-containing vinyl monomers, quaternary ammonium salt group-containing vinyl monomers, vinyl amides, α -olefins, and dienes.
Examples of the aromatic vinyl monomer include styrene, α -methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methoxystyrene, 2-hydroxymethylstyrene and 1-vinylnaphthalene.
Examples of the heterocyclic ring-containing vinyl monomer include 2-vinylthiophene, N-methyl-2-vinylpyrrole, 2-vinylpyridine, and 4-vinylpyridine.
Examples of the vinyl carboxylate include vinyl acetate, vinyl pivalate, and vinyl benzoate.
Examples of the vinyl monomer having a tertiary amino group include N, N-dimethylallylammonium.
Examples of the quaternary ammonium salt group-containing vinyl monomer include N-methacryloylaminoethyl-N, N, N-dimethylbenzylammonium chloride and the like.
Examples of the vinyl amides include N-vinylformamide, N-vinylacetamide, 1-vinyl-2-pyrrolidone, and N-vinyl-epsilon-caprolactam.
Examples of the α -olefin include 1-hexene, 1-octene, and 1-decene.
Examples of the diene include butadiene, isoprene, 4-methyl-1, 4-hexadiene, and 7-methyl-1, 6-octadiene.
Examples of the vinyl monomer having a reactive functional group other than the (b4) (meth) acrylic acid based monomer include a vinyl monomer having a hydroxyl group, a vinyl monomer having a carboxyl group, and a vinyl monomer having an epoxy group.
Examples of the vinyl monomer having a hydroxyl group include p-hydroxystyrene and allyl alcohol.
Examples of the vinyl monomer having a carboxyl group include crotonic acid, maleic acid, itaconic acid, citraconic acid, cinnamic acid, and (meth) acrylic acid.
Examples of the epoxy group-containing vinyl monomer include 2-allyloxirane, glycidyl vinyl ether, and 3, 4-epoxycyclohexyl vinyl ether.
The copolymer (A) may be any of a random copolymer, a block copolymer, a graft copolymer, and the like.
The weight average molecular weight (Mw) of the copolymer (a) is 20 ten thousand or more, preferably 40 ten thousand or more, more preferably 50 ten thousand or more, further preferably 60 ten thousand or more, and 200 ten thousand or less, preferably 180 ten thousand or less, more preferably 150 ten thousand or less, further preferably 130 ten thousand or less. (A) If the Mw of the copolymer is less than 20 ten thousand, the aggregating force may be insufficient and the heat resistance may be lowered or the adherend surface may be contaminated, and if it exceeds 200 ten thousand, the coating workability of the pressure-sensitive adhesive composition may be deteriorated. The method for measuring the weight average molecular weight (Mw) will be described later.
The molecular weight distribution (PDI) of the copolymer (A) is less than 3.0, preferably less than 2.5, more preferably less than 2.4, and particularly preferably less than 2.0. The smaller the PDI, the narrower the breadth of the molecular weight distribution, and the more uniform the molecular weight, and when the PDI value is 1.0, the narrowest the breadth of the molecular weight distribution. When the PDI is less than 3.0, the content of a copolymer having a smaller molecular weight or a copolymer having a larger molecular weight is lower than that of a designed copolymer, and the adhesive force is improved. In the present invention, the molecular weight distribution (PDI) is a value calculated from (weight average molecular weight (Mw))/(number average molecular weight (Mn)), and the measurement methods of Mw and Mn will be described later.
The glass transition temperature (Tg) of the copolymer (A) is preferably-80 ℃ or higher, more preferably-70 ℃ or higher, preferably 20 ℃ or lower, and still more preferably 0 ℃ or lower. When the glass transition temperature is-80 ℃ or higher, sufficient cohesive force is imparted to the adhesive composition, and the durability of the adhesive layer is improved, and when the glass transition temperature is 20 ℃ or lower, the adhesion of the adhesive layer to the support base material is increased, and peeling or the like is suppressed, and the durability is improved.
The glass transition temperature (Tg) of the copolymer (a) is a value calculated from the following FOX formula (numerical formula (1)). In the numerical formula (1), Tg represents the glass transition temperature (. degree. C.) of the copolymer. Tgi represents the glass transition temperature (. degree.C.) at which vinyl monomer i forms a homopolymer. Wi represents the mass ratio of the vinyl monomer i in the total vinyl monomers forming the copolymer, and Σ Wi is 1. i is a natural number from 1 to n.
Figure BDA0002283925610000091
The glass transition temperatures of representative homopolymers are described in table 1.
TABLE 1
For short Name of monomer Glass transition temperature (. degree. C.)
MA Acrylic acid methyl ester 10
BA Acrylic acid butyl ester -54
2-EHA 2-ethylhexyl acrylate -70
LA Acrylic acid lauryl alcohol ester -23
CHA Acrylic acid cyclohexyl ester 19
MEA Acrylic acid methoxy ethyl ester -50
HEA Hydroxy ethyl acrylate -15
4-HBA Acrylic acid 4-hydroxybutyl ester -40
AA Acrylic acid 106
DMAAm N, N-dimethylacrylamide 89
The copolymer (A) is prepared by free radical polymerization of a vinyl monomer by a living radical polymerization method. The conventional radical polymerization method (free chemical polymerization method) tends to cause deactivation of the growing end in addition to the initiation reaction and the growth reaction, and also in the termination reaction and the chain transfer reaction, and to form a polymer mixture having various molecular weights and a nonuniform composition. The living radical polymerization method is not easy to generate termination reaction or chain transfer while keeping the simplicity and the universality of the existing radical polymerization method, and can lead the growth end to grow without inactivation, thereby easily preparing the polymer with precisely controlled molecular weight distribution and uniform composition.
Therefore, the copolymer produced by the living radical polymerization method is considered to have the following advantages: the low molecular weight component (oligomer) is small, and the adherend is less contaminated when used in the pressure-sensitive adhesive composition. Since the reactive functional groups are uniformly distributed in the copolymer, it is considered that the amount of the reactive functional groups reactive with the isocyanate-based crosslinking agent of the copolymer produced by the living radical polymerization method is increased, and the crosslinking delay occurs, compared with the copolymer produced by the radical polymerization method, and a long curing period is required.
In the living radical polymerization method, a random copolymer can be formed by using a mixture of monomers (vinyl monomers) constituting the copolymer (a). Further, a block copolymer can also be formed by sequentially reacting vinyl monomers constituting the copolymer. For example, in the case of a diblock copolymer, there may be mentioned: a method of preparing a first block and polymerizing a vinyl monomer constituting a second block on the first block; a method of preparing the second block and then polymerizing the vinyl monomer constituting the first block on the second block, and the like. In the case of a triblock copolymer, there may be mentioned: a method of preparing a first block, polymerizing a vinyl monomer constituting a second block on the first block, and further polymerizing a vinyl monomer constituting a third block, and the like.
In the living radical polymerization method, the following methods are used depending on the method for stabilizing the polymerization growth end: a method using a transition metal catalyst such as copper, ruthenium, nickel, or iron (ATRP method); a method using a sulfur-based reversible chain transfer agent (RAFT method); a method using an organotellurium compound (TERP method), and the like. The ATRP method may not be used unless the acidic group of the vinyl monomer having an acidic group is protected because an amine-based complex compound is used. When a plurality of vinyl monomers are used in the RAFT method, there are cases where it is difficult to form a low molecular weight distribution and there are problems such as sulfur odor and coloring. Among these methods, the TERP method is preferably used from the viewpoint of the variety of vinyl monomers that can be used, the molecular weight control in the polymer region, the composition uniformity, or the coloring.
The TERP method is a method of polymerizing a radical polymerizable compound (vinyl monomer) using an organotellurium compound as a chain transfer agent, and is described in, for example, international publication No. 2004/14848, international publication No. 2004/14962, international publication No. 2004/072126, and international publication No. 2004/096870.
Specific polymerization methods of the TERP method include the following (a) to (d).
(a) A method for polymerizing a vinyl monomer using an organotellurium compound represented by formula (1).
(b) A method for polymerizing a vinyl monomer using a mixture of an organotellurium compound represented by formula (1) and an azo polymerization initiator.
(c) A method for polymerizing a vinyl monomer using a mixture of an organic tellurium compound represented by formula (1) and an organic ditelluride represented by formula (2).
(d) A method for polymerizing a vinyl monomer using a mixture of an organic tellurium compound represented by formula (1), an azo polymerization initiator, and an organic ditelluride represented by formula (2).
