JP2017043725A - Pressure-sensitive adhesive, pressure-sensitive adhesive film, and optical laminate using the same - Google Patents

Abstract

The problem to be solved by the present invention is that when used in a pressure-sensitive adhesive film, it has excellent removability and is lifted from an adherend after being exposed to a high temperature environment or a high temperature and high humidity environment. To provide a pressure-sensitive adhesive that hardly peels off and a pressure-sensitive adhesive film using the pressure-sensitive adhesive. A pressure sensitive adhesive comprising a copolymer (A) having a weight average molecular weight of 100,000 to 2,000,000 and a silane compound (B) having a primary or secondary amino group, The copolymer (A) is a pressure-sensitive adhesive containing the following compounds (a1), (a2) and (a3) as monomers constituting the copolymer (A). Α, β-unsaturated double bond group-containing compound having one or more hydroxyl groups (a1) α, β-unsaturated double bond group-containing compound having one or more carbonyl groups (a2) hydroxyl groups and carbonyl groups No α, β-unsaturated double bond group-containing compound (a3) (however, compound (a2) does not have a hydroxyl group) [Selection] None

Description

    The present invention relates to a pressure-sensitive adhesive that can be used for members such as plastic and glass.

    Display devices such as liquid crystal displays used in various devices such as home and commercial appliances such as electronic calculators, electronic watches, mobile phones, and televisions are becoming larger, especially liquid crystal televisions and plasma televisions. The increase in size is remarkable. In recent years, touch panel type liquid crystal displays such as smartphones and tablets are rapidly spreading, and a large market expansion is expected in the future. On the other hand, liquid crystal displays are also used in in-vehicle devices such as car navigation systems, and are required to have durability that can be used in harsh interior environments such as high-temperature and high-humidity atmospheres.

For such display devices, various films such as an antireflection film for preventing reflection from an external light source and a protective film (protection film) for preventing scratches on the surface of the display device are usually used. For example, in a liquid crystal cell member constituting an LCD (liquid crystal display), a polarizing film or a retardation film is laminated.
In addition to being used as a display device, a touch panel function may be provided on the surface to be used as an input device. Also for the touch panel, a protective film, an antireflection film, an ITO (tin-doped indium oxide) vapor deposited resin film, or the like is used.
Such a film is attached to an adherend via a pressure-sensitive adhesive and used in a display device. Since the pressure-sensitive adhesive used in the display device is required to have excellent transparency, a pressure-sensitive adhesive mainly composed of an acrylic resin is generally used.

  By the way, among the various films described above, the polarizing film generally has a three-layer structure in which both surfaces of a polyvinyl alcohol polarizer are sandwiched between triacetyl cellulose-based and cycloolefin-based protective films. For this reason, in a polarizing film, since the dimensional change characteristic of the material which comprises each layer differs, it is easy to produce the warp by the dimensional change accompanying the change of temperature or humidity.

On the other hand, for example, in an inspection process for a laminate in which a polarizing film is attached to a glass surface for a liquid crystal cell in an LCD manufacturing process, the polarizing film or the like is peeled off when there is air or dust entrainment during lamination. A new polarizing film or the like is reapplied. This re-pasting is also called “rework”.
However, since the laminated body after sticking is generally inspected after being stored at a high temperature for a certain period of time to improve adhesion, not only does the peel strength increase during that time, but it becomes difficult to peel off the polarizing film, After the releasability (sometimes referred to as reworkability) of the polarizing film was lowered and peeled off, contamination such as adhesive residue or cloudiness sometimes occurred on the glass surface.

In addition, since the polyvinyl alcohol film in the polarizing film undergoes a large dimensional change under high temperature or high temperature and high humidity conditions, for example, a laminate comprising a polarizing film / adhesive layer / glass is placed under high temperature or high temperature and high humidity conditions. If the dimensions of the polarizing film are changed, bubbles may be generated at the interface between the adhesive layer and the glass (foaming phenomenon), or the polarizing film may be lifted from the glass and peeled off (floating / peeling phenomenon).
Therefore, by adjusting the molecular weight of the pressure-sensitive adhesive and the degree of crosslinking of the pressure-sensitive adhesive and increasing the adhesive strength, the polarizing film does not foam, float, or peel even under harsh environments against dimensional changes. An attempt was made to do so.

  However, simply trying to resist the dimensional change of the polarizing film simply by increasing the adhesive force, the stress distribution due to the dimensional change of the polarizing film that occurs under high temperature or high temperature and high humidity conditions becomes non-uniform, and the stress is polarized. It concentrates on the four corners and the peripheral edge of the film. As a result, in the display device using the polarizing film, there is a problem that light leaks from the peripheral end portion of the display device, so-called white spots (sometimes referred to as a light leakage phenomenon) occur.

On the other hand, various pressure-sensitive adhesives have been proposed.
For example, as a pressure-sensitive adhesive for a pressure-sensitive adhesive optical film, a pressure-sensitive adhesive layer is obtained by adding a low molecular weight material such as a plasticizer to a resin copolymerized with an α, β-unsaturated double bond group-containing compound. A pressure-sensitive adhesive is disclosed that moderately softens and imparts stress relaxation properties (see, for example, Patent Document 1).

  Further, for example, pressure-sensitive adhesives are known which are blended with resins having different molecular weights, copolymerized with an α, β-unsaturated double bond group-containing compound, and further contain a large amount of a crosslinking agent containing an isocyanate group. (For example, refer to Patent Document 2).

  Further, for example, in addition to a pressure-sensitive adhesive containing a resin obtained by copolymerizing an α, β-unsaturated double bond group-containing compound and a cross-linking agent, an adhesive obtained by using a polyurethane resin in combination with a general resin is known. (See Patent Document 3).

However, an optical pressure-sensitive adhesive film using the pressure-sensitive adhesive described in Patent Documents 1 to 3 is exposed to a high temperature or a high temperature and high humidity condition for a long time after being attached to an adherend. And at the peripheral edge of the optical film, extremely small bubbles formed of a resin obtained by copolymerizing a self-crosslinked product of an isocyanate group-containing crosslinking agent or a low molecular weight α, β-unsaturated double bond group-containing compound are streaked. It occurs in a continuous state. This phenomenon is called a “crack” because very small bubbles that appear as streaks look like a kind of crack.
In addition, about 10 bubbles of 10 μm or less, which cannot be confirmed unless using an electron microscope, are generated in the center part per 10 m ² .
Further, in a display device of 19 inches or more, the luminance of the light source must be set high from the viewpoint of easy viewing. The pressure-sensitive adhesive film for optical use (also referred to as optical adhesive film) formed by laminating and using the pressure-sensitive adhesive described in Patent Document 1 was not regarded as a problem in a display device of less than 19 inches. . However, due to cross-linking shrinkage due to the cross-linking agent and insufficient adhesion, there is also a problem that white spots are conspicuous in a display device using a high-intensity light source used at 19 inches or more.

  Further, for example, as a pressure-sensitive adhesive that does not cause appearance defects such as floating and peeling even in a high humidity and high temperature environment by using the obtained copolymer, α, β-unsaturated double containing an aromatic ring A copolymer resin obtained by copolymerizing a linking group-containing compound is disclosed (see Patent Document 4), and a heterocycle-containing α, β-unsaturated double bond group-containing compound is copolymerized. It is disclosed (see Patent Document 5). Further, a copolymer resin obtained by copolymerizing an α, β-unsaturated double bond group-containing compound having a carboxyl group and a weight average molecular weight of 700,000 or more, and an α, β-unsaturation having a weight average molecular weight of 800 to 50,000. A technique for improving stress relaxation properties by using in combination with a copolymer resin obtained by copolymerizing a double bond group-containing compound has been disclosed (see Patent Document 6).

  However, the copolymer resin obtained by copolymerizing an α, β-unsaturated double bond group-containing compound containing an aromatic ring or a heterocyclic ring disclosed herein has an extremely high solution viscosity, and is optically When creating pressure-sensitive adhesive films (adhesive films for optics), it is difficult to create unless the non-volatile content is reduced as much as possible. . Further, the obtained pressure-sensitive adhesive film for optical use (optical adhesive film) does not cause floating or peeling under a heat aging environment of 80 ° C. or 60 ° C.-90% relative humidity, but it is a more severe environment. Below, for example, in an environment of heat aging at 100 ° C. or moisture heat aging at 85 ° C.-90% relative humidity, the durability is not sufficient, and the cohesive force is remarkably reduced, and cracks and foaming are likely to occur. There was also.

  On the other hand, in order to impart removability, a low molecular weight acrylic polymer having a high acid value and a weight average molecular weight of 0.2 to 100,000 is used for a high molecular weight acrylic polymer having a weight average molecular weight of 500,000 or more. A technique for blending is disclosed (see Patent Document 7).

  Furthermore, a technique for improving the stress relaxation property by using together an acrylic polymer having a carboxyl group and a weight average molecular weight of 700,000 or more and an acrylic polymer having a weight average molecular weight of 800 to 50,000 is disclosed. (See Patent Document 8).

  In addition, a technique for improving durability and adhesive properties under heating and humidification conditions by using a block polymer using two or more kinds of monomers is disclosed (see Patent Document 9).

  Moreover, depolarization is caused by the water-dispersed pressure-sensitive adhesive containing an acrylic resin having a glass transition temperature of −55 ° C. or higher and lower than 0 ° C. and an acrylic resin having a glass transition temperature of 0 ° C. or higher and 180 ° C. or lower. A technique that is difficult and that imparts reworkability and recyclability has been disclosed (see Patent Document 10).

  Further, a technique for improving a good adhesive force is disclosed by a water-dispersed pressure-sensitive adhesive mainly composed of an acrylic copolymer copolymerized with a monomer having a phosphonyl group and containing a phosphate ester compound ( (See Patent Document 11).

  However, the pressure-sensitive adhesive described in Patent Document 7 has a problem that the drying conditions of the pressure-sensitive adhesive are limited. Further, the pressure-sensitive adhesive described in Patent Document 8 has a problem that the cohesive force is remarkably reduced, and the pressure-sensitive adhesive described in Patent Document 9 has a problem that the transmittance under heating and humidification conditions is decreased. In addition, the pressure-sensitive adhesives described in Patent Documents 10 and 11 have a problem of contaminating an adherend such as glass due to the influence of various additives used in the pressure-sensitive adhesive and the hygroscopicity associated therewith. .

  Further, as a crosslinking agent to be used, an adhesive containing an acrylic resin and an epoxy resin is disclosed (see Patent Document 12). Further, an adhesive using an acrylic resin and ethyleneimine is disclosed (see Patent Document 13). Furthermore, an adhesive using an acrylic resin having a carboxyl group, a hydroxyl group, and an epoxy group is disclosed (see Patent Document 14). Moreover, the adhesive agent with which the carboxyl group containing macropolyol and the carbodiimide group containing compound were mix | blended is disclosed (refer patent document 15).

  However, in Patent Document 12, in the acrylic resin and the epoxy resin, the functional group capable of crosslinking reaction with the epoxy group is not incorporated in the acrylic resin, the crosslinking reactivity of the epoxy group is poor, and the epoxy resin may remain. There is. When the remaining epoxy resin is hydrolyzed, two hydroxyl groups are generated, and the heat and moisture resistance and water resistance may be lowered. Moreover, in patent document 13, since the water solubility of ethyleneimine is high, the heat-and-moisture resistance and the water resistance fall, or the storage stability of ethyleneimine is bad, it may cause adhesion failure. Furthermore, in Patent Document 14, two or more functional groups capable of crosslinking reaction are copolymerized in the acrylic resin, and the pot life (also referred to as pot life) and storage stability are reduced by the self-crosslinking reaction. There is a case. Patent Document 15 is a system utilizing the reaction between a carboxyl group and a carbodiimide group, but the crosslinking reactivity between the carboxyl group and the carbodiimide group is high, and the storage stability may deteriorate, and the carbodiimide group-containing compound If the amount is reduced, the cohesive force after the cross-linking reaction may be insufficient, and it may not be possible to secure a balance of adhesive strength.

In view of such a situation, while maintaining high heat resistance and high heat-and-moisture resistance, a decrease in pressure-sensitive adhesive properties and optical properties is suppressed, and it can be used from film label applications to electrical and optical applications. A highly sensitive pressure sensitive adhesive has been desired.
Furthermore, a pressure-sensitive adhesive having both transparency, solubility in resin and solvent (compatibility), and heat-and-moisture resistance has been desired.

Japanese Patent Laid-Open No. 9-87593 JP 2001-049200 A JP 2003-073646 A JP 2003-193012 A JP 2007-277510 A JP 2004-069975 A JP 2010-1000071 A JP 2004-069975 A Japanese Patent Application Laid-Open No. 2013-082772 JP 2014-001365 A JP 2008-266506 A Japanese Examined Patent Publication No.59-037034 JP 05-287250 A Japanese Patent Laid-Open No. 11-061069 JP 2010-159339 A

    The problem to be solved by the present invention is to solve the above-mentioned problems, and when used in a pressure-sensitive adhesive film, it has excellent removability and is exposed after being exposed to a high temperature environment or a high temperature and high humidity environment. It is an object of the present invention to provide a pressure-sensitive adhesive that hardly causes floating or peeling from a body and a pressure-sensitive adhesive film using the pressure-sensitive adhesive. Further, when used for fixing a polarizing plate, the light leakage evaluation is good, it has a good adhesive force that can maintain high transparency even when exposed to a high temperature and high humidity environment, To provide a pressure-sensitive adhesive that does not contaminate a body and a pressure-sensitive adhesive film using the same.

  As a result of intensive studies to solve the above problems, the present inventors have found that the object can be achieved by the pressure-sensitive adhesive shown below, and have completed the present invention.

That is, an embodiment of the present invention is a pressure-sensitive adhesive comprising a copolymer (A) having a weight average molecular weight of 100,000 to 2,000,000 and a silane compound (B) having a primary or secondary amino group. The copolymer (A) relates to a pressure-sensitive adhesive containing the following compounds (a1), (a2) and (a3) as monomers constituting the copolymer (A).
Α, β-unsaturated double bond group-containing compound (a1) having one or more hydroxyl groups
Α, β-unsaturated double bond group-containing compound having one or more carbonyl groups (a2)
Α, β-unsaturated double bond group-containing compound having no hydroxyl group or carbonyl group (a3)
(However, the compound (a2) does not have a hydroxyl group)

In addition, in an embodiment of the present invention, the total amount of the compounds (a1), (a2) and (a3) constituting the copolymer (A) is 100% by weight,
0.1 to 30% by weight of compound (a1),
0.1 to 30% by weight of compound (a2),
Compound (a3) is 40 to 99.8% by weight,
It is related with the above-mentioned pressure sensitive adhesive.

  An embodiment of the present invention also relates to the pressure-sensitive adhesive, wherein the silane compound (B) having a primary or secondary amino group has a primary or secondary amine value of 100 to 600 mgKOH / g.

  In another embodiment of the present invention, the compound (a3) has an alkyl group having 2 to 20 carbon atoms, and the homopolymer has a glass transition temperature of -80 to 0 ° C. The present invention relates to the pressure-sensitive adhesive containing the double bond group-containing compound (a3-1).

  The embodiment of the present invention further relates to the pressure-sensitive adhesive containing the reactive compound (C) having one or more functional groups capable of reacting with the hydroxyl group in the copolymer (A).

  In addition, an embodiment of the present invention relates to a pressure-sensitive adhesive film, wherein an adhesive layer containing the pressure-sensitive adhesive is laminated on at least one surface of the substrate (G).

  Moreover, the embodiment of this invention is related with the said pressure sensitive adhesive film whose base material (G) is a transparent film (H).

  Moreover, the embodiment of this invention is related with the said pressure sensitive adhesive film whose transparent film (H) is optical film (I).

  In addition, an embodiment of the present invention relates to an optical laminate in which the optical film (I), an adhesive layer containing the pressure-sensitive adhesive, and glass are sequentially laminated.

  According to the present invention, it is preferably used for adhesion of optical members that can form a pressure-sensitive adhesive layer excellent in adhesion to an adherend, removability (reworkability), heat resistance, moist heat resistance and transparency. A pressure-sensitive adhesive that can be used is provided, and further, the use of the pressure-sensitive adhesive does not cause foaming or peeling even at high temperature or high humidity, and stress caused by expansion or contraction of an optical film such as a polarizing film. It has become possible to provide an optical laminate that reduces the concentration and does not cause light leakage such as uneven color and whitening in the liquid crystal display device.

Hereinafter, embodiments of the present invention will be described.
The pressure-sensitive adhesive of the present invention contains a copolymer (A) having a weight average molecular weight of 100,000 to 2,000,000 and a silane compound (B) having a primary or secondary amino group. An adhesive, wherein the copolymer (A) is a pressure-sensitive adhesive containing the following compounds (a1), (a2), and (a3) as monomer units constituting the copolymer (A). It is a feature.
Α, β-unsaturated double bond group-containing compound (a1) having one or more hydroxyl groups
Α, β-unsaturated double bond group-containing compound having one or more carbonyl groups (a2)
Α, β-unsaturated double bond group-containing compound having no hydroxyl group or carbonyl group (a3)
(However, the compound (a2) does not have a hydroxyl group)

  In this specification, “(meth) acryl”, “(meth) acryloyl”, “(meth) acrylic acid”, “(meth) acrylate”, “(meth) acryloyloxy”, and “(meth) allyl” Unless otherwise specified, “acrylic or methacrylic”, “acryloyl or methacryloyl”, “acrylic acid or methacrylic acid”, “acrylate or methacrylate”, “acryloyloxy or methacryloyloxy”, And “allyl or methallyl”.

Hereinafter, the components of the pressure-sensitive adhesive will be specifically described.
<Copolymer (A)>
The copolymer (A) includes, as monomers, an α, β-unsaturated double bond group-containing compound (a1) having one or more hydroxyl groups and an α, β-unsaturated compound having one or more carbonyl groups. A copolymer comprising a saturated double bond group-containing compound (a2) and an α, β-unsaturated double bond group-containing compound (a3) having no hydroxyl group or carbonyl group, and polymerizing a mixture of these monomers Can be manufactured.
First, the α, β-unsaturated double bond group-containing compound (a1) having one or more hydroxyl groups, which is a monomer unit constituting the copolymer (A), will be described.
The α, β-unsaturated double bond group-containing compound (a1) having one or more hydroxyl groups includes one or more hydroxyl groups and one or more α, β-unsaturated double bonds in the structure. And a compound having a hydroxyl group in the molecule and having no cyclic structure (a1-1) and a compound having a hydroxyl group in the molecule and having a cyclic structure (a1-2) it can. Specific examples include the following compounds.

  Of the α, β-unsaturated double bond group-containing compound (a1) having one or more hydroxyl groups, the compound (a1-1) having a hydroxyl group and not having a cyclic structure includes a hydroxyl group in the structure. For example, 2-hydroxyethyl (meth) acrylate, 1-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth) acrylic acid 3 -Hydroxypropyl, 1-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, (meth) acrylic acid 6 -Hydroxyhexyl, 8-hydroxyoctyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylic acid ester , (Meth) acrylic acid 10-hydroxydecyl, (meth) acrylic acid 12-hydroxylauryl, (meth) acrylic acid ethyl-α- (hydroxymethyl), monofunctional (meth) acrylic acid glycerol, or (meth) acrylic Fatty acid ester-based (meth) acrylic acid ester such as glycidyl lauric acid ester, glycidyl oleic acid (meth) acrylate, glycidyl stearate (meth) acrylate, or 2- (acryloyloxy) ethyl 6-hydroxyhexa (Meth) acrylic acid ester having a hydroxyl group at the terminal, obtained by ring-opening addition of ε-caprolactone to the hydroxyl group-containing α, β-ethylenically unsaturated double bond group-containing compound such as nonate, The hydroxyl group-containing α, β-ethylenically unsaturated double bond group Ethylene oxide relative to organic compounds, propylene oxide, alkylene oxide addition was repeated adding an alkylene oxide such as butylene oxide (meth) aliphatic hydroxyl group-containing acrylic acid ester (meth) acrylate;

  For example, hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether, hydroxyhexyl vinyl ether, hydroxyoctyl vinyl ether, hydroxydecyl vinyl ether, hydroxydodecyl vinyl ether, hydroxyoctadecyl vinyl ether, glyceryl vinyl ether, triethylene glycol monovinyl ether, tetraethylene glycol monovinyl ether, triethylene glycol Hydroxyl-containing aliphatic vinyl ethers such as methylolpropane monovinyl ether, pentaerythritol monovinyl ether, or alkylene oxide-added vinyl ether having a hydroxyl group at the terminal where alkylene oxide such as ethylene oxide or propylene oxide is repeatedly added;

  For example, (meth) allyl alcohol, isopropenyl alcohol, dimethyl (meth) allyl alcohol, hydroxyethyl (meth) allyl ether, hydroxypropyl (meth) allyl ether, hydroxybutyl (meth) allyl ether, hydroxyhexyl (meth) allyl ether , Hydroxyoctyl (meth) allyl ether, hydroxydecyl (meth) allyl ether, hydroxydodecyl (meth) allyl ether, hydroxyoctadecyl (meth) allyl ether, glyceryl (meth) allyl ether, or alkylene oxides such as ethylene oxide and propylene oxide Hydroxyl group-containing aliphatic (meth) allyl alcohols such as alkylene oxide addition system (meth) allyl ether having a hydroxyl group at the terminal of repeating addition of Or (meth) allyl ethers;

  For example, α, β-unsaturated double bond group-containing compounds having a plurality of hydroxyl groups such as propenediol, butenediol, heptenediol, octenediol, and glycerol di (meth) acrylate;

  For example, hydroxyl groups such as N-hydroxyethyl (meth) acrylamide, N-hydroxypropyl (meth) acrylamide, N-hydroxybutyl (meth) acrylamide, N-hydroxyhexyl (meth) acrylamide, N-hydroxyoctyl (meth) acrylamide, etc. Of (meth) acrylamides;

  Examples thereof include monomers having a hydroxyl group and a vinyl group such as vinyl alcohol, but are not particularly limited thereto. These may use only 1 type or may use multiple types together. As the compound (a1-1), from the viewpoint of adhesion to the substrate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, ε -Caprolactone 1-2 mol addition (meth) acrylic acid 2-hydroxyethyl etc., C2-C18 alpha, beta-unsaturated double bond group containing compound is especially preferable.