Figure BDA0002283925610000111
[ in the formula (1), R1Is an alkyl group, an aryl group or an aromatic heterocyclic group having 1 to 8 carbon atoms. R2And R3Each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R4Is an alkyl group having 1 to 8 carbon atoms, an aryl group, a substituted aryl group, an aromatic heterocyclic group, an alkoxy group, an acyl group, an amide group, an oxycarbonyl group, a cyano group, an allyl group or a propargyl group.]
R1-Te-Te-R1 (2)
[ in the formula (2), R1Represents an alkyl group having 1 to 8 carbon atoms, an aryl group or an aromatic heterocyclic group.]
R1The group is an alkyl group having 1 to 8 carbon atoms, an aryl group or an aromatic heterocyclic group, and is specifically as follows.
Examples of the alkyl group having 1 to 8 carbon atoms include a straight-chain or branched alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group and an octyl group, and a cyclic alkyl group such as a cyclohexyl group. The alkyl group is preferably a linear or branched alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group or an ethyl group.
Examples of the aryl group include phenyl and naphthyl.
Examples of the aromatic heterocyclic group include a pyridyl group, a furyl group, and a thienyl group.
R2And R3The groups are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and each group is as follows.
Examples of the alkyl group having 1 to 8 carbon atoms include a straight-chain or branched alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group, and a cyclic alkyl group such as a cyclohexyl group. The alkyl group is preferably a linear or branched alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group or an ethyl group.
R4The group is an alkyl group having 1 to 8 carbon atoms, an aryl group, a substituted aryl group, an aromatic heterocyclic group, an alkoxy group, an acyl group, an amide group, an oxycarbonyl group, a cyano group, an allyl group or a propargyl group, and is specifically as follows.
Examples of the alkyl group having 1 to 8 carbon atoms include a straight-chain or branched alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group, and a cyclic alkyl group such as a cyclohexyl group. The alkyl group is preferably a linear or branched alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group or an ethyl group.
Examples of the aryl group include phenyl and naphthyl. Phenyl is preferred.
Examples of the substituted aryl group include a substituted phenyl group and a substituted naphthyl group. Examples of the substituent of the substituted aryl group include a halogen atom, a hydroxyl group, an alkoxy group, an amino group, a nitro group, a cyano group and-COR41The carbonyl-containing group (R) shown41Alkyl group having 1 to 8 carbon atoms, aryl group, alkoxy group or aryloxy group having 1 to 8 carbon atoms), sulfonyl group, trifluoromethyl group, etc. Further, these substituents are preferably substituted for one or two.
Examples of the aromatic heterocyclic group include a pyridyl group, a furyl group, and a thienyl group.
The alkoxy group is preferably a group in which an alkyl group having 1 to 8 carbon atoms is bonded to an oxygen atom, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, a tert-butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, and an octyloxy group.
Examples of the acyl group include an acetyl group, a propionyl group, and a benzoyl group.
Amide group, there may be mentioned-CONR421R422(R421、R422Each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group).
Oxycarbonyl radical, preferably-COOR43(R43Hydrogen atom, alkyl group having 1 to 8 carbon atoms, or aryl group), and examples thereof include carboxyl group, methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, n-butoxycarbonyl group, sec-butoxycarbonyl group, tert-butoxycarbonyl group, n-pentyloxycarbonyl group, phenoxycarbonyl group, and the like. Preferable oxycarbonyl group includes methoxycarbonyl group and ethoxycarbonyl group.
Allyl radical, there may be mentioned-CR441R442-CR443＝CR444R445(R441、R442Each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R443、R444、R445Each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group, and each substituent may be bonded to each other in a cyclic structure).
Propargyl, as exemplified by-CR451R452-C≡CR453(R451、R452Is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R453A hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group or a silyl group).
Specific examples of the organotellurium compound represented by the formula (1) include (methyltelluromethyl) benzene, (methyltelluromethyl) naphthalene, ethyl-2-methyl-2-methyltelluro-propionate, ethyl-2-methyl-2-n-butyltelluro-propionate, (2-trimethylsilyloxyethyl) -2-methyl-2-methyltelluro-propionate, all of the organic tellurium compounds described in (2-hydroxyethyl) -2-methyl-2-methyltelluro-propionate or (3-trimethylsilylpropargyl) -2-methyl-2-methyltelluro-propionate, International publication No. 2004/14848, International publication No. 2004/14962, International publication No. 2004/072126 and International publication No. 2004/096870.
Specific examples of the organic ditelluride represented by the formula (2) include dimethyl ditelluride, diethyl ditelluride, di-n-propyl ditelluride, diisopropyl ditelluride, dicyclopropyl ditelluride, di-n-butyl ditelluride, di-sec-butyl ditelluride, di-tert-butyl ditelluride, dicyclobutyl ditelluride, diphenyl ditolyl ditelluride, bis (p-methoxyphenyl) ditelluride, bis (p-aminophenyl) ditelluride, bis (p-nitrophenyl) ditelluride, bis (p-cyanophenyl) ditelluride, bis (p-sulfonylphenyl) ditelluride, dinaphthyl ditelluride and bipyridyl ditelluride.
The azo polymerization initiator is not particularly limited as long as it is an azo polymerization initiator used in general radical polymerization. Examples thereof include 2,2 '-azobis (isobutyronitrile) (AIBN), 2' -azobis (2-methylbutyronitrile) (AMBN), 2 '-azobis (2, 4-dimethylvaleronitrile) (ADVN), 1' -azobis (1-cyclohexanecarbonitrile) (ACHN), dimethyl 2,2 '-azobisisobutyrate (MAIB), 4' -azobis (4-cyanovaleric acid) (ACVA), 1 '-azobis (1-acetoxy-1-phenylethane), 2' -azobis (2-methylbutyronide), 2 '-azobis (4-methoxy-2, 4-dimethylvaleronitrile) (V-70), 2' -azobis (2-methylaminopropane) dihydrochloride, 2,2 ' -azobis [2- (2-imidazolin-2-yl) propane ], 2 ' -azobis [ 2-methyl-N- (2-hydroxyethyl) propionamide ], 2 ' -azobis (2,4, 4-trimethylpentane), 2-cyano-2-propylazoformamide, 2 ' -azobis (N-butyl-2-methylpropionamide), 2 ' -azobis (N-cyclohexyl-2-methylpropionamide), and the like.
In the polymerization step, an azo polymerization initiator and/or an organic ditelluride of formula (2) is further mixed with the vinyl monomer and the organic tellurium compound of formula (1) depending on the type of the vinyl monomer in the vessel after the substitution with the inert gas for the purpose of promoting the reaction, controlling the molecular weight and the molecular weight distribution, and the like. In this case, examples of the inert gas include nitrogen, argon, helium and the like. Argon and nitrogen are preferred.
In the polymerization methods of (a), (b), (c) and (d), the amount of the vinyl monomer to be used may be appropriately adjusted depending on the physical properties, molecular weight and the like of the target copolymer, but it is generally preferable to set the vinyl monomer to 200 to 30000 moles with respect to 1 mole of the organotellurium compound of formula (1). It is noted that the molecular weight of the objective copolymer can also be increased by increasing the amount of the vinyl monomer to be used in an amount of 1 mol relative to the organotellurium compound of formula (1).
In the polymerization method of the above (b), when the organic tellurium compound of the formula (1) and the azo polymerization initiator are used in combination, it is generally preferable that the azo polymerization initiator is used in an amount of 0.01 to 10 moles based on 1 mole of the organic tellurium compound of the formula (1).
In the polymerization method of the above (c), when the organic tellurium compound of the formula (1) and the organic ditelluride of the formula (2) are used in combination, it is generally preferable that the organic ditelluride of the formula (2) is used in an amount of 0.01 to 100 moles based on 1 mole of the organic tellurium compound of the formula (1) as the amount of the organic ditelluride of the formula (2).
In the polymerization method of the above (d), when the organic tellurium compound of the formula (1), the organic ditelluride of the formula (2) and the azo polymerization initiator are used in combination, it is preferable that the azo polymerization initiator is used in an amount of usually 0.01 to 100 moles based on 1 mole of the total amount of the organic tellurium compound of the formula (1) and the organic ditelluride of the formula (2).
The polymerization reaction may be carried out without a solvent, but may be carried out by stirring the mixture using an aprotic solvent or a protic solvent which is generally used in radical polymerization. Examples of the aprotic solvent that can be used include benzene, toluene, N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), acetone, 2-butanone (methyl ethyl ketone), dioxane, propylene glycol monomethyl ether acetate, chloroform, carbon tetrachloride, Tetrahydrofuran (THF), ethyl acetate, propylene glycol monomethyl ether acetate, and trifluoromethylbenzene. Examples of the protic solvent include water, methanol, ethanol, isopropanol, n-butanol, ethyl cellosolve, butyl cellosolve, 1-methoxy-2-propanol, diacetone alcohol, and hexafluoroisopropanol.