  Of the α, β-unsaturated double bond group-containing compound (a1) having one or more hydroxyl groups, the compound (a1-2) having a hydroxyl group and having a cyclic structure includes a hydroxyl group and a cyclic group in the structure. If it has both of a structure, there will be no restriction | limiting in particular, For example, (meth) acrylic acid 1,2-cyclohexanedimethanol, (meth) acrylic acid 1,3-cyclohexanedimethanol, (meth) acrylic acid 1,4 -Cyclohexanedimethanol, 2-hydroxy-3-phenoxymethyl (meth) acrylate, 2-hydroxy-3-phenoxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, (meth) 2-hydroxy-3-phenoxybutyl acrylate, 2-hydroxy-3-phenoxydecyl (meth) acrylate, (meth) acrylic It has a hydroxyl group and a hydrocarbon ring such as 2-hydroxy-3-phenoxyoctadecyl oxalate, monohydroxyethyl phthalate (meth) acrylate, 2- (4-benzoyl-3-hydroxyphenoxy) ethyl (meth) acrylate (meta ) Acrylic esters;

  For example, 2-hydroxy-4- {2- (meth) acryloyloxy} ethoxybenzophenone, 2-hydroxy-4- {2- (meth) acryloyloxy} butoxybenzophenone, 2,2′-dihydroxy-4- {2- Hydroxyl group-containing benzophenone-based (meth) acrylic esters such as (meth) acryloyloxy} ethoxybenzophenone, 2-hydroxy-4- {2- (meth) acryloyloxy} ethoxy-4 ′-(2-hydroxyethoxy) benzophenone;

  For example, 2- (2′-hydroxy-5 ′-(meth) acryloyloxyethylphenyl) -2H-benzotriazole, 2- (2′-hydroxy-5 ′-(meth) acryloyloxyethylphenyl) -5-chloro -2H-benzotriazole, 2- (2'-hydroxy-5 '-(meth) acryloyloxypropylphenyl) -2H-benzotriazole; 2- (2'-hydroxy-5'-(meth) acryloyloxypropylphenyl) -5-chloro-2H-benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5 '-(meth) acryloyloxyethylphenyl) -2H-benzotriazole, and 2- (2'-hydroxy -3'-tert-butyl-5 '-(meth) acryloyloxyethylphenyl) -5-chloro-2H-ben Hydroxyl group-containing benzotriazole-based triazole (meth) acrylic acid esters;

  For example, 2,4-diphenyl-6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis (2-methylphenyl) -6- [2- Hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis (2-methoxyphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy }]-S-triazine, 2,4-bis (2-ethylphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis ( 2-Ethoxyphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis (2,4-dimethylphenyl) -6- [2- Hydroxy-4- {2- Meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis (2,4-diethoxylphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S- Hydroxyl-containing triazines such as triazine and 2,4-bis (2,4-diethylphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy})]-S-triazine (meta ) Acrylic acid esters and the like, and these may be used alone or in combination of two or more.

  As the compound (a1-2), (meth) acrylic acid 1,2-cyclohexanedimethanol, (meth) acrylic acid 1,3-cyclohexanedi, in terms of durability such as heat resistance, moist heat resistance, and water resistance. Methanol, (meth) acrylic acid 1,4-cyclohexanedimethanol, (meth) acrylic acid 2-hydroxy-3-phenoxypropyl and the like are particularly preferable.

  Thus, by copolymerizing the compound (a1), a preferable polymerization rate is obtained, and it becomes easy to control the molecular weight and the crosslinking density of the copolymer (A). Accordingly, when the copolymer (A) is used as a pressure-sensitive adhesive, it is possible to form a crosslinked coating film having high cohesive strength. Moreover, since the crosslinking reactivity accompanying the condensation reaction with the siloxy group contained in the silane compound (B) having a primary or secondary amino group, which will be described later, is improved and the cohesive force can be improved, the optical used for the optical member When manufacturing a laminated body, not only heat resistance, heat-and-moisture resistance, water resistance, etc. are excellent, but it becomes easy to provide sufficient workability.

The α, β-unsaturated double bond group-containing compound (a2) having one or more carbonyl groups, which is a monomer unit constituting the copolymer (A), will be described.
The α, β-unsaturated double bond group-containing compound (a2) having one or more carbonyl groups is an α, β-unsaturated double bond group-containing compound having at least one carbonyl group as a substituent. However, the compound (a2) does not have a hydroxyl group. In addition, among the α, β-unsaturated double bond group-containing compounds, when having a (meth) acryloyl group, the carbon-oxygen double bond in the (meth) acryloyl group is bonded to the “carbonyl group”. Shall not be included.
As the α, β-unsaturated double bond group-containing compound (a2) having one or more carbonyl groups in the molecule, the carbonyl group-containing compound (a2-1) derived from an acyl group or a formyl group, The carbonyl group can be classified into an carbonyl group-containing compound (a2-2) derived from an ester group, and the carbonyl group-containing compound (a2-3) derived from a carboxyl group. However, an acid anhydride is also contained in a carboxyl group. Specific examples include the following compounds.

  More specifically, examples of the carbonyl group-containing compound (a2-1) in which the carbonyl group is an acyl group or a formyl group include (meth) acrylic acid (methoxycarbonyl) methyl, (meth) acrylic acid (methoxycarbonyl) Ethyl, (meth) acrylic acid (methoxycarbonyl) propyl, (meth) acrylic acid (methoxycarbonyl) butyl, (meth) acrylic acid (methoxycarbonyl) decyl, (meth) acrylic acid (ethoxycarbonyl) methyl, (meth) acrylic Acid (ethoxycarbonyl) ethyl, (meth) acrylic acid (ethoxycarbonyl) propyl, (meth) acrylic acid (ethoxycarbonyl) butyl, (meth) acrylic acid (ethoxycarbonyl) hexyl, (meth) acrylic acid (ethoxycarbonyl) octyl , (Meth) acrylic acid 2- (ethoxycarbonyloxy) ) Ethyl, 2- (ethoxycarbonyloxy) propyl (meth) acrylate, 2- (ethoxycarbonyloxy) butyl (meth) acrylate, 2- (ethoxycarbonyloxy) hexyl (meth) acrylate, (meth) acrylic acid 2- (Ethoxycarbonyloxy) octyl, 2- (propoxycarbonyloxy) ethyl (meth) acrylate, 2- (butoxycarbonyloxy) ethyl (meth) acrylate, 2- (butoxycarbonyloxy) butyl (meth) acrylate Aliphatic (meth) acrylic acid esters having one carbonyl group such as 2- (octyloxycarbonyloxy) ethyl (meth) acrylate and 2- (octyloxycarbonyloxy) butyl (meth) acrylate;

  For example, 2-oxobutanoylethyl (meth) acrylate, 2-oxobutanoylpropyl (meth) acrylate, 2-oxobutanoylbutyl (meth) acrylate, 2-oxobutanoylhexyl (meth) acrylate, (Meth) acrylic acid 2-oxobutanoyloctyl, (meth) acrylic acid 2-oxobutanoyldecyl, (meth) acrylic acid 2-oxobutanoyldodecyl, (meth) acrylic acid 3-oxobutanoylethyl, ) 3-oxobutanoylpropyl acrylate, 3-oxobutanoylbutyl (meth) acrylate, 3-oxobutanoylhexyl (meth) acrylate, 3-oxobutanoyloctyl (meth) acrylate, (meth) acrylic 3-oxobutanoyldecyl acid, 3-oxobutanoyldodecyl (meth) acrylate (Meth) acrylic acid 4-cyanooxobutanoylethyl, (meth) acrylic acid 4-cyanooxobutanoylpropyl, (meth) acrylic acid 4-cyanooxobutanoylbutyl, (meth) acrylic acid 4-cyanooxobutanoyl Ruhexyl, 4-cyanooxobutanoyloctyl (meth) acrylate, 2,3-di (oxobutanoyl) propyl (meth) acrylate, 2,3-di (oxobutanoyl) butyl (meth) acrylate, ( Aliphatic (meth) acrylic acid esters having two carbonyl groups such as 2,3-di (oxobutanoyl) hexyl (meth) acrylate and 2,3-di (oxobutanoyl) octyl (meth) acrylate Kind;

For example, methyl 4- (methoxycarbonyl) benzene (meth) acrylate, (meth) acrylic acid-9-methoxycarbonyl-5-oxo-4-oxa-tricyclo [4.2.1.0 ^3,7 ] non- 2-yl, (meth) acrylic acid-10-methoxycarbonyl-5-oxo-4-oxa-tricyclo [5.2.1.0 ^3,8 ] non-2-yl, (meth) acrylic acid-4- Methoxycarbonyl-6-oxo-7-oxa-bicyclo [3.2.1] oct-2-yl, (meth) acrylic acid-4-methoxycarbonyl-7-oxo-8-oxa-bicyclo [3.3. 1] (meth) acrylic acid cyclic esters having a carbonyl group such as octa-2-yl;

  For example, N- (2-oxobutanoylethyl) (meth) acrylamide, N- (2-oxobutanoylpropyl) (meth) acrylamide, N- (2-oxobutanoylbutyl) (meth) acrylamide, N- ( It has a carbonyl group such as 2-oxobutanoylhexyl) (meth) acrylamide, N- (2-oxobutanoyloctyl) (meth) acrylamide, N- (1,1-dimethyl-3-oxobutyl) (meth) acrylamide, etc. (Meth) acrylamides;

  For example, vinyl acetoacetate, vinyl acetopropionate, vinyl acetoisobutyrate, vinyl acetobutyrate, vinyl acetovalerate, vinyl acetohexanoate, vinyl aceto-2-ethylhexanoate, vinyl aceto-n-octanoate, vinyl acetodecanoate, acetodecane Vinyl acetate, vinyl acetooctadecanoate, vinyl acetopivalate, vinyl acetocaprate, vinyl acetocrotonate, vinyl acetosorbate, vinyl propanoyl acetate, vinyl butyryl acetate, vinyl isobutyryl acetate, vinyl palmitoyl acetate, vinyl stearoyl acetate, vinyl pyroyl acetate , Vinyl propanoyl valerate, vinyl butyryl valerate, vinyl isobutyryl valerate, palmitoyl vinyl valerate, stearoyl valerate, pyrvoyl Vinyl ester compounds such aceto fatty acids having a carbonyl group of vinyl Rerin acid, and the like;

  For example, vinyl ether compounds having a carbonyl group such as 2-acetoacetoxyethyl vinyl ether, 2-acetoacetoxybutyl vinyl ether, 2-acetoacetoxyhexyl vinyl ether, 2-acetoacetoxyoctyl vinyl ether;

  For example, acetoacetic acid (meth) allyl, acetopropionic acid (meth) allyl, acetoisobutyric acid (meth) allyl, acetobutyric acid (meth) allyl, acetovaleric acid (meth) allyl, acetohexanoic acid (meth) allyl, aceto-2- Ethylhexanoic acid (meth) allyl, aceto-n-octanoic acid (meth) allyl, acetodecanoic acid (meth) allyl, acetodecanoic acid (meth) allyl, acetooctadecanoic acid (meth) allyl, acetopivalic acid (meth) allyl, acetocaprin Acid (meth) allyl, acetocrotonic acid (meth) allyl, acetosorbic acid (meth) allyl, propanoyl acetate (meth) allyl, butyryl acetate (meth) allyl, isobutyryl acetate (meth) allyl, palmitoyl acetate (meth) allyl, Stearoyl acetate (meth) allyl, (meth) allyl Aliphatic (meth) allyl compounds having an acyl group such as hydrate and the like. It is not limited to these, Only 1 type may be used or multiple types may be used together.