The amount of the solvent to be used may be suitably adjusted, and is, for example, preferably 0.01ml or more, more preferably 0.05ml or more, further preferably 0.1ml or more, preferably 50ml or less, more preferably 10ml or less, further preferably 1ml or less, based on 1g of the vinyl monomer.
Next, the mixture was stirred. The reaction temperature and reaction time may be appropriately adjusted depending on the molecular weight or molecular weight distribution of the copolymer to be obtained, but the reaction is usually carried out at 0 ℃ to 150 ℃ for 1 minute to 100 hours under stirring. The TERP process can achieve high yields and precise molecular weight distributions even at low polymerization temperatures and short polymerization times. At this time, the pressure is usually normal pressure, but may be increased or decreased.
After the polymerization reaction is completed, the target copolymer can be isolated and purified by removing the solvent and the residual vinyl monomer from the obtained reaction mixture by a usual isolation and purification means. Further, the reaction mixture may be used as it is in the adhesive composition, if the physical properties of the adhesive composition are not adversely affected.
The growing end of the copolymer obtained by polymerization is-Ter1(in the formula, R1As above), although the tellurium atom is continuously deactivated by the operation in the air after the completion of the polymerization reaction, it may remain. Since a copolymer having tellurium atoms remaining at the terminal ends is colored or has poor thermal stability, it is preferable to remove the tellurium atoms.
As a method for removing tellurium atoms, the following method can be used: a radical reduction method using tributylstannane, a thiol compound, or the like; adsorption method using active carbon, silica gel, active alumina, active white clay, molecular sieve and high molecular adsorbent; a method of adsorbing a metal with an ion exchange resin or the like; a liquid-liquid extraction method or a solid-liquid extraction method in which a peroxide such as hydrogen peroxide or benzoyl peroxide is added or air or oxygen is blown into the system to oxidatively decompose tellurium atoms at the terminal of the copolymer and the residual tellurium compounds are removed by water washing or a suitable solvent; a purification method in a solution state such as ultrafiltration, in which only substances having a molecular weight of not more than a specific molecular weight are extracted and removed. Further, these methods may be used in combination. Incidentally, the copolymer produced by the TERP method sometimes contains a metal compound (more than 0ppm) derived from the chain transfer agent as an impurity. The tellurium content in the copolymer produced by the TERP method is preferably 1000ppm or less, more preferably 400ppm or less, and further preferably 200ppm or less.
((B) isocyanate-based crosslinking agent)
The adhesive composition contains (B) an isocyanate-based crosslinking agent. The isocyanate-based crosslinking agent is a compound having two or more isocyanate groups (including an isocyanate-regenerating functional group temporarily protecting an isocyanate group with a blocking agent, a polymerization agent, or the like) in one molecule. The isocyanate-based crosslinking agent (B) may be used alone or in combination of two or more.
Examples of the isocyanate crosslinking agent include aromatic isocyanates such as toluene diisocyanate and xylene diisocyanate, alicyclic isocyanates such as isophorone diisocyanate, and aliphatic isocyanates such as hexamethylene diisocyanate.
More specifically, for example, one or two or more selected from the following may be used: lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate; alicyclic isocyanates such as cyclopentene diisocyanate, cyclohexene diisocyanate and isophorone diisocyanate; aromatic diisocyanates such as 2, 4-tolylene diisocyanate, 4' -diphenylmethane diisocyanate, xylylene diisocyanate, and polymethylene polyphenyl isocyanate; isocyanate addition products such as trimethylolpropane/tolylene diisocyanate trimer addition products, trimethylolpropane/hexamethylene diisocyanate trimer addition products, and isocyanurate products of hexamethylene diisocyanate; trimethylolpropane adduct of xylene diisocyanate; trimethylolpropane adduct of hexamethylene diisocyanate; polyether polyisocyanates, polyester polyisocyanates, addition products of these with various polyols, polyfunctional polyisocyanates such as isocyanurate bonds, biuret bonds, allophanate bonds, and the like. Among these, the use of aliphatic isocyanates is preferable because the reaction rate is high.
The content of the isocyanate-based crosslinking agent (B) in the adhesive composition is preferably 0.01 part by mass or more, more preferably 0.1 part by mass or more, further preferably 1 part by mass or more, preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and further preferably 10 parts by mass or less, relative to 100 parts by mass of the copolymer (a). When the content of the crosslinking agent is small, the cohesive force is insufficient, and when the content of the crosslinking agent is too large, the crosslinking density is too high, and the adhesive force is lowered, which is not preferable.
In the pressure-sensitive adhesive composition, the molar ratio of the isocyanate group of the (B) isocyanate-based crosslinking agent to the reactive functional group of the (a) copolymer (molar amount of isocyanate group/molar amount of reactive functional group) is preferably 0.001 or more, more preferably 0.01 or more, further preferably 0.1 or more, preferably 10 or less, more preferably 5 or less, and further preferably 2 or less.
((C) Metal chelate)
The adhesive composition contains (C) a metal chelate compound. This can shorten the curing time in forming the pressure-sensitive adhesive composition, and can suppress re-peeling of the pressure-sensitive adhesive film obtained. The (C) metal chelate compound means a complex in which a ligand having two or more coordinating atoms forms a ring and is bonded to a central metal. The metal chelate (C) may be used alone or in combination of two or more.
Examples of the metal constituting the metal chelate compound (C) include one or more metal atoms selected from the group consisting of aluminum, zirconium, titanium, zinc, barium, calcium, copper, strontium, chromium, cobalt, iron, indium, magnesium, manganese and nickel. Among them, at least one metal atom selected from aluminum, zirconium, titanium and zinc is preferable. The metal chelate compound (C) preferably does not contain tin as a constituent metal.
In the metal chelate compound (C), the coordination number is not particularly limited, and may be selected within an appropriate range in consideration of the kind of metal atom to be used and the intended effect. In the (C) metal chelate compound, the coordination number of the metal atom may be 3 to 20, preferably 4 to 16. The "coordination number" in the present invention means the number of coordination bonds formed between the metal atom and the ligand.
Examples of the ligand (chelating agent) constituting the metal chelate (C) include polyaminocarboxylic acids, hydroxycarboxylic acids, and condensed phosphates. The (C) metal chelate compound preferably contains a ligand represented by the following formula (3).
Figure BDA0002283925610000161
[ in the formula, R11And R12Each independently represents hydrogen, alkyl or alkoxy.]
The R is11Or R12The alkyl group is preferably an alkyl group having 1 to 8 carbon atoms. Examples of the alkyl group having 1 to 8 carbon atoms include a straight-chain or branched alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group and an octyl group, and a cyclic alkyl group such as a cyclohexyl group. The alkyl group is preferably a linear or branched alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group or an ethyl group.
The R is11Or R12The alkoxy group is preferably a group in which an alkyl group having 1 to 8 carbon atoms is bonded to an oxygen atom, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, a tert-butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, and an octyloxy group.
Examples of the ligand contained in the metal chelate compound (C) include acetylacetone-based ligands, acetoacetic ester-based ligands, pyruvic acid-based ligands, lactic acid-based ligands, carboxylic acid-based ligands, citric acid-based ligands, and diol-based ligands. Examples thereof include acetylacetone, alkyl acetoacetate, alkylene diamine tetraacetate, diisoalkoxy alkyl bisacetoacetate, diisopropoxy alkyl bisacetoacetate, di-n-alkoxy alkyl bisacetoacetate, and hydroxyalkylene diamine triacetate.
Examples of the metal chelate compound (C) include zirconium chelate compounds such as zirconium tetraacetylacetonate, zirconium tributoxydmonoacetylacetonate, zirconium monobutyloxyacetylacetonate bis (ethylacetoacetate), and zirconium dibutoxybis (ethylacetoacetate); titanium chelate compounds such as titanium ethylacetoacetate, titanium diisopropoxybis (acetylacetonato), titanium tetraacetylacetonate, and titanium diisopropoxybis (ethylacetoacetate); aluminum chelates such as aluminum tris (acetylacetonate), aluminum bis (ethylacetoacetate) monoacetylacetonate, aluminum tris (ethylacetoacetate), aluminum ethyl acetoacetate diisopropoxide, and aluminum alkyl acetoacetate diisopropoxide; zinc chelates such as zinc (II) bisacetoacetonate monohydrate; barium chelates such as barium (II) bis (acetylacetonate) dihydrate, and calcium chelates such as calcium (II) bis (acetylacetonate) dihydrate; copper (II) chelates such as copper bisacetylacetonate; strontium chelates such as strontium (II) bis (acetylacetonate) dihydrate; chromium chelates such as tris (acetylacetonate) chromium; cobalt chelates such as tris (acetylacetonate) cobalt (III) and bis (acetylacetonate) cobalt (II) dihydrate; iron chelates such as iron (III) tris (acetylacetonate), iron (II) bis (acetylacetonate) dihydrate; indium chelates such as tris (acetylacetonate) indium; magnesium chelates such as magnesium (II) bis (acetylacetonate) dihydrate; manganese chelates such as manganese (II) bis (acetylacetonate) dihydrate; nickel chelates such as nickel (II) bisacetoacetonate dihydrate, and the like. Among them, preferred are zirconium chelate complexes and titanium chelate complexes.
The content of the metal chelate compound (C) in the pressure-sensitive adhesive composition of the present invention is preferably 0.01 part by mass or more, more preferably 0.02 part by mass or more, further preferably 0.04 part by mass or more, preferably 0.5 part by mass or less, more preferably 0.4 part by mass or less, further preferably 0.3 part by mass or less, based on 100 parts by mass of the copolymer (a). By setting the content of the (C) metal chelate compound in the above range, excellent crosslinking promoting effect and re-peeling suppressing effect can be obtained.
Here, if a metal compound derived from a chain transfer agent used in living radical polymerization is contained in the pressure-sensitive adhesive composition, the metal compound reacts with an adherend and is likely to be re-peeled. The adhesive composition of the present invention can inhibit re-peeling by containing the metal chelate (C). The metal compound derived from the chain transfer agent differs depending on the living radical polymerization method, and examples thereof include a tellurium compound in the case of the TERP method, and a copper compound, a ruthenium compound, a nickel compound, and an iron compound in the case of the ATRP method.
When the copolymer (a) contains the chain transfer agent-derived metal compound, the content of the metal chelate compound (C) in the adhesive composition is preferably 2 parts by mass or more, more preferably 2.5 parts by mass or more, further preferably 4 parts by mass or more, preferably 40 parts by mass or less, more preferably 35 parts by mass or less, and further preferably 30 parts by mass or less, based on the equivalent of the metal of the chain transfer agent-derived metal compound contained in the copolymer (a). By adjusting the mass ratio of the metal compound derived from the chain transfer agent to the metal chelate (C), re-exfoliation can be suppressed.
The adhesive composition of the present invention can promote the reaction between the reactive functional group of the copolymer (a) and the isocyanate crosslinking agent (B) by incorporating the metal chelate compound (C). Therefore, the adhesive composition of the present invention can shorten the curing period in forming the adhesive layer without adding an organotin compound. Therefore, the content of the organotin compound in the adhesive composition of the present invention is 3% by mass or less, more preferably 1% by mass or less, and still more preferably 0.5% by mass or less. The binder composition of the present invention preferably does not contain an organotin compound. The organotin compound is used as a crosslinking accelerator, and examples thereof include dibutyltin laurate, dibutyltin dioctoate and the like.
(other additives)
In addition to the copolymer (A), the isocyanate-based crosslinking agent (B), and the metal chelate compound (C), other additives may be blended and used in the adhesive composition of the present invention. Examples of the other additives include the following.
The adhesive composition may be used by adding (D) a crosslinking retarder as required. The crosslinking retarder (D) is a compound capable of blocking an isocyanate group of the crosslinking agent in the adhesive composition containing the isocyanate crosslinking agent to suppress an excessive increase in viscosity of the adhesive composition. (D) The kind of the crosslinking retarder is not particularly limited, and for example, β -diketones such as acetylacetone, hexane-2, 4-dione, heptane-2, 4-dione, octane-2, 4-dione, etc.; beta-ketoesters such as methyl acetoacetate, ethyl acetoacetate, propyl acetoacetate, butyl acetoacetate, octyl acetoacetate, oleyl acetoacetate, lauryl acetoacetate, and stearyl acetoacetate; benzoylacetone, and the like. The crosslinking retarder (D) is preferably a substance capable of functioning as a chelating agent, and is preferably a beta-diketone or a beta-ketoester.
The content of the crosslinking retarder (D) which can be blended in the adhesive composition is preferably 1 part by mass or more, more preferably 2 parts by mass or more, further preferably 3 parts by mass or more, preferably 40 parts by mass or less, more preferably 30 parts by mass or less, further preferably 15 parts by mass or less, relative to 100 parts by mass of the copolymer (a). By adjusting the content of the crosslinking retarder (D) to the above range, the excessive increase in viscosity or gelation of the pressure-sensitive adhesive composition can be suppressed after the isocyanate-based crosslinking agent (B) is blended into the pressure-sensitive adhesive composition, and the storage stability (storage time) of the pressure-sensitive adhesive composition can be extended.
When a compound that functions as a chelating agent is used as the crosslinking retarder (D), the mass ratio (chelating agent component/metal component) of the total amount of the chelating agent (ligand) component and the crosslinking retarder (D) in the (C) metal chelate compound to the total amount of the metal component derived from the chain transfer agent in the (a) copolymer and the metal component in the (C) metal chelate compound is preferably 100 or more, more preferably 150 or more, further preferably 200 or more, preferably 1000 or less, and more preferably 900 or less.
The adhesive composition of the present invention may be used by adding a silane coupling agent as needed. The silane coupling agent is not particularly limited, and examples thereof include epoxy group-containing silane coupling agents such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane and 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane; amino group-containing silane coupling agents such as 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-triethoxysilyl-N- (1, 3-dimethylbutylidene) propylamine, and N-phenyl-gamma-aminopropyltrimethoxysilane; (meth) acrylic group-containing silane coupling agents such as 3-acryloxypropyltrimethoxysilane and 3-methacryloxypropyltriethoxysilane; and isocyanate group-containing silane coupling agents such as 3-isocyanatopropyltriethoxysilane.
The content of the silane coupling agent which can be blended in the adhesive composition is preferably 1 part by mass or less, more preferably 0.01 part by mass to 1 part by mass, and still more preferably 0.02 part by mass to 0.6 part by mass, based on 100 parts by mass of the copolymer (a). By adjusting the content of the silane coupling agent to the above range, the water resistance at the interface can be improved when the pressure-sensitive adhesive layer is applied to a hydrophilic adherend such as glass.
The pressure-sensitive adhesive composition of the present invention may be used by blending, if necessary, a crosslinking agent other than the isocyanate-based crosslinking agent (B). (B) Examples of the crosslinking agent other than the isocyanate crosslinking agent include epoxy crosslinking agents. The epoxy crosslinking agent is a polyfunctional epoxy compound having two or more epoxy groups in one molecule. Examples of the epoxy-based crosslinking agent include bisphenol A, epichlorohydrin-based epoxy-based resins, ethylene glycidyl ether, N, N, N ', N' -tetraglycidyl-m-xylylenediamine, diglycidylaniline, diaminoglycidyl amine, 1, 3-bis (N, N-diglycidylaminomethyl) cyclohexane, 1, 6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, sorbitol polyglycidyl ether, glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, polyglycerol polyglycidyl ether, sorbitan polyglycidyl ether, trimethylolpropane polyglycidyl ether, Adipic acid diglycidyl ester, o-phthalic acid diglycidyl ester, tris (2-hydroxyethyl) isocyanurate triglycidyl ester, resorcinol diglycidyl ether, bisphenol-S-diglycidyl ether, and the like.
The content of the epoxy crosslinking agent to be blended in the adhesive composition is preferably 0.01 to 5 parts by mass, more preferably 0.01 to 4 parts by mass, and still more preferably 0.02 to 3 parts by mass, based on 100 parts by mass of the copolymer (a). By adjusting the content of the epoxy crosslinking agent to the above range, the aggregating power or heat resistance can be further improved.
The pressure-sensitive adhesive composition of the present invention may be used by blending, if necessary, a resin for imparting tackiness other than the copolymer (A). Examples of the resin for imparting adhesiveness include rosin resins such as rosin ester resins, terpene resins such as terpene phenol resins, and petroleum resins. Among them, rosin ester resins and terpene phenol resins are preferable.