  Examples of the carbonyl group-containing compound (a2-2) in which the carbonyl group is derived from an ester group include vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caprate, vinyl laurate, vinyl versatate, vinyl pivalate, Vinyl esters of carboxylic acids such as vinyl palmitate and vinyl stearate;

  For example, vinyl benzoylformate, vinyl benzoyl acetate, vinyl benzoylpropionate, vinyl benzoylbutyrate, vinyl benzoylvalerate, vinyl benzoylhexanoate, vinyl benzoyldodecanoate, 1-naphthoylvinyl acetate, 1-naphthoylpropionate, 1- Naphthoyl vinyl butyrate, 1-naphthoyl vinyl valerate, 1-naphtho vinyl hexanoate, 2-naphtho vinyl acetate, 2-naphtho vinyl propionate, 2-naphtho vinyl butyrate, 2-naphtho vinyl butyrate, 2- Vinyl naphthoyl hexanoate, vinyl nicotinoyl acetate, vinyl nicotinoyl propionate, vinyl nicotinoyl butyrate, vinyl nicotinoyl valerate, vinyl nicotinoyl hexanoate, vinyl nicotinoyl decanoate, nicotine Vinyl dodecanoate, vinyl isonicotinoyl acetate, vinyl isonicotinoyl propionate, vinyl isonicotinoyl butyrate, vinyl isonicotinoyl valerate, vinyl isonicotinoyl hexanoate, vinyl isonicotinoyl decanoate, vinyl isonicotinoyl dodecanoate, 2-furoyl Vinyl acetate, vinyl 2-furoylpropionate, vinyl 2-furoylbutyrate, vinyl 2-furoylvalerate, vinyl 2-furoylhexanoate, vinyl 2-furoyldecanoate, vinyl 2-furoyldodecanoate, 3-furoyl Vinyl acetate, vinyl 3-furoylpropionate, vinyl 3-furoylbutyrate, vinyl 3-furoylvalerate, vinyl 3-furoylhexanoate, vinyl 3-furoyldecanoate, vinyl 3-furoyldodecanoate, vinyl anthraniloyl acetate Fragrance having a carbonyl group derived from an ester group such as vinyl anthraniloyl propionate, vinyl anthraniloyl butyrate, vinyl anthraniloyl valerate, vinyl anthraniloyl hexanoate, vinyl anthraniloyl decanoate, vinyl anthraniloyl decanoate Family vinyl esters;

  For example, 4- (2-t-ethoxycarbonylethyloxy) styrene, 4- (2-t-butoxycarbonylethyloxy) styrene, 4- (2-t-butoxycarbonylethyloxy) -α-methylstyrene, 4- ( 2-t-butoxycarbonylpropyloxy) styrene-based vinyl compounds having a carbonyl group derived from an ester group such as styrene;

  For example, mono-long-chain alkyl ester cyclic compounds of dicarboxylic acids such as vinyl phenylnonyl succinate, vinyl phenyl methyl decyl hexahydrophthalate, vinyl phenyl ethyl dodecyl terephthalate;

For example, monopolyalkylene oxide esters of dicarboxylic acids such as vinyl phenyl poly (ethylene oxide) succinate, vinyl phenyl methyl poly (ethylene oxide) hexahydrophthalate, vinyl phenyl ethyl poly (ethylene oxide) terephthalate;
Polyalkylene oxides such as methyl 4-vinylbenzoate poly (ethylene oxide), ethyl polyvinylbenzoate poly (ethylene oxide), methyl 4-isopropenylbenzoate poly (propylene oxide), ethyl polyisopropylenylbenzoate poly (propylene oxide) Vinyl benzoate or isopropenyl benzoate compounds having a moiety;

  For example, saturation of acetic acid (meth) allyl, propionic acid (meth) allyl, butyric acid (meth) allyl, capric acid (meth) allyl, lauric acid (meth) allyl, allyl octylate, coconut oil fatty acid allyl, pivalate allyl, etc. (Meth) allyl esters of carboxylic acids;

  For example, cis-diallyl succinate, diallyl 2-methylidene succinate, vinyl (E) -but-2-enoate, (Z) -octadeca-9-enoate, (9Z, 12Z, 15Z) -octadeca-9, Alkenyl compounds containing polyfunctional unsaturated bonds such as vinyl 12,15-trienoate;

  For example, benzoyl formate (meth) allyl, benzoyl acetate (meth) allyl, benzoylpropionate (meth) allyl, benzoylbutyrate (meth) allyl, benzoylvalerate (meth) allyl, benzoylhexanoic acid (meth) allyl, benzoyldodecanoic acid (Meth) allyl, 1-naphthoylacetic acid (meth) allyl, 1-naphthoylpropionic acid (meth) allyl, 1-naphthoylbutyric acid (meth) allyl, 1-naphthoylvaleric acid (meth) allyl, 1-naphthoylhexane Acid (meth) allyl, 2-naphthoylacetic acid (meth) allyl, 2-naphthoylpropionic acid (meth) allyl, 2-naphthoylbutyric acid (meth) allyl, 2-naphthoylvaleric acid (meth) allyl, 2-naphthoyl Fragrance with carbonyl group derived from ester group such as hexanoic acid (meth) allyl Although (meth) allyl compounds and the like of the system include, but is not particularly limited thereto. These may use only 1 type or may use multiple types together.

  Examples of the carbonyl group-containing compound (a2-3) in which the carbonyl group is derived from a carboxyl group include 2-carboxyethyl (meth) acrylate, 2-carboxypropyl (meth) acrylate, and 3-carboxypropyl (meth) acrylate. 4-carboxybutyl (meth) acrylate, aconitic acid, glutaconic acid, aconitic acid, penicillic acid, citronellic acid, maleic acid, fumaric acid, monomethylmaleic acid, monomethylfumaric acid, cinnamic acid, α-chlorosorbic acid, Citraconic acid, mesaconic acid, itaconic acid, tiglic acid, angelic acid, senetic acid, crotonic acid, isocrotonic acid, mucobromic acid, mucochloric acid, sorbic acid, muconic acid, gellanic acid, 4- (meth) acrylamidobutanoic acid, 6- (Meth) acrylamide hexanoic acid, 2- (meth) a Polylactone-based (meth) acrylic acid ester having a carboxyl group at the terminal by ring-opening addition of lactone ring, such as liloyloxyethyl succinate, mono (meth) acrylic acid ω-carboxypolycaprolactone ester, ethylene oxide, propylene oxide, etc. A succinic acid to which the alkylene oxide is repeatedly added has a carboxyl group at one end and a carboxyl group-containing fat such as a succinic (meth) acrylic acid ester having a (meth) acryloyl group at the other end Group α, β-unsaturated double bond group-containing carboxylic acids and acid anhydrides thereof;

  For example, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxypropyl phthalate, 2- (meth) acryloyloxybutyl phthalate, 2- (meth) acryloyl Oxyhexyl phthalate, 2- (meth) acryloyloxyoctyl phthalate, 2- (meth) acryloyloxydecyl phthalate, 2-vinylbenzoic acid, 3-vinylbenzoic acid, 4-vinylbenzoic acid, 4-isopropenylbenzenecarboxylic acid, Carboxylic acids such as cinnamic acid, 7-amino-3-vinyl-3-cephem-4-carboxylic acid and the like, and carboxylic acids containing alicyclic and aromatic rings containing aromatic groups and aromatic rings, and acid anhydrides thereof Are not limited to these. Absent. These may use only 1 type or may use multiple types together.

As described above, the copolymer (A) preferably has a carbonyl group in the side chain, and is copolymerized with an α, β-unsaturated double bond group-containing compound (a2) having one or more carbonyl groups. By doing so, it can be introduced into the copolymer (A). In this way, when the silane compound (B) having an amino group described below is blended by having a carbonyl group, the carbonyl group and the amino group are cross-linked by the interaction accompanying the formation of a covalent bond such as a Michael addition reaction. It is preferable to use a carbonyl group-containing compound (a2-1) in which the carbonyl group is an acyl group or a formyl group.
In view of the addition reactivity between a carbonyl group and an amino group, an acyl group or a formyl group-derived carbonyl group is more preferable than an ester group-derived carbonyl group or a carboxyl group-derived carbonyl group because a crosslinked structure is more easily formed. . The reactivity of the amino group and the carbonyl group is in the order of (high reactivity) formyl group ≧ acyl group> carboxyl group> ester group (low reactivity). In order to act, it is determined by the degree to which the carbonyl carbon is positively charged.
Thus, coating is performed using a pressure-sensitive adhesive containing a copolymer (A) obtained by copolymerizing an α, β-unsaturated double bond group-containing compound (a2) having one or more carbonyl groups. Even if the formed adhesive film is attached to an adherend and exposed to heat and humidification heat conditions for a long time, deterioration due to foaming, floating and peeling is remarkably suppressed, and durability such as heat resistance and moisture heat resistance Has the advantage of significantly improving.

  Among the carbonyl group-containing compounds (a2), in view of Michael addition reactivity, price, and industrial availability, acrylic acid (methoxycarbonyl) methyl, methacrylic acid (methoxycarbonyl) methyl, acrylic acid 2 -Oxobutanoylethyl, 2-oxobutanoylethyl methacrylate, N- (1,1-dimethyl-3-oxobutyl) acrylamide are particularly preferred.

In the copolymer (A), the α, β-unsaturated double bond group-containing compound (a3) having no hydroxyl group and carbonyl group, which is a monomer unit constituting the copolymer (A), will be described.
The compound (a3) is a compound containing an α, β-unsaturated double bond group that does not have both a hydroxyl group and a carbonyl group in the molecule, and contains the component (a3) in the copolymer (A). This makes it easy to increase the efficiency of the copolymerization reaction with the compound (a1) and the compound (a2). In addition, the viscosity of the copolymer (A) can be easily reduced, and the workability during coating can be easily improved. In addition, the glass transition temperature (hereinafter referred to as Tg) of the coated product is controlled to improve the adhesiveness (also referred to as tack), and the cohesive strength of the coating film is improved so that the heat resistance, water resistance, and other resistances are improved. It is possible to form a good pressure-sensitive adhesive layer.
Among the compounds (a3), an α, β-unsaturated double bond group having an alkyl group having 2 to 20 carbon atoms such that the Tg of a homopolymer (also referred to as a homopolymer) is −80 to 0 ° C. The containing compound (a3-1) is preferred. By using the compound (a3-1) as a monomer unit constituting the copolymer, it becomes possible to impart tack to the copolymer (A), and it can be usefully used as a pressure-sensitive adhesive. It becomes possible.

Here, the glass transition temperature (Tg) is measured using a differential scanning calorimeter (DSC) described later, but can be theoretically calculated by the following FOX equation.
<FOX type> 1 / Tg = W1 / Tg1 + W2 / Tg2 + ... + Wi / Tgi + ... + Wn / Tgn
[In the above FOX formula, the glass transition temperature of a homopolymer of each compound constituting a polymer comprising n kinds of α, β-unsaturated double bond group-containing compounds is Tgi (K), and the mass fraction of each compound The rate is Wi, (W1 + W2 + ... + Wi + ... Wn = 1). ]

  Furthermore, the value described in literature can be used for Tg of a homopolymer. As such documents, for example, the following documents can be referred to: Mitsubishi Rayon Co., Ltd. acrylic ester catalog (2001 edition); Osaka Organic Chemical Industry Co., Ltd. catalog (2009 edition); Hitachi Chemical Co., Ltd. funkrill catalog ( 2007 edition); and "POLYMER HANDBOOK" 3rd edition, pages 209-277, John Wiley & Sons, Inc. 1989. In addition, Tg of the copolymer (A) was determined using the below-mentioned differential scanning calorimeter (DSC).

  Of the compound (a3), an α, β-unsaturated double bond group-containing compound having an alkyl group having 2 to 20 carbon atoms and a homopolymer having a glass transition temperature (Tg) of −80 to 0 ° C. Examples of (a3-1) include ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, pentyl acrylate, isoamyl acrylate, (meta ) Hexyl acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 3,4-dimethylhexyl (meth) acrylate, (meth) Nonyl acrylate, isononyl (meth) acrylate, 3,4-dimethylheptyl (meth) acrylate, (meth) acrylic Examples include (meth) acrylic acid alkyl esters such as decyl acid, lauryl (meth) acrylate, and isostearyl acrylate. Among these, n-butyl acrylate and 2-ethylhexyl acrylate are likely to exhibit good tack. This is preferable. These may be used alone or in combination of two or more.

  Among the compounds (a3), an α, β-unsaturated double bond group-containing compound (a3−) having an alkyl group having 2 to 20 carbon atoms and having a homopolymer having a glass transition temperature of −80 to 0 ° C. As the α, β-unsaturated double bond group-containing compound (a3-2) other than 1), the viscosity, durability, optical properties, or coating suitability of the pressure-sensitive adhesive containing the copolymer (A) Based on the above, it is possible to appropriately select an α, β-unsaturated double bond group-containing compound other than the compound (a3-1). However, the compound (a3) does not include the compound (a1) and the compound (a2). Examples of such α, β-unsaturated double bond group-containing compound (a3-2) include α, β-unsaturated double bond group-containing compounds having a primary or secondary amino group (a3-2-2). 1) and an α, β-unsaturated double bond group-containing compound (a3-2-2) having no primary or secondary amino group. However, since the activity of active hydrogen contained in the amino group is low, the compound (a3-2-1) does not contain a carbamoyl group of an acrylamide compound.

In this specification, the amino group means a generic name of monovalent residues excluding hydrogen atoms on nitrogen atoms in ammonia, primary amines, and secondary amines, and refers to primary amino groups, secondary amino groups. The term “tertiary amino group” means a monovalent residue obtained by removing a hydrogen atom on a nitrogen atom in ammonia, primary amine and secondary amine, respectively.
As the secondary amino group, an N-alkylamino group and an N-arylamino group are preferable. The tertiary amino group is preferably an N, N-dialkylamino group, an N, N-diarylamino group, or an N-alkyl-N-arylamino group.

  As the α, β-unsaturated double bond group-containing compound (a3-2-1) having a primary or secondary amino group in the compound (a3-2), for example, (meth) acrylic acid N— Methylaminoethyl, N-ethylaminoethyl (meth) acrylate, N-propylaminoethyl (meth) acrylate, N-butylaminoethyl (meth) acrylate, N-tributylaminoethyl (meth) acrylate, (meth ) (Meth) acrylic acid esters having a primary or secondary amino group such as tetramethylpiperidinyl acrylate;

  For example, (meth) acrylic acid hydrazide, 2- (2-furyl) -3- (5-nitro-2-furyl) (meth) acrylic acid hydrazide, β- (2-furanyl) (meth) acrylic acid N2, N2 (Meth) acrylic acid esters having a hydrazino group such as bis (2-chloroethyl) hydrazide, N- (m-vinylphenyl) acrylohydrazide;

  For example, vinyl compounds having a hydrazino group such as p-vinylbenzhydrazide, 4-vinylbenzenesulfonic acid hydrazide, 2- [2- (5-nitro-2-furyl) vinyl] -4-quinolinecarbohydrazide

  For example, vinylamine, methylvinylamine, ethylvinylamine, propylvinylamine, butylvinylamine, 2-vinylimidazole, 2-vinylpiperazine, 4-vinylpiperazine, 2-vinylpyrrole, 2-methyl-5-vinyl-1H- Vinyl compounds having a primary or secondary amino group such as pyrrole, 2-vinyl-1H-benzimidazole, 2-vinyl-5,6-dimethyl-1H-benzimidazole, 2-vinylindazole;

  For example, (meth) allylamine, 2- (meth) allylimidazole, 2- (meth) allylpiperazine, 4- (meth) allylpiperazine, 2- (meth) allylpyrrole, 4- (meth) allyl-3,5- (Meth) allyl compounds having a primary or secondary amino group such as dimethyl-1H-pyrazole;

  Examples thereof include alkenyl group-containing compounds having a primary or secondary amino group such as maleimide, N- [2- (1H-imidazol-5-yl) ethyl] (meth) acrylamide, and the like. It is not limited. These may be used alone or in combination of two or more.

  Of the compound (a3-2), the α, β-unsaturated double bond group-containing compound (a3-2-2) having no primary or secondary amino group includes, for example, methyl (meth) acrylate , Ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl (meth) acrylate, pentyl methacrylate, isoamyl methacrylate, (meta ) (Meth) acrylic acid alkyl esters whose Tg of homopolymer exceeds 0 ° C., such as stearyl acrylate;

  For example, (meth) acrylic acid (meth) allyl, (meth) acrylic acid 1-butenyl, (meth) acrylic acid 2-butenyl, (meth) acrylic acid 3-butenyl, (meth) acrylic acid 1,3-methyl- 3-butenyl, (meth) acrylic acid 2-chloro-2-propenyl, (meth) acrylic acid 3-chloro-2-propenyl, (meth) acrylic acid 2- (2-propenyloxy) ethyl, (meth) acrylic acid 2- Propenyl lactyl, 3,7-dimethyloct-6-en-1-yl (meth) acrylate, (meth) acrylic acid (E) -3,7-dimethyloct-2,6-dien-1-yl, (Meth) acrylic acid esters further containing an unsaturated double bond group such as rosinyl (meth) acrylate, cinnamyl (meth) acrylate, vinyl (meth) acrylate;

  For example, perfluoromethyl (meth) acrylate, perfluoroethyl (meth) acrylate, perfluoropropyl (meth) acrylate, perfluorobutyl (meth) acrylate, perfluorooctyl (meth) acrylate, (meth) Trifluoromethylmethyl acrylate, 2-trifluoromethylethyl (meth) acrylate, diperfluoromethylmethyl (meth) acrylate, 2-perfluoroethylethyl (meth) acrylate, 2-par (meth) acrylate Fluoromethyl-2-perfluoroethylmethyl, triperfluoromethylmethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate , (Meth) acrylic acid 2-perfluorode Ruechiru, (meth) (meth) acrylic acid perfluoroalkyl esters such as 2-perfluoro-hexadecyl acrylate;

  For example, fluorine-containing vinyl compounds such as perfluorovinyl, perfluoropropene, perfluoro (propyl vinyl ether), vinylidene fluoride;

  For example, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-propoxyethyl (meth) acrylate, 3-propoxyethyl (meth) acrylate, 2-butoxy (meth) acrylate Alkoxy group-containing (meth) acrylic acid esters such as ethyl, 3-butoxyethyl (meth) acrylate, 4-butoxyethyl (meth) acrylate;

  For example, (meth) acrylic acid esters of (meth) acrylic acid having an alkylene oxide moiety that does not have a hydroxyl group at the terminal with an alkylene oxide adduct such as ethylene oxide or propylene oxide;

  For example, halogenated alkenyl compounds such as vinyl chloride, vinylidene chloride and allyl chloride;

  For example, methyl vinyl ether, ethyl vinyl ether, 2-chlorovinyl ether, n-propyl vinyl ether, allyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, n-pentyl vinyl ether, isopentyl vinyl ether, tert -Pentyl vinyl ether, n-hexyl vinyl ether, isohexyl vinyl ether, 2-ethylbutyl vinyl ether, 2-ethylhexyl vinyl ether, n-heptyl vinyl ether, n-octyl vinyl ether, isooctyl vinyl ether, nonyl vinyl ether, decyl vinyl ether, dodecyl vinyl ether, hexadecyl vinyl ether , Octade Ruvinyl ether, ethoxymethyl vinyl ether, 2-methoxyethyl vinyl ether, 2-ethoxyethyl vinyl ether, 2-butoxyethyl vinyl ether, acetoxymethyl vinyl ether, 2-acetoxyethyl vinyl ether, 3-acetoxypropyl vinyl ether, 4-acetoxybutyl vinyl ether, 4-ethoxy Butyl vinyl ether, 2- (2-methoxyethoxy) ethyl vinyl ether, 3-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether, diethylene glycol methyl vinyl ether, diethylene glycol ethyl vinyl ether, diethylene glycol butyl vinyl ether, etc. The aliphatic bi Ethers;

  For example, ethylene glycol divinyl ether, diethylene glycol divinyl ether (DEGVE), triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, tripropylene glycol divinyl ether, polypropylene glycol Divinyl ether, butanediol divinyl ether, neopentyl glycol divinyl ether, hexanediol divinyl ether, nonanediol divinyl ether, hydroquinone divinyl ether, 1,4-cyclohexanediol divinyl ether (CHODVE), 1,4-cyclohexanedimethanol divinyl ether ( HDVE), trimethylolpropane trivinyl ether, ethylene oxide-added trimethylolpropane trivinyl ether (TMPEOTVE), pentaerythritol tetravinyl ether, ethylene oxide-added pentaerythritol tetravinyl ether, ditrimethylolpropane tetravinyl ether, dipentaerythritol hexavinyl ether, etc. Vinyl ethers;

  For example, 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltripropoxysilane, 3- (meth) acryloyloxypropyltributoxysilane 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropylmethyldiethoxysilane, 3- (meth) acryloyloxypropylethyldimethoxysilane, 3- (meth) acryloyloxypropylbutyldimethoxysilane, 3- (meth) acryloyloxypropylethyldipropoxysilane, 3- (meth) acryloyloxypropylmethyldiethoxysilane, 3- (meth) acryloyloxypropyltrime Kishishiran, 3- (meth) acryloyloxy propyl triethoxysilane, 3- (meth) acryloyl alkoxysilyl group-containing (meth) acrylic acid esters such as propyl tripropoxysilane;

  For example, (meth) allyltrimethoxysilane, (meth) allyltriethoxysilane, (meth) allylaminotrimethylsilane, diethoxyethylvinylsilane, trimethoxyvinylsilane, triethoxyvinylsilane, tripropoxyvinylsilane, vinyltris (2-methoxyethoxy) (Meth) allyl compounds containing alkoxysilyl groups such as silane, or vinyl compounds;

  For example, halogen-containing silyl group-containing α, β-unsaturated double bond group-containing compounds such as (meth) allylchlorosilane, (meth) allylbromosilane, trichlorovinylsilane;

  For example, di (meth) acrylic acid ethylene oxide, di (meth) acrylic acid triethylene oxide, di (meth) acrylic acid tetraethylene oxide, di (meth) acrylic acid polyethylene oxide, di (meth) acrylic acid propylene oxide, di (Meth) acrylic acid dipropylene oxide, di (meth) acrylic acid tripropylene oxide, di (meth) acrylic acid polypropylene oxide, di (meth) acrylic acid butene oxide, di (meth) acrylic acid pentane oxide, di (meth) 2,2-dimethylpropyl acrylate, hydroxypivalylhydroxypivalate di (meth) acrylate, hydroxypivalylhydroxypivalate hydroxypivalate dicaprolactonate, 1,6-hexane di (meth) acrylate Gio Di (meth) acrylic acid 1,2-hexanediol, di (meth) acrylic acid 1,5-hexanediol, di (meth) acrylic acid 2,5-hexanediol, di (meth) acrylic acid 1,7- Heptanediol, 1,8-octanediol di (meth) acrylic acid, 1,2-octanediol di (meth) acrylic acid, 1,9-nonanediol di (meth) acrylic acid, 1, di (meth) acrylic acid 1, 2-decanediol, di (meth) acrylic acid 1,10-decanediol, di (meth) acrylic acid 1,2-decanediol, di (meth) acrylic acid 1,12-dodecanediol, di (meth) acrylic acid 1,2-dodecanediol, di (meth) acrylic acid 1,14-tetradecanediol, di (meth) acrylic acid 1,2-tetradecanediol, di (meth) a 1,16-hexadecanediol silylate, 1,2-hexadecanediol di (meth) acrylate, 2-methyl-2,4-pentanediol di (meth) acrylate, 3-methyl-1 di (meth) acrylate , 5-pentanediol, 2-methyl-2-propyl-1,3-propanediol di (meth) acrylate, 2,4-dimethyl-2,4-pentanediol di (meth) acrylate, di (meth) 2,2-diethyl-1,3-propanediol acrylate, 2,2,4-trimethyl-1,3-pentanediol di (meth) acrylate, dimethyloloctane di (meth) acrylate, di (meth) 2-ethyl-1,3-hexanediol acrylate, 2,5-dimethyl-2,5-hexanediol di (meth) acrylate, 2-methyl di (meth) acrylate , 8-octanediol, 2-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, 2,4-diethyl-1,5-pentanediol di (meth) acrylate, di (meth) 2-methyl-2-propyl-1,3-propanediol acrylate, 2,4-dimethyl-2,4-pentanediol di (meth) acrylate, 2,2-diethyl-1, di (meth) acrylate 3-propanediol, 2,2,4-trimethyl-1,3-pentanediol di (meth) acrylate, dimethyloloctane di (meth) acrylate, 2-ethyl-1,3-di (meth) acrylate Hexanediol, 2,5-dimethyl-2,5-hexanediol di (meth) acrylate, 2-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, di (meth) acrylate ) Bifunctional (meth) acrylic acid esters such as 2,4-diethyl-1,5-pentanediol acrylate, 1,1,1-trishydroxymethylethane di (meth) acrylate;