The rosin ester resin is a resin obtained by esterifying a rosin resin containing rosin acid as a main component, a disproportionated rosin resin, a hydrogenated rosin resin, a dimer of a resin acid such as rosin acid (polymerized rosin resin), or the like with an alcohol. The hydroxyl value can be adjusted by not using a part of the hydroxyl groups of the alcohol used for esterification but containing them in the resin. Examples of the alcohol include polyhydric alcohols such as ethylene glycol, glycerol, and pentaerythritol. The resin obtained by esterifying a rosin resin is a rosin ester resin, the resin obtained by esterifying a disproportionated rosin resin is a disproportionated rosin ester resin, the resin obtained by esterifying a hydrogenated rosin resin is a hydrogenated rosin ester resin, and the resin obtained by esterifying a polymerized rosin resin is a polymerized rosin ester resin. The terpene phenol resin refers to a resin obtained by polymerizing a terpene in the presence of a phenol.
The content of the adhesion-imparting resin which can be blended in the adhesive composition is preferably 5 to 40 parts by mass with respect to 100 parts by mass of the copolymer (A). By adjusting the content of the resin imparting adhesiveness to the above range, the fixation load peelability of the adhesive film to an adherend can be improved.
The pressure-sensitive adhesive composition of the present invention may further contain, as required, dyes, pigments, optical brighteners, wetting agents, surface tension control agents, tackifiers, mildewcides, preservatives, oxygen absorbers, ultraviolet absorbers, near infrared absorbers, water-soluble delustering agents, antioxidants, perfumes, metal deactivators, nucleating agents, antistatic agents, alkylating agents, flame retardants, lubricants, processing aids, and the like, and these may be appropriately selected and used depending on the use or purpose of use of the pressure-sensitive adhesive.
(method for producing adhesive composition)
The adhesive composition can be prepared by mixing the copolymer (a), the isocyanate-based crosslinking agent (B), the metal chelate compound (C), and other additives used as needed. The adhesive composition may also be a solution diluted to a viscosity suitable for forming an adhesive layer by containing a solvent from the preparation of the (a) copolymer or further adding an appropriate solvent.
Examples of the solvent include aliphatic hydrocarbons such as hexane and heptane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as methylene chloride and ethylene chloride; ketones such as acetone, methyl ethyl ketone, 2-pentanone, isophorone, and cyclohexanone; esters such as ethyl acetate and butyl acetate; cellosolve solvents such as ethyl cellosolve; glycol ether solvents such as propylene glycol monomethyl ether. These solvents may be used alone or in combination of two or more.
The amount of the solvent to be used is not particularly limited as long as the adhesive composition has a viscosity suitable for application, and is suitably adjusted, but from the viewpoint of applicability, the solid content concentration of the adhesive composition is preferably 10 to 95 mass%.
(use of adhesive composition)
The adhesive composition is not particularly limited in use and can be used for a wide range of uses, but is particularly preferably used for optical uses such as the production of optical products and optical parts.
The optical product is a product utilizing optical characteristics (for example, polarization, light refraction, light scattering, light reflection, light transmission, light absorption, light diffraction, optical rotation, visibility, and the like) in the product. Examples of the optical product include a liquid crystal display device, an organic EL (electroluminescence) display device, a PDP (plasma display panel), a display device such as electronic paper, an input device such as a touch panel, and a device in which these display devices and input devices are appropriately combined.
The optical member refers to a member having the optical characteristics. Examples of the optical member include members constituting an instrument (optical instrument) such as the display device (image display device) and the input device, and members used in these instruments. Examples of the optical member include a polarizing plate, a wavelength plate, a phase difference plate, an optical compensation film, a luminance enhancement film, a light guide plate, a reflection film, an antireflection film, a transparent conductive film (ITO film), a design film, a decorative film, a surface protection plate, a prism, a lens, a color filter, a transparent substrate, and a member obtained by laminating these (these may be collectively referred to as an "optical film"). The "plate" and "film" include plate-like, film-like, sheet-like forms, and the like, and for example, "polarizing film" includes "polarizing plate" and "polarizer". As described above, the "optical member" of the present invention includes members (design films, decorative films, surface protection films, and the like) that serve as decoration, protection, and the like while maintaining the visibility and excellent appearance of a display such as a display device or an input device.
The material constituting the optical member is not particularly limited, and examples thereof include glass, acrylic resin, polycarbonate, polyethylene terephthalate, and metal (including metal oxide).
<2 > adhesive film
The adhesive film of the present invention has a substrate film and an adhesive layer formed of the adhesive composition. The adhesive layer is formed on at least one side or at least a part of the substrate film. The "film" in the present invention also includes tapes and sheets.
The thickness of the base film is not particularly limited and may be appropriately selected, but is usually preferably 10 μm or more, more preferably 20 μm or more, preferably 250 μm or less, and more preferably 200 μm or less.
The substrate film may be appropriately selected and used according to the use of the adhesive film, and for example, when the adhesive film is used for optical use, a transparent substrate film is preferable. Transparent substrate refers to a transparent substrate. Examples of the transparent base film include polyester resins such as polyethylene terephthalate (PET); acrylic resins such as polymethyl methacrylate (PMMA); and films made of plastic materials such as polycarbonate, triacetyl cellulose (TAC), polysulfone, polyacrylate, polyimide, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, and ethylene-propylene copolymer. The plastic materials may be used alone or in combination of two or more. Among them, PET is preferable in terms of excellent mechanical strength and dimensional stability. Further, TAC is preferable in that the phase difference in the film surface is very small. That is, the transparent substrate film is preferably a PET film (particularly a biaxially stretched PET film) or a TAC film.
The total light transmittance of the transparent substrate film in the visible light wavelength region (JIS K7361-1(1997)) is not particularly limited, but is preferably 85% or more. By setting the total light transmittance to 85% or more, the visibility of the display of the optical product, the display quality, and the like, and the appearance of the optical product are less likely to be adversely affected due to excellent transparency.
The base film may be subjected to surface treatment on one side or both sides by an oxidation method, a roughening method, or the like as desired in order to improve adhesion to a layer provided on the surface thereof. Examples of the oxidation method include corona discharge treatment, plasma treatment, chromic acid treatment (wet type), flame treatment, hot air treatment, ozone/ultraviolet irradiation treatment, and the like. The method of forming the concavities and convexities may be a sand blast method, a solvent treatment method, or the like. These surface treatment methods may be appropriately selected depending on the kind of the base film, but in general, a corona discharge treatment method is preferably used from the viewpoint of effects, workability, and the like. Further, as the substrate film, a film having one side or both sides subjected to plasma treatment may be used.
The thickness of the adhesive layer may be appropriately adjusted according to the use of the adhesive film. For example, the thickness is preferably 0.1 to 20 μm in the case of protective film application (micro-adhesion), and 10 to 350 μm in the case of OCA application (strong adhesion).
The gel content of the pressure-sensitive adhesive layer is preferably 30% to 100%, more preferably 40% to 100%, further preferably 50% to 100%, and particularly preferably 80% to 100%, from the viewpoint of durability and adhesive force. If the gel content is too low, insufficient durability due to insufficient aggregating force and paste residue during peeling are likely to occur. The gel content can be controlled by the amount of the crosslinking agent blended in the adhesive composition, the crosslinking treatment temperature, and the crosslinking treatment time.
The method for forming the adhesive layer is not particularly limited, and examples thereof include the following methods (1) and (2).
(1) A method of coating the adhesive composition on one side or both sides of the substrate film using various coating apparatuses, drying to remove the solvent, and curing as needed.
(2) A method of applying the adhesive composition to the release surface of the release film whose surface has been subjected to release treatment using various coating apparatuses, drying to remove the solvent, curing as needed, and transferring the resultant film to one or both surfaces of the base film.
Examples of the coating device include a reverse roll coater, a gravure coater, a forward roll coater, a knife coater, a wire bar coater, a doctor blade coater, a slit die coater, a curtain coater, and a dip coater.
The drying temperature for drying and removing the solvent is preferably 40 to 200 ℃, more preferably 60 to 180 ℃. The drying time is preferably 5 seconds to 20 minutes, more preferably 10 seconds to 10 minutes. Examples of the drying method include hot air, near infrared rays, and high frequency waves. The curing conditions include, for example, about 23 ℃ for 3 to 7 days.
The adhesive film may have a separator (separation film) on the surface of the adhesive layer before use. Instead of using a separate film, a separate layer may be provided on the surface of the base film opposite to the surface on which the adhesive layer is laminated, and the base film may be wound into a roll or stacked in a stacked state so that the exposed surface side of the adhesive layer contacts the surface of the separate layer. The separator is used as a protective material for the adhesive layer and is peeled off when the adhesive film of the present invention is attached to an adherend.
Examples of the separator include a film obtained by coating a release agent such as a silicone resin on paper such as cellophane paper, coated paper, and laminated paper, and various plastic films. As the plastic film used for the separator, plastic films listed as substrate films can be suitably used. The thickness of the separator is not particularly limited, but is usually 10 μm to 150 μm.