  For example, 1,2,3-propanetriol tri (meth) acrylate, 2-methylpentane-2,2,4-triol tri (meth) acrylate, trimethylolhexane tri (meth) acrylate, tri (meth) Trimethylol octane acrylate, 2,2-bis (hydroxymethyl) 1,3-propanediol tri (meth) acrylate, 1,1,1-trishydroxymethylethane tri (meth) acrylate, tri (meth) acryl Trifunctional (meth) acrylic acid esters such as 1,1,1-trishydroxymethylpropane acid and pentaerythritol tri (meth) acrylate;

  For example, tetra (meth) acrylic acid pentaerythritol, tetra (meth) acrylic acid ethoxylated pentaerythritol, tetra (meth) acrylic acid ditrimethylolpropane, hexa (meth) acrylic acid dipentaerythritol, tetra (meth) acrylic acid 2, 2-bis (hydroxymethyl) 1,3-propanediol, tetra (meth) acrylic acid 2,2-bis (hydroxymethyl) 1,3-propanediol tetracaprolactonate, tetra (meth) acrylic acid di1, 2,3-propanetriol, tetra (meth) acrylate di-2-methylpentane-2,4-diol, tetra (meth) acrylate di-2-methylpentane-2,4-diol tetracaprolactonate, tetra ( (Meth) acrylic acid di-2,2-dimethylpropane-1,3- All, tetra (meth) acrylate ditrimethylolbutane, tetra (meth) acrylate ditrimethylolhexane, tetra (meth) acrylate ditrimethyloloctane, tetra (meth) acrylate di-2,2-bis (hydroxymethyl) 1, 3-propanediol, hexa (meth) acrylate di-2,2-bis (hydroxymethyl) 1,3-propanediol, hexa (meth) acrylate tri-2,2-bis (hydroxymethyl) 1,3-propanediol , Hepta (meth) acrylic acid tri-2,2-bis (hydroxymethyl) 1,3-propanediol, octa (meth) acrylic acid tri-2,2-bis (hydroxymethyl) 1,3-propanediol, hepta (meta ) Di2,2-bis (hydroxymethyl) 1,3-propanediol acrylate Polyfunctional (meth) acrylic acid esters or tetrafunctional such real sharp emission oxide;

For example, cyclohexyl (meth) acrylate, 1-methyl-1-cyclopentyl (meth) acrylate, 1-ethyl-1-cyclopentyl (meth) acrylate, 1-isopropyl-1-cyclopentyl (meth) acrylate, (meth ) 1-methyl-1-cyclohexyl acrylate, 1-ethyl-1-cyclohexyl (meth) acrylate, 1-isopropyl-1-cyclohexyl (meth) acrylate, 1-ethyl-1-cyclooctyl (meth) acrylate Benzyl (meth) acrylate, iso-bornyl (meth) acrylate, phenyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, 2-oxo-1,2-phenylethyl (meth) acrylate, (Meth) acrylic acid 2-oxo-1,2-diphenylethyl, (meth) acrylic acid 1 Naphthyl, 2-naphthyl (meth) acrylate, 1-naphthylmethyl (meth) acrylate, 1-anthryl (meth) acrylate, 2-anthryl (meth) acrylate, 9-anthryl (meth) acrylate, (meth ) 9-anthrylmethyl acrylate, 2-methyladamantyl-2-yl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyl (meth) acrylate Oxyethyl, 2-ethyladamantyl-2-yl (meth) acrylate, 2-n-propyladamantyl-2-yl (meth) acrylate, 2-isopropyladamantyl-2-yl (meth) acrylate, (meth) 1- (adamantan-1-yl) -1-methylethyl acrylate, 1- (ada) (meth) acrylic acid Ntan-1-yl) -1-ethylethyl, 1- (adamantan-1-yl) -1-methylpropyl (meth) acrylate, 1- (adamantan-1-yl) -1-ethylpropyl (meth) acrylate , (Meth) acrylic acid-5-oxo-4-oxa-tricyclo [4.2.1.0 ^3,7 ] non-2-yl, (meth) acrylic acid-5-oxo-4-oxa-tricyclo [ 5.2.1.0 ^3,8 ] dec-2-yl, dihydro-α-terpinyl (meth) acrylate, (meth) acrylic acid-6-oxo-7-oxa-bicyclo [3.2.1] (Meth) acrylic acid such as octa-2-yl, (meth) acrylic acid-7-oxo-8-oxa-bicyclo [3.3.1] oct-2-yl, (meth) acrylic acid-o-2-propenylphenyl ) Acrylic acid cyclic esters;

  For example, di (meth) acrylic acid tricyclodecane dihydroxymethyl, di (meth) acrylic acid tricyclodecane dihydroxymethyl dicaprolactonate, di (meth) acrylic acid 1,2-adamantanediol, di (meth) acrylic acid 1 , 3-adamantanediol, 1,4-adamantanediol di (meth) acrylate, tricyclodecanyl dimethylol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, di (meth) acrylate di Cyclopentenyl, dicyclopentenyloxyethyl di (meth) acrylate, 1,4-bis (2-hydroxypropyl) benzene di (meth) acrylate, 1,3-bis (2-hydroxypropyl) di (meth) acrylate ) Benzene, di (meth) acrylic acid-2,2-bis (hydroxyphenyl) propyl Tetraethylene oxide adduct of bread, tetraethylene oxide adduct of 2,2-bis (hydroxyphenyl) methane di (meth) acrylate, tetraethylene oxide of di (meth) acrylic acid-4,4′-sulfonyldiphenol Adduct, tetraethylene oxide adduct of di (meth) acrylic acid-water-added 2,2-bis (hydroxyphenyl) propane, di (meth) acrylic acid-water-added 2,2-bis (hydroxyphenyl) methane tetra Ethylene oxide adduct, di (meth) acrylic acid-water-added 2,2-bis (hydroxyphenyl) propane, di (2-methyl) propenoic acid-water-added 2,2-bis (hydroxyphenyl) methane, di (meta ) Tetraethylene oxide adduct of acrylic acid-2,2-bis (hydroxyphenyl) propane-dicapro Bifunctional (meth) acrylic acid cyclic esters such as lactonate, tetraethylene oxide adduct of di (meth) acrylic acid-2,2-bis (hydroxyphenyl) methane-dicaprolactonate;

  For example, cyclohexyl vinyl ether, cyclohexyl methyl vinyl ether, cyclohexyl ethyl vinyl ether, menthyl vinyl ether, tetrahydrofurfuryl vinyl ether, norbornenyl vinyl ether, 1-adamantyl vinyl ether, 2-adamantyl vinyl ether, phenyl vinyl ether, benzyl vinyl ether, 1-naphthyl vinyl ether, 2- Cyclic compounds containing a vinyl ether group such as naphthyl vinyl ether;

  For example, 5-vinylbicyclo [2.2.1] hept-2-ene, 2,5-bis (allyloxy) norbornane, 5-vinyl-2,3-oxirane norbornane, 2- (2-propenyl) bicyclo [2 2.1] alicyclic vinyl compounds such as heptane, 5-vinylbicyclo [2.2.1] hept-2-ene, 2-ethenylideneadamantane, 1-allyladamantane;

  For example, styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2-methoxystyrene, 3-methoxystyrene, 4-methoxystyrene, 4-t-butoxystyrene, 4-t- Butoxy-α-methylstyrene, 4- (2-ethyl-2-propoxy) styrene, 4- (2-ethyl-2-propoxy) -α-methylstyrene, 4- (1-ethoxyethoxy) styrene, 4- ( 1-ethoxyethoxy) -α-methylstyrene, 1-butylstyrene, 1-chloro-4-isopropenylbenzene and other styrene aromatic vinyl compounds;

  For example, vinyl phenyl pentyl ether, vinyl phenyl hexyl ether, vinyl phenyl heptyl ether, vinyl phenyl octyl ether, vinyl phenyl nonyl ether, vinyl phenyl decyl ether, vinyl phenyl undecyl ether, vinyl phenyl dodecyl ether, vinyl phenyl tridecyl ether, vinyl Phenyl tetradecyl ether, vinyl phenyl pentadecyl ether, vinyl phenyl hexadecyl ether, vinyl phenyl heptadecyl ether, vinyl phenyl octadecyl ether, vinyl phenyl nonadecyl ether, vinyl phenyl eicosyl ether, vinyl phenyl henecosyl ether, vinyl phenyl doco Sil ether, vinyl phenyl methyl butyl ether, vinyl phenyl Rupentyl ether, vinyl phenyl methyl hexyl ether, vinyl phenyl methyl heptyl ether, vinyl phenyl methyl octyl ether, vinyl phenyl methyl nonyl ether, vinyl phenyl methyl decyl ether, vinyl phenyl methyl undecyl ether, vinyl phenyl methyl dodecyl ether, vinyl phenyl methyl Tridecyl ether, vinyl phenylmethyl tetradecyl ether, vinyl phenyl methyl pentadecyl ether, vinyl phenyl methyl hexadecyl ether, vinyl phenyl methyl heptadecyl ether, vinyl phenyl methyl octadecyl ether, vinyl phenyl methyl nonadecyl ether, vinyl phenyl methyl eicosyl Ether, vinyl phenyl methyl henecosyl ether, vinyl Aromatic vinyl ether compounds having a long chain alkyl group, such as E methylpropenylmethyl docosyl ether;

  For example, vinyl ester type having a monopolyalkylene oxide ester site of dicarboxylic acid such as vinyl phenyl poly (ethylene oxide) succinate, vinyl phenyl methyl poly (ethylene oxide) hexahydrophthalate, vinyl phenyl ethyl poly (ethylene oxide) terephthalate, etc. Compounds;

  For example, hexyl 4-vinylbenzoate, octyl 4-vinylbenzoate, nonyl 4-vinylbenzoate, decyl 4-vinylbenzoate, dodecyl 4-vinylbenzoate, tetradecyl 4-vinylbenzoate, hexadecyl 4-vinylbenzoate , Octadecyl 4-vinylbenzoate, eicosyl 4-vinylbenzoate, docosyl 4-vinylbenzoate, hexyl 4-isopropenylbenzoate, octyl 4-isopropenylbenzoate, nonyl 4-isopropenylbenzoate, 4-isopropenyl Decyl benzoate, 4-isopropenylbenzoic acid dodecyl, 4-isopropenylbenzoic acid tetradecyl, 4-isopropenylbenzoic acid hexadecyl, 4-isopropenylbenzoic acid octadecyl, 4-isopropenylbenzoic acid eicosyl, 4-isopropenylbenzoic acid Docosil How long chain vinyl benzoic acid ester or isopropenyl benzoic acid ester compounds having an alkyl group;

  For example, tetra (ethylene oxide) vinyl phenyl ether, methyl tetra (ethylene oxide) vinyl phenyl ether, ethyl tetra (ethylene oxide) vinyl phenyl ether, propyl tetra (ethylene oxide) vinyl phenyl ether, n-butyl tetra (ethylene oxide) vinyl phenyl ether , N-pentyltetra (ethylene oxide) vinyl phenyl ether, tetra (propylene oxide) vinyl phenyl ether, methyl tetra (propylene oxide) vinyl phenyl ether, ethyl tetra (propylene oxide) vinyl phenyl ether, propoxy tetra (propylene oxide) vinyl phenyl ether N-butyltetra (propylene oxide) vinyl phenyl ether, n Pentaxytetra (propylene oxide) vinyl phenyl ether, poly (ethylene oxide) vinyl phenyl ether, methyl poly (ethylene oxide) vinyl phenyl ether, ethyl poly (ethylene oxide) vinyl phenyl ether, poly (propylene oxide) vinyl phenyl ether, methyl poly (propene Oxide) Vinyl phenyl ether compounds having a long-chain polyalkylene oxide moiety such as vinyl phenyl ether, ethyl poly (propylene oxide) ethenyl phenyl ether;

  For example, poly (ethylene oxide) poly (ethylene oxide) vinyl phenyl ethyl ether, methyl poly (ethylene oxide) vinyl phenyl ethyl ether, ethyl poly (ethylene oxide) vinyl phenyl ethyl ether, poly (oxypropylene) vinyl phenyl ethyl ether, methyl poly (propylene Oxide) vinyl phenyl ethyl ether compounds having a long-chain polyalkylene oxide moiety such as vinyl phenyl ethyl ether and ethyl poly (propylene oxide) vinyl phenyl ethyl ether;

  For example, vinyl benzyl ether, methyl poly (ethylene oxide) vinyl benzyl ether, ethyl poly (ethylene oxide) ethenyl benzyl ether, poly (propylene oxide) vinyl benzyl ether, methyl vinyl poly (propylene oxide) vinyl benzyl ether, ethyl poly (propylene oxide) Vinyl benzyl ether compounds having a long-chain polyalkylene oxide moiety such as vinyl benzyl ether;

  For example, isopropenyl phenylmethyl butyl ether, isopropenyl phenyl methyl pentyl ether, isopropenyl phenyl methyl hexyl ether, isopropenyl phenyl methyl heptyl ether, isopropenyl phenyl methyl octyl ether, isopropenyl phenyl methyl nonyl ether, isopropenyl phenyl methyl decyl ether, Isopropenyl phenylmethyl undecyl ether, isopropenyl phenyl methyl dodecyl ether, isopropenyl phenyl methyl tridecyl ether, isopropenyl phenyl methyl tetradecyl ether, isopropenyl phenyl methyl pentadecyl ether, isopropenyl phenyl methyl hexadecyl ether, isopropenyl phenyl Methyl heptadecyl ether, Isopropenyl phenyl having a long chain alkyl group such as isopropenyl phenyl methyl octadecyl ether, isopropenyl phenyl methyl nonadecyl ether, isopropenyl phenyl methyl eicosyl ether, isopropenyl phenyl methyl heneicosyl ether, isopropenyl phenyl methyl docosyl ether Ether compounds;

  For example, poly (ethylene oxide) isopropenyl phenyl ether, methyl poly (ethylene oxide) isopropenyl phenyl ether, ethyl poly (ethylene oxide) isopropenyl phenyl ether, poly (propylene oxide) isopropenyl phenyl ether, methyl poly (propylene oxide) isopropenyl phenyl Ether, ethyl poly (propylene oxide) isopropenyl phenyl ether, poly (ethylene oxide) isopropenyl benzyl ether, methyl poly (ethylene oxide) isopropenyl benzyl ether, ethyl poly (ethylene oxide) isopropenyl benzyl ether, poly (propylene oxide) isopropenyl benzyl ether Ether, methyl poly (propylene oxide) Isopropenyl ether-based compound having a polyalkylene oxide moiety, such as a source propenyl benzyl ether;

  For example, dienes such as allene, 1,2-butadiene, 1,3-butadiene, 2-methyl-1,3-butadiene, 2-chloro-1,3-butadiene;

  For example, ethylene, propylene, 1-butene, 2-butene, 2-methylpropene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene 1-docosene, 1-tetracocene, 1-hexacocene, 1-octacocene, 1-triacontene, 1-dotriacontene, 1-tetratoacontene, 1-hexatriacontene, 1-octatriacontene, 1-tetraconten And alkenes such as polybutene-1, polypentene-1, and poly-4-methylpentene-1;

  For example, carboxyl group-containing aliphatic α, β-unsaturated double bond group-containing carboxylic acids such as (meth) acrylic acid and (meth) acrylic acid dimer, and acid anhydrides thereof;

  For example, (meth) acrylic acid cyclic esters containing a sulfonyl group, such as (meth) acrylic acid sulfophenoxyethyl, (meth) acrylic acid sulfocyclohexyl, (meth) acrylic acid sulfobenzyl;

  For example, sulfonyl group-containing compounds such as (meth) acryloyloxyethyldimethylbenzylammonium-p-toluenesulfonate, (meth) acryloyloxyethyltrimethylammonium-p-toluenesulfonate, (meth) acryloylaminopropyltrimethylammonium-p-toluenesulfonate Metal salts and ammonium salts of (meth) acrylic acid cyclic esters;

  For example, (meth) acrylamides containing sulfonyl groups such as (meth) acrylamide sulfonic acid, tert-butyl- (meth) acrylamide sulfonic acid, (meth) acrylamide-2-methyl-1-propanesulfonic acid;

  For example, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminopropyl (meth) acrylate, pentamethylpiperidinyl (meth) acrylate, 4- (pyrimidine (2-yl) piperazin-1-yl (meth) acrylate (meth) acrylic acid esters having a tertiary amino group;

  For example, imide (meth) acrylate, 2- (4-oxazolin-3-yl) ethyl (meth) acrylate, di (meth) acrylic acid ethoxylated isocyanuric acid, tri (meth) acrylic acid ethoxylated isocyanuric acid, ε-caprolactone Heterocyclic structures containing oxygen atoms in addition to nitrogen atoms such as modified tris- (2-acryloyloxyethyl) isocyanurate, di (meth) acrylic acid isocyanuric acid ethylene oxide modification, tri (meth) acrylic acid isocyanuric acid ethylene oxide modification Cyclic amino group-containing (meth) acrylic acid esters having;

  For example, (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, N-propyl (Meth) acrylamide, N-tert-butyl (meth) acrylamide, N-hexyl (meth) acrylamide, N-octyl (meth) acrylamide, N-nonyl (meth) acrylamide, N-tricosyl (meth) acrylamide, N-nonadecyl (Meth) acrylamide, N-docosyl (meth) acrylamide, N-methylene (meth) acrylamide, N-tridecyl (meth) acrylamide, N- (5,5-dimethylhexyl) (meth) acrylamide, crotonamide, maleami , Fumaramide, mesaconamide, citraconic amide, itaconic amide, 2-methylprop-2-enoylamine, N, N-dimethyl (meth) acrylamide, N, N-diethyl- (meth) acrylamide, N- [3- (N ′, N Aliphatic (meth) acrylamides such as' -dimethylamino) propyl]-(meth) acrylamide, N- (dibutylaminomethyl) (meth) acrylamide;

  For example, N-methoxymethyl (meth) acrylamide, N-methoxyethyl (meth) acrylamide, N-methoxypropyl (meth) acrylamide, N-methoxybutyl (meth) acrylamide, N-methoxyhexyl (meth) acrylamide, N-methoxy Octyl (meth) acrylamide, N-methoxydecyl (meth) acrylamide, N-methoxydodecyl (meth) acrylamide, N-methoxyoctadecyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-ethoxyethyl (meth) acrylamide N-ethoxypropyl (meth) acrylamide, N-ethoxybutyl (meth) acrylamide, N-ethoxyhexyl (meth) acrylamide, N-ethoxyoctyl (meth) acrylamide, N-iso Roxymethyl (meth) acrylamide, N-isopropoxyethyl (meth) acrylamide, N-isopropoxypropyl (meth) acrylamide, N-isopropoxybutyl (meth) acrylamide, N-isopropoxyhexyl (meth) acrylamide, N-isopropoxy Octyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-butoxyethyl (meth) acrylamide, N-butoxypropyl (meth) acrylamide, N-butoxybutyl (meth) acrylamide, N-butoxyhexyl (meth) acrylamide N-butoxyoctyl (meth) acrylamide, N-isobutoxymethyl (meth) acrylamide, N-isobutoxyethyl (meth) acrylamide, N-isobutoxypropyl (meth) Acrylamide, N-isobutoxybutyl (meth) acrylamide, N-isobutoxyhexyl (meth) acrylamide, N-isobutoxyoctyl (meth) acrylamide, N- (pentoxymethyl) (meth) acrylamide, N-1-methyl- N-alkoxy group-containing (meth) acrylamides such as 2-methoxyethyl (meth) acrylamide, N, N-di (methoxymethyl) (meth) acrylamide, N, N-di (ethoxymethyl) (meth) acrylamide;

  For example, (meth) acrylamides having a tertiary amino group such as dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide;

  For example, N- (4-carbamoylphenyl) (meth) acrylamide, β- (2-furyl) (meth) acrylamide, 2,3-bis (2-furyl) acrylamide, N- (9H-fluoren-2-yl) (Meth) acrylamide, N-[(R) -1-phenylethyl] (meth) acrylamide, N-[(S) -1-phenylethyl] (meth) acrylamide, (Z) -N-methyl-3- ( Phenyl) (meth) acrylamide, (Z) -3- (phenyl) (meth) acrylamide, N, N-diethyl-3-phenyl (meth) acrylamide, (Z) -N, N-dimethyl-3- (phenyl) (Meth) acrylamides containing cyclic structures such as (meth) acrylamide

  For example, heterocyclic acrylamides such as 4-acryloylmorpholine, N- (oxetane-3-ylmethoxymethyl) (meth) acrylamide, N- (oxetane-2-ylmethoxymethyl) (meth) acrylamide;

  For example, amide-based vinyl compounds such as N-vinyl-N-methanamide and N-vinylacetamide;

  For example, vinyl compounds containing tertiary amino groups such as N-ethyl-N-nitrosovinylamine;

  For example, heterocyclic α, β- of maleimide derivatives having both nitrogen and oxygen atoms such as methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide, etc. Unsaturated double bond group-containing compounds;

  For example, 2-vinyl oxazole, 2-phenyl-4-vinyl oxazole, 2-phenyl-5-vinyl oxazole, 5-ethoxy-2-vinyl oxazole, 3-vinyl-5-nitrosoxazole, 2-vinyl-4,5 -It has a heterocyclic structure containing an oxygen atom in addition to a nitrogen atom such as diphenyloxazole, 2-vinyl-2-oxazoline, 4,4-dimethyl-2-vinyl-2-oxazolin-5-one, 2-vinylbenzoxazole Vinyl group-containing compounds;