The adhesive film of the present invention may be a functional adhesive film having an adhesive layer on one surface of a substrate film and a functional layer on the other surface. Examples of the functional layer include a coating layer having functions such as scratch resistance, antireflection, antiglare property (anti-glare property), antifouling property, fingerprint resistance, chemical resistance, and glass scattering resistance. As a method for forming the functional layer, a known method can be used. The functional layer may be formed by laminating layers for exhibiting functions such as antiglare properties, antifouling properties, fingerprint resistance, and chemical resistance. For example, by forming the hard coat layer in a laminated structure of a layer excellent in scratch resistance and a layer excellent in antiglare property, a hard coat layer excellent in both scratch resistance and antiglare property can be obtained.
<3. image display device >
The image display device of the present invention is characterized by comprising the adhesive film. Examples of the image display device include a liquid crystal display, an organic EL (electroluminescence) display, a plasma display, and electronic paper.
The adhesive film may be an optical film, specifically a polarizing plate, a wavelength plate, a retardation plate, an optical compensation film, a luminance enhancement film, a light guide plate, a reflection film, an antireflection film, a transparent conductive film (ITO film), a design film, a decorative film, a surface protection plate, or the like.
By preparing the display device using the optical member having the adhesive film of the present invention or the adhesive film of the present invention, an image display device having the adhesive film of the present invention can be obtained.
Examples
The present invention will be described in further detail below with reference to specific examples. The present invention is not limited to the following examples, and can be carried out with appropriate modifications within a scope not changing the gist thereof. The polymerization rate, weight average molecular weight (Mw), molecular weight distribution (PDI), solid content, viscosity, adhesive force of the pressure-sensitive adhesive composition, adhesive force after heating, paste residue, peeling force from the separator, and gel content of the copolymer were evaluated by the following methods.
The meanings of the abbreviations are as follows.
BTEE: ethyl-2-methyl-2-n-butyl tellurium-propionate
V-70: 2, 2' -azobis (4-methoxy-2, 4-dimethylvaleronitrile)
2, 2' -azobis (4-methoxy-2, 4-dimethylvaleronitrile) (V-70)
MA: acrylic acid methyl ester
BA: acrylic acid butyl ester
2-EHA: 2-ethylhexyl acrylate
LA: acrylic acid lauryl alcohol ester
CHA: acrylic acid cyclohexyl ester
4-HBA: acrylic acid 4-hydroxybutyl ester
HEA: hydroxy ethyl acrylate
ACOEt: ethyl acetate
(polymerization ratio)
Measurement was carried out using a Nuclear Magnetic Resonance (NMR) measuring apparatus (model: AVANCE500 (frequency 500MHz) manufactured by Bruker BioSpin Co., Ltd.)1H-NMR (solvent: CDCl)3Internal standard: trimethylsilane (TMS)). From the obtained NMR spectrum, the integral ratio of the peak derived from the vinyl group of the monomer to the peak derived from the ester side chain of the polymer was obtained, and the polymerization rate of the monomer was calculated.
(weight average molecular weight (Mw) and molecular weight distribution (PDI))
The measurement was carried out by Gel Permeation Chromatography (GPC) using a high performance liquid chromatograph (model: HLC-8320GPC, manufactured by Tosoh corporation). Two TSKgel Super MultIcore HZ-H columns (manufactured by Tosoh corporation) were used for the column, a tetrahydrofuran solution was used for the mobile phase, and a differential refractometer was used as the detector. The measurement conditions were: the column temperature was 40 ℃, the sample concentration was 10mg/mL, the sample injection amount was 10. mu.L, and the flow rate was 0.2 mL/min. A calibration curve (calibration curve) was prepared using polystyrene (molecular weights 2,890,000, 1,090,000, 775,000, 427,000, 190,000, 96,400, 37,900, 10,200, 2,630, and 440) as a standard substance, and the weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured. From these measured values, a molecular weight distribution (PDI ═ Mw/Mn) was calculated.
(solid content)
A copolymer solution having a mass of W1 (about 1.0g) was weighed into an aluminum cup (mass W0) and dried under reduced pressure at 130 ℃ for 1 hour. The mass of the aluminum cup containing the dried copolymer was weighed (W2), and the solid content was calculated from the following formula.
Solid content (% by mass) [ (W2-W0)/W1) ] X100
(viscosity)
The viscosity was measured at 25 ℃ at a spindle rotation speed of 60rpm using a type B viscometer (trade name: TVB-15, manufactured by Toyobo industries Co., Ltd.) with a M3 spindle.
< preparation of copolymer >
(Synthesis example 1)
A flask equipped with an argon gas line and a stirrer was charged with 2-EHA (475.0g), 4-HBA (25.0g), V-70(45.7mg) and ACOEt (377.2g), and after replacement with argon gas, BTEE (111.1mg) was added to the flask to conduct a reaction at 33 ℃ for 20 hours to conduct polymerization. The polymerization rate was 88.5%.
After the reaction, ACOEt was added to the reaction solution to obtain a solution of copolymer a. The Mw of the obtained copolymer A was 974,000, PDI was 2.34, Tg was-69 ℃, the content of 4-HBA in the copolymer was 5% by mass, and the amount of reactive functional groups in 100g of the copolymer was 0.03 mol. The copolymer solution had a solid content of 22.3% by mass and a viscosity of 3,881 mPas. Incidentally, the content of each structural unit and the amount of the reactive functional group in the copolymer were calculated based on the addition ratio of the vinyl monomer used for the polymerization reaction.
After drying the solution of the copolymer A, the solution was subjected to ashing treatment, and it was confirmed by inductively coupled plasma mass spectrometry (ICP/MS) that the amount of the tellurium compound was 106ppm in terms of metal relative to the solid content of the solution of the copolymer A.
(Synthesis example 2)
A flask equipped with an argon gas inlet and a stirrer was charged with BA (475g), 4-HBA (25g), V-70(61.7mg) and ACOEt (377.2g), and after replacement with argon gas, BTEE (200.9mg) was added to conduct a reaction at 33 ℃ for 30 hours to conduct polymerization. The polymerization rate was 86.2%.
After the reaction, ACOEt was added to the reaction solution to obtain a solution of copolymer B. The Mw of the obtained copolymer B was 701,000, PDI was 1.63, Tg was-53 ℃, the content of 4-HBA in the copolymer was 5% by mass, and the amount of reactive functional groups in 100g of the copolymer was 0.03 mol. The copolymer solution had a solid content of 19.8% by mass and a viscosity of 2,364 mPas. Incidentally, the content of each structural unit and the amount of the reactive functional group in the copolymer were calculated based on the addition ratio of the vinyl monomer used for the polymerization reaction.
After drying the solution of the copolymer B, the solution was subjected to ashing treatment, and it was confirmed by inductively coupled plasma mass spectrometry (ICP/MS) that the amount of the tellurium compound was 197ppm in terms of metal relative to the solid content of the solution of the copolymer B.
(Synthesis example 3)
A flask equipped with an argon gas line and a stirrer was charged with BA (300g), 2-EHA (75g), CHA (100g), HEA (25g), V-70(38.8mg) and ACOEt (377.2g), and after replacement with argon gas, BTEE (111.0mg) was added to conduct a reaction at 33 ℃ for 22 hours to conduct polymerization. The polymerization rate was 81.1%.
After the reaction, ACOEt was added to the reaction solution to obtain a solution of copolymer C. The Mw of the obtained copolymer C was 941,000, PDI was 1.95, Tg was-44 ℃, the content of HEA in the copolymer was 5% by mass, and the amount of reactive functional groups in 100g of the copolymer was 0.04 mol. The copolymer solution had a solid content of 17.6% by mass and a viscosity of 4368 mPas. Incidentally, the content of each structural unit and the amount of the reactive functional group in the copolymer were calculated based on the addition ratio of the vinyl monomer used for the polymerization reaction.
After drying the solution of the copolymer C, the solution was subjected to ashing treatment, and it was confirmed by inductively coupled plasma mass spectrometry (ICP/MS) that the amount of the tellurium compound was 128ppm in terms of metal relative to the solid content of the solution of the copolymer C.
(Synthesis example 4)
A flask equipped with an argon gas line and a stirrer was charged with MA (50g), 2-EHA (350g), LA (75g), 4-HBA (25g), V-70(57.1mg) and ACOEt (333.3g), and after replacement with argon gas, BTEE (299.87mg) was added to conduct a reaction at 33 ℃ for 21 hours to conduct polymerization. The polymerization rate was 89.4%.
After the reaction, ACOEt was added to the reaction solution to obtain a solution of copolymer D. The Mw of the obtained copolymer D was 478,000, PDI was 1.78, Tg was-56 ℃, the content of 4-HBA in the copolymer was 5% by mass, and the amount of reactive functional groups in 100g of the copolymer was 0.03 mol. The copolymer solution had a solid content of 42.4% by mass and a viscosity of 7070 mPas. Incidentally, the content of each structural unit and the amount of the reactive functional group in the copolymer were calculated based on the addition ratio of the vinyl monomer used for the polymerization reaction.
After drying the solution of the copolymer D, the ashing treatment was performed, and it was confirmed by inductively coupled plasma mass spectrometry (ICP/MS) that the amount of the tellurium compound was 285ppm in terms of metal relative to the solid content of the solution of the copolymer D.
< preparation of adhesive composition >
(adhesive composition No.1)
To 448.4 parts by mass of the solution of the copolymer A obtained in Synthesis example 1 (copolymer component 100 parts by mass, ACOEt 348.4 parts by mass) were added 6.31 parts by mass of an isocyanate compound, 0.08 part by mass of a zirconium chelate complex, 13.9 parts by mass of acetylacetone, and ACOEt 196.6 parts by mass, and the mixture was stirred to obtain adhesive composition No. 1.
(adhesive composition Nos. 2 to 28)
Adhesive composition nos. 2 to 28 were prepared in the same manner as adhesive composition No.1, except that the formulations were changed as described in tables 2 to 4. The amounts of the solvents in tables 2 to 4 are the total amount of ACOEt contained in the copolymer solution and ACOEt to be further added in preparing the adhesive composition.
TABLE 2
TABLE 3
TABLE 4
Figure BDA0002283925610000263
< preparation of adhesive film >
(adhesive film No.1)
Adhesive composition No.1 was coated on a polyethylene terephthalate (PET) film (thickness 125 μm) so that the thickness of the adhesive composition after drying was 7 μm. The adhesive film No.1 having the adhesive layer was prepared by drying the PET film coated with the adhesive composition at 100 ℃ for 1 minute. A separator (thickness: 25 μm, manufactured by Toray film processing Co., Ltd. "セ ラ ピ ー ル (registered trademark) WZ") was attached to the obtained pressure-sensitive adhesive layer, and the resultant was left to stand at 23 ℃ for 1 week for curing.
(adhesive film No.2 to 5)
Adhesive film Nos. 2 to 5 were prepared in the same manner as adhesive film No.1 except that adhesive composition No.1 was changed to adhesive composition Nos. 2 to 5.
(adhesive film No.6)
Adhesive composition No.6 was coated on a PET film (thickness 125 μm) so that the thickness of the adhesive composition after drying was 10 μm. The adhesive film coated with the adhesive composition was dried at 100 ℃ for 2 minutes to prepare an adhesive film having an adhesive layer. A separator (thickness: 25 μm, manufactured by Toray film processing Co., Ltd. "セ ラ ピ ー ル (registered trademark) WZ") was attached to the obtained pressure-sensitive adhesive layer, and the resultant was left to stand at 23 ℃ for 1 week for curing.
(adhesive film Nos. 7 to 19)
Adhesive film Nos. 7 to 19 were prepared in the same manner as adhesive film No.6 except that adhesive composition No.6 was changed to adhesive composition Nos. 7 to 19.
(adhesive film No.20)
Adhesive composition No.20 was coated on a PET film (thickness 50 μm) so that the thickness of the adhesive composition after drying was 10 μm. The adhesive film coated with the adhesive composition was dried at 100 ℃ for 2 minutes to prepare an adhesive film having an adhesive layer. A separator (thickness: 25 μm, "HY-PS 11" available from Toshima Kagaku Co., Ltd.) was attached to the obtained pressure-sensitive adhesive layer, and the resultant was left to stand at 40 ℃ for 3 days for curing.
(adhesive film Nos. 21 to 28)
Adhesive film Nos. 21 to 28 were prepared in the same manner as adhesive film No.20 except that adhesive composition No.20 was changed to adhesive composition Nos. 21 to 28.
< evaluation of adhesive film >
(IR Peak intensity ratio)
With respect to the adhesive layers of adhesive films No.1 to 5, the curing period was evaluated for 3 hours and 7 days (1 week)Residual amount of isocyanate group. By measuring 2275cm as antisymmetric stretching IR peak of isocyanate group-1The residual amount of isocyanate groups was evaluated. The measurement was performed by a total reflection method (ATR method) using a fourier transform infrared spectrophotometer (FT-IR). The strength ratio with respect to the peak strength after 3 hours curing period of the adhesive film No.5 is given in Table 5.
(adhesive force)
The adhesive force of the adhesive film was measured according to the method for measuring adhesive force of JIS Z0237(2009) (method 1: test method of peeling tape and sheet 180 ° with respect to stainless steel test plate). Specifically, an adherend (stainless steel plate (SUS 304BA) Ra 50nm (JIS B0601 (1994)) whose surface was cleaned was pressed with a pressing device (roller mass: 2kg), and the adhesive force at 180 ℃ peeling from the adherend was measured. The test temperature was 23 ℃ and the peeling speed was 300 mm/min. The adhesive film had a width of 25mm and a length of 300 mm. After the start of the measurement, the first 25mm length measurement was ignored, and the adhesive force measurement values of 50mm length which were subsequently peeled from the test plate were averaged.
(adhesive force after heating)
After the adhesive film was pressed against an adherend in the same manner as in the measurement of the adhesive force, the resultant was heated at 150 ℃ for 1 hour and then cooled at room temperature (23 ℃) for 1 hour. After cooling, the adhesion at 180 ° peel was measured in the same manner as the above adhesion. Further, the rate of increase in adhesive force by heating was calculated according to the following formula.
Percent increase (%) × 100 (adhesive force after heating/adhesive force without heating) × 100
(adherend paste residue after measurement of adhesive force)
In the measurement of the adhesive force after the heating, the adherend after the adhesive film was peeled off was visually observed to confirm whether or not there was a paste residue on the adherend. The evaluation results were "good" for no paste remaining and "x" for paste remaining.
(Peel force)
The peel force at the time of peeling the release film was measured according to the method for measuring the peel force of JIS Z0237(2009) (method 4: test method for peeling the release liner 180 ° from the adhesive surface of the tape and the sheet). Specifically, the adhesive film was fixed to a stainless steel plate with a double-sided adhesive tape, and the peel force was measured when the separator was peeled off at 180 ° from the adhesive film. The test temperature was 23 ℃ and the peeling speed was 300 mm/min. The width of the release film and adhesive film was 25mm and the length was 300 mm. After the start of the measurement, the measurement values of the first 25mm length were ignored, and the measurement values of the peeling force of 50mm length from the adhesive film after the peeling were averaged.
(peeling force after heating)
For adhesive films Nos. 1 to 5, the adhesive film to which the separator was attached was heated at 100 ℃ for 1 hour and then cooled at 23 ℃ for 1 hour. For adhesive films Nos. 6 to 28, the adhesive film to which the separator was attached was heated at 150 ℃ for 1 hour, and then cooled at 23 ℃ for 1 hour. After cooling, the peel force at 180 ° peel was measured in the same manner as the peel force. Further, the rate of increase in peeling force by heating was calculated according to the following formula.
Percent increase (%) (peeling force after heating/peeling force without heating) × 100
(gel content)
The adhesive composition is applied to a separator and dried at 100 ℃ for 1 minute (adhesive composition Nos. 1 to 5) or dried at 100 ℃ for 2 minutes (adhesive composition Nos. 6 to 28). Then, the film was left to stand at 23 ℃ for 1 week for curing, and the pressure-sensitive adhesive layer formed on the separator was peeled off.
An adhesive layer having a mass of W1 (about 0.10g) was weighed on a stainless steel wire mesh (400 mesh) having a mass of W0, and soaked in ethyl acetate at 60 ℃ for 24 hours. Then, the adhesive layer and the stainless steel wire mesh were taken out of ethyl acetate, dried at 23 ℃ for 24 hours, and further dried under reduced pressure at 130 ℃ for 1 hour. After drying, the weight W2 of the stainless steel wire mesh comprising the dried adhesive layer was measured and the gel content was calculated according to the following formula.