  For example, 1-vinylpyrrole, 1-vinyl-2-imidazoline, 1-vinyl-2-methyl-2-imidazoline, 1-vinylimidazole, 1-vinyl-1H-pyrazole, 1-vinyl-3,5-dimethyl- 1H-pyrazole, 3-methyl-5-phenyl-1-vinylpyrazole, 1-vinylindole, 1-vinyl-2-methyl-1H-indole, 1-vinylisoindole, 1-vinyl-1H-benzimidazole, 1 -Vinylindazole, 1-vinylquinoline, 1-vinylisoxaline, 1-vinylquinazoline, 1-vinylcinnoline, 1-vinylcarbazole, 1,1'-divinyl-2,2'-bi (1H-imidazole) N-vinyl-2-pyrrolidone, N-vinyl-ε-caprolactam, 1-vinylpyridin-2 (1H) -one, -Vinyl-2 (1H) -pyridinethione, 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 6-methyl-2-ethenylpyridine, 2-vinylpyrimidine, 2-vinylpyrazine, 2-methyl- 5-vinylpyrazine, 2-methyl-6-vinylpyrazine, 2,5-dimethyl-3-vinylpyrazine, 2-vinylpyridazine, 2-vinylquinoline, 4-vinylquinoline, 2-vinylisoquinoline, 2-vinylisoquino Sarin, 2-vinylquinoxaline, 2-vinylquinazoline, 2-vinylcinnoline, 1-vinyl-1H-benzimidazole, 1-vinyl-5,6-dimethyl-1H-benzimidazole, 1-vinylindazole, 1-vinyl Quinoline, 1-vinylquinoline, 1-vinylisoquinoline, 1-vinylisoxaline, 1-biquinone Luquinoxaline, 1-vinylquinazoline, 1-vinylcinnoline, 1-benzyl-2-vinylpiperazine, 1-benzyl-3-vinylpiperazine, 1,4-dimethyl-3-vinylpiperazine, 2-vinyl-4, Nitrogen-containing heterogeneous compounds such as 6-diamino-1,3,5-triazine, 6-vinyl-1,3,5-dimethyl-2,4-diamine and 3-vinyl-1,2,4,5-tetrazine Cyclic amino group-containing vinyl compounds having a ring;

  For example, bifunctional vinyl compounds such as 2,3-divinylpyridine, 2,4-divinylpyridine, 2,5-divinylpyridine, 2,6-divinylpyridine, 1-methyl-4,5-divinyl-1H-imidazole, etc. Kind;

  For example, 1- (meth) allyl-3,5-dimethyl-1H-pyrazole, 1- (1-methylpropyl) -5- (meth) allylpyrimidine, 1- (meth) allyl-5-isopropylpyrimidine, 1- (Meth) allylpyridine, 1- (meth) allylpyridine, 2- (meth) allylpyridine, 4- (meth) allylpyridine, 3,6-dihydro-4- (meth) allylpyridine, 5- (1-methyl) Propyl) -5- (meth) allylpyrimidine, 5- (meth) allyl-5-isopropylpyrimidine, 3,6-dihydro-1- (meth) allylpyridine, 1- (meth) allyl-1H-imidazole, 1- (Meth) allyl-2-methyl-1H-imidazole, 1- (meth) allyl-3-methyl-1H-imidazol-3-ium, 1- (meth) allyl-3-ethyl 1H-imidazol-3-ium, 5-bromo-1- (meth) allyl-1H-pyrazole, 1- (meth) allylpiperazine, 1- (meth) allyl-5,5-diethylpyrimidine, N- (meth) Allyl-s-triazine-2,4,6-triamine, N- (meth) allyl-4,6-dichloro-1,3-5-triazine-2-amine, 1- (meth) allyl-1H-benzimidazole 1- (meth) allyl-3-methyl-1H-indazole, 1- (meth) allyl-4-methyl-1H-indazole, N- (meth) allylquinolin-4-amine, di (meth) allylquinoline, 1,2-di (meth) allyl-1,2-dihydroisoquinoline, 2- (meth) allyl-1H-indole, 3- (meth) allyl-1H-indole, 2- (meth) allylin Tetrazole, 3-phenyl-4- (meth) allyl isoquinoline, 9- (meth) cyclic amino group-containing (meth) allyl cyclic compounds having a heterocyclic nitrogen-containing and allyl -9H- carbazole;

  For example, 2-vinylthiazol, 4-methyl-5-vinylthiazole, 2-vinylbenzothiazole, 2- [2- (1-naphthyl) vinyl] benzothiazole, 2- [2- (dimethylamino) vinyl] benzo Vinyl group-containing compounds having a heterocyclic structure containing a sulfur atom in addition to a nitrogen atom, such as thiazole;

  For example, (meth) acrylic acid glycidyl, (meth) acrylic acid (3,4-epoxycyclohexyl) methyl, (meth) acrylic acid 9,10-epoxyoctadecanoic anhydride, (meth) acrylic acid 4-hydroxybutylglycidyl ether (Meth) acrylic acid 3,4-epoxycyclo [5.2.1.02,6] decan-1-yl ester, (meth) acrylic acid 2-[(1,2-epoxy-4,7-methano (Meth) acrylic acid esters having an epoxy group such as (hydrindan-5-yl) oxy] ethyl ester;

  For example, it has an epoxy group such as glycidyl cinnamate, (meth) allyl glycidyl ether, 1,3-butadiene monooxirane, vinylcyclohexene monooxirane, 1- (meth) allyloxy-2,3-epoxypropane (allyl glycidyl ether) Examples include alkenyl group-containing compounds.

  For example, (meth) acrylic acid (3-methyl-3-oxetanyl) methyl, (meth) acrylic acid (3-ethyl-3-oxetanyl) methyl, (meth) acrylic acid (3-n-propyl-3-oxetanyl) Methyl, (meth) acrylic acid (3-isopropyl-3-oxetanyl) methyl, (meth) acrylic acid (3-methyl-3-oxetanyl) ethyl, (meth) acrylic acid (3-ethyl-3-oxetanyl) ethyl, (Meth) acrylic acid (3-n-propyl-3-oxetanyl) ethyl, (meth) acrylic acid (3-isopropyl-3-oxetanyl) ethyl, (meth) acrylic acid (2,4-dimethyl-3-oxetanyl) Methyl, (meth) acrylic acid (2,3,4-trimethyl-3-oxetanyl) methyl, (meth) acrylic acid (3-ethyl-2- Til-3-oxetanyl) methyl, (meth) acrylic acid (3-ethyl-2,4-dimethyl-3-oxetanyl) methyl, (meth) acrylic acid (3-methyl-3-oxetanyl) ethoxymethyl, (meth) (Meth) acrylic acid esters having an oxetanyl group such as acrylic acid (3-ethyl-3-oxetanyl) ethoxymethyl;

  For example, 2-vinyloxetane, 3-vinyloxetane, 4-vinyloxetane-2-one, 3,3-bis (vinyloxymethyl) oxetane, 3-ethyl-3- (4-vinyloxycyclohexyloxymethyl) oxetane, Vinyl group-containing compounds having an oxetanyl group such as 3-ethyl-3- (vinyloxymethyl) oxetane;

  For example, 3- (meth) allyloxyoxetane, 3- (meth) allyloxymethyl-3-methyloxetane, 3- (meth) allyloxetane-3-ol, 4-oxooxetane-2-carboxylic acid (meth) allyl Oxetanyl such as 2-methyl-2- (meth) allyl-4-propyloxetane, 4α-((meth) allyloxymethyl) oxetane-2-one, 3-chloromethyl-3- (meth) allyloxymethyl-oxetane (Meth) allyl group-containing compounds having a group;

  For example, (meth) acrylic acid tetrahydrofurfuryl, (meth) acrylic acid-2-oxotetrahydropyran-4-yl, (meth) acrylic acid-4-methyl-2-oxotetrahydropyran-4-yl, (meth) 4-ethyl-2-oxotetrahydropyran-4-yl acrylate, 4-propyl-2-oxotetrahydropyran-4-yl (meth) acrylate, (meth) acrylic acid-5-oxotetrahydrofuran-3- , (Meth) acrylic acid-2,2-dimethyl-5-oxotetrahydrofuran-3-yl, (meth) acrylic acid-4,4-dimethyl-5-oxotetrahydrofuran-3-yl, (meth) acrylic acid- 2-oxotetrahydrofuran-3-yl, (meth) acrylic acid-4,4-dimethyl-2-oxotetrahydrofuran N-3-yl, (meth) acrylic acid-5,5-dimethyl-2-oxotetrahydrofuran-3-yl, (meth) acrylic acid-2-oxotetrahydrofuran-3-yl, (meth) acrylic acid-5- Oxotetrahydrofuran-2-ylmethyl, (meth) acrylic acid-3,3-dimethyl-5-oxotetrahydrofuran-2-ylmethyl, (meth) acrylic acid-4,4-dimethyl-5-oxotetrahydrofuran-2-ylmethyl, etc. 5-membered or higher cyclic ether group-containing (meth) acrylic acid esters having one or more oxygen atoms in the ring;

  For example, 2-vinyl furan, 3-vinyl furan, 5-vinyl furan-2-methanol, 5-vinyl furan-2-carbaldehyde, 2- [2- (2,4,6-trinitrophenyl) vinyl] furan 2-[(E) -2- (2-thienyl) vinyl] furan, 4,5-dihydro-4β-tert-butyl-3β-vinylfuran-2 (3H) -one, 2-vinyloxytetrahydropyran, (3S) -3α-vinyltetrahydro-2H-pyran-4α-ol, 4-vinyltetrahydro-2H-pyran-2-one, (2S) -2-vinyltetrahydro-2H-pyran, 4-methoxy-6- [ (E) -2-phenylvinyl] -2H-pyran-2-one and other cyclic ether group-containing vinyl compounds having one or more oxygen atoms in the ring;

  For example, 2- (meth) allyl furan, 2- (meth) allyl furan, (meth) allyl 2-furan carboxylic acid, 2-methyl-2- (meth) allyl-furan-3 (2H) -one, 2, 3-dimethyl-4- (2-phenyl (meth) allyl) furan, 2-methyl-3- (meth) allyl-4- (2-phenyl (meth) allyl) furan, 3- (meth) allyl-4, 5-dihydro-5-methyl-3-phenylfuran-2 (3H) -one, 4-allyltetrahydro-2H-pyran-2-one, 5α-allyltetrahydro-2H-pyran-2-one, 6-allyltetrahydro -H-pyran-2-one and the like include 5-membered or higher cyclic ether group-containing (meth) allyl group-containing compounds having one or more oxygen atoms in the ring, but are particularly limited thereto. is not. These may be used alone or in combination of two or more.

  [Alpha] other than [alpha], [beta] -unsaturated double bond group-containing compound (a3-1) having an alkyl group having 2 to 20 carbon atoms and having a homopolymer having a glass transition temperature of -80 to 0 [deg.] C. , Β-unsaturated double bond group-containing compound (a3-2) is preferably a compound having a (meth) acryloyl group from the viewpoint of reactivity, and particularly preferably including a compound having an acryloyl group.

Examples of the α, β-unsaturated double bond group-containing compound (a3-2) include the α, β-unsaturated double bond group-containing compound having the primary or secondary amino group (a3-2-1). ), And α, β-unsaturated double bond group-containing compound (a3-2-2) having no primary or secondary amino group can be used. In consideration of interaction such as Michael addition reaction with the silane compound (B) having a group, α, β-unsaturated double bond group-containing compound having no primary or secondary amino group (a3-2-2 ) Is preferably used.
When the compound (a3-2-1) is used, a Michael addition reaction or the like is performed between the carbonyl group contained in the compound (a2) and the amino group contained in the compound (a3-2-1). Since interaction is likely to occur, it is preferable to adjust the amount used appropriately so as not to inhibit the reaction between the carbonyl group contained in the compound (a2) and the silane compound (B) having an amino group described later.

  In the α, β