Gel content (% by mass) [ (W2-W0)/W1) ] X100
TABLE 5
TABLE 6
Figure BDA0002283925610000292
TABLE 7
Figure BDA0002283925610000301
TABLE 8
Figure BDA0002283925610000302
Isocyanate compound (b): manufactured by Asahi Kasei corporation, デ ュ ラ ネ ー ト (registered trademark) TPA-100
Zirconium chelate complexes: manufactured by Songban Fine chemical Co., Ltd., オ ル ガ チ ッ ク ス (registered trademark) ZC-150 (zirconium tetraacetylacetonate)
Titanium chelate complexes: manufactured by Songban Fine chemical Co., Ltd., オ ル ガ チ ッ ク ス (registered trademark) TC-750 (diisopropoxy bis (ethylacetoacetate) titanium)
Aluminum chelate complexes: chuanjian Fine chemical products manufactured by Kagaku K.K., ア ル ミ キ レ ー ト A (tris (acetylacetonate) aluminum)
Organotin compound: manufactured by Nidonghua Kabushiki Kaisha ネ オ ス タ ン (registered trademark) U810 (dioctyltin)
Amine compound: 1, 4-diazabicyclo [2.2.2] octane manufactured by Tokyo Chemicals K.K
As shown in Table 5, when a zirconium chelate complex or a titanium chelate complex was used as the crosslinking accelerator (binder compositions Nos. 1 and 2), the IR peak intensity ratio was small even when the curing period was 3 hours. Therefore, these chelates were found to have crosslinking accelerating ability, as with the organotin compound (adhesive composition No. 3). When an amine compound was used as the crosslinking accelerator (adhesive composition No.4), the IR peak intensity ratio was 1.0 at a curing time of 3 hours. Namely, the amine compound was found to have no crosslinking accelerating ability.
As shown in table 5, in the case where an organotin compound was used as the crosslinking accelerator (adhesive film No.3), the increase rate of the peeling force by heating was larger than that in the case where the crosslinking accelerator was not used (adhesive film No. 5). On the other hand, when a zirconium chelate complex or a titanium chelate complex is used as a crosslinking accelerator (adhesive films nos. 1 and 2), the rate of increase in peeling force by heating is small, and the occurrence of heavy peeling is suppressed.
As shown in tables 6 to 8, when a metal chelate (zirconium chelate, titanium chelate, aluminum chelate) was used as the crosslinking accelerator (adhesive films nos. 6 to 13, 16 and 17), the rate of increase in the adhesive force to the adherend by heating was smaller than that when the crosslinking accelerator was not used (adhesive films nos. 15 and 19). Further, in the case where a crosslinking accelerator was not used for the copolymer a (adhesive film No.15), the adhesive force after heating was greatly increased, and the adherend was contaminated. In contrast, adhesive films nos. 6 to 14 were inhibited from increasing in adhesive strength by heating, and were free from contamination of the adherend. In adhesive film No.19, although the adhesive force after heating was greatly increased, no adherend contamination was observed. This is considered to be because the copolymer B has a higher aggregating power than the copolymer A. Further, with respect to adhesive films nos. 22, 25 and 28, it is considered that curing conditions at the time of preparing the adhesive films or the thickness of the film as the substrate are different.
The present invention includes the following embodiments.
An adhesive composition comprising (A) a (meth) acrylic copolymer having a reactive functional group, (B) an isocyanate-based crosslinking agent, and (C) a metal chelate compound, wherein the (meth) acrylic copolymer (A) is obtained by living radical polymerization, has a weight average molecular weight of 20 to 200 ten thousand, and has a molecular weight distribution (PDI) of less than 3.0.
Embodiment 2 the pressure-sensitive adhesive composition according to embodiment 1, wherein the content of the metal chelate compound (C) is 2 parts by mass or more based on 1 part by mass of a metal equivalent of a metal compound derived from a chain transfer agent contained in the (meth) acrylic copolymer (a).
Embodiment 3 the adhesive composition according to embodiment 1 or 2, wherein the reactive functional group of the (meth) acrylic copolymer (a) is at least one selected from the group consisting of a hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, a phosphino group, and an epoxy group.
Embodiment 4 the adhesive composition according to any one of embodiments 1 to 3, wherein the (meth) acrylic copolymer (A) contains 0.1 to 20% by mass of a structural unit derived from a vinyl monomer having a reactive functional group, based on 100% by mass of the entire copolymer.
(embodiment 5) the adhesive composition according to any one of embodiments 1 to 4, wherein the (meth) acrylic copolymer (A) contains 80% by mass or more of a structural unit derived from a (meth) acrylic acid-based monomer per 100% by mass of the entire copolymer.
Embodiment 6 the adhesive composition according to any one of embodiments 1 to 5, wherein the content of the isocyanate-based crosslinking agent (B) is 0.01 to 20 parts by mass relative to 100 parts by mass of the (meth) acrylic copolymer.
Embodiment 7 the adhesive composition according to any one of embodiments 1 to 6, wherein the metal chelate compound (C) contains at least one metal atom selected from the group consisting of aluminum, zirconium, titanium, zinc, barium, calcium, copper, strontium, chromium, cobalt, iron, indium, magnesium, manganese, and nickel.
Embodiment 8 the adhesive composition according to any one of embodiments 1 to 7, wherein the metal chelate compound (C) contains a ligand represented by the following formula (3).
Figure BDA0002283925610000321
[ in the formula, R11And R12Each independently represents hydrogen, alkyl or alkoxy.]
Embodiment 9 the adhesive composition according to any one of embodiments 1 to 8, wherein the content of the metal chelate compound (C) is 0.01 to 0.5 parts by mass based on 100 parts by mass of the (meth) acrylic copolymer.
(embodiment 10) the adhesive composition according to any one of embodiments 1 to 9, further comprising (D) a crosslinking retarder.
(embodiment 11) the adhesive composition according to any one of embodiments 1 to 10, which is for optical use.
(embodiment 12) an adhesive film comprising a base film and an adhesive layer, wherein the adhesive layer is formed from the adhesive composition according to any one of embodiments 1 to 11.
(embodiment 13) an image display device comprising the adhesive film according to embodiment 12.

Claims (13)

1. An adhesive composition comprising (A) a (meth) acrylic copolymer having a reactive functional group, (B) an isocyanate-based crosslinking agent, and (C) a metal chelate compound,
wherein the (meth) acrylic copolymer (A) is obtained by living radical polymerization, and has a weight average molecular weight of 20 to 200 ten thousand and a molecular weight distribution PDI of less than 3.0.
2. The adhesive composition according to claim 1, wherein the content of the metal chelate compound (C) is 2 parts by mass or more per 1 part by mass of a metal equivalent of a metal compound derived from a chain transfer agent contained in the (meth) acrylic copolymer (A).
3. The adhesive composition according to claim 1 or 2, wherein the reactive functional group of the (a) (meth) acrylic copolymer is at least one selected from the group consisting of a hydroxyl group, a carboxyl group, a sulfonic group, a phosphoric group, a phosphonic group, a phosphino group, and an epoxy group.
4. The adhesive composition according to any one of claims 1 to 3, wherein the (meth) acrylic copolymer (A) contains 0.1 to 20% by mass of a structural unit derived from a vinyl monomer having a reactive functional group, based on 100% by mass of the total copolymer.
5. The adhesive composition according to any one of claims 1 to 4, wherein the (meth) acrylic copolymer (A) contains 80% by mass or more of a structural unit derived from a (meth) acrylic acid-based monomer per 100% by mass of the entire copolymer.
6. The adhesive composition according to any one of claims 1 to 5, wherein the content of the isocyanate-based crosslinking agent (B) is 0.01 to 20 parts by mass relative to 100 parts by mass of the (meth) acrylic copolymer.
7. The adhesive composition according to any one of claims 1 to 6, wherein the (C) metal chelate compound contains at least one metal atom selected from the group consisting of aluminum, zirconium, titanium, zinc, barium, calcium, copper, strontium, chromium, cobalt, iron, indium, magnesium, manganese, and nickel.
8. The adhesive composition according to any one of claims 1 to 7, wherein the (C) metal chelate compound contains a ligand represented by the following formula (3),
Figure FDA0002283925600000011
in the formula, R11And R12Each independently represents hydrogen, alkyl or alkoxy.
9. The adhesive composition according to any one of claims 1 to 8, wherein the content of the metal chelate compound (C) is 0.01 to 0.5 parts by mass based on 100 parts by mass of the (meth) acrylic copolymer.
10. The adhesive composition according to any one of claims 1 to 9, further comprising (D) a crosslinking retarder.
11. The adhesive composition according to any one of claims 1 to 10, which is for optical use.
12. An adhesive film comprising a substrate film and an adhesive layer, wherein the adhesive layer is formed from the adhesive composition according to any one of claims 1 to 11.
13. An image display device comprising the adhesive film according to claim 12.
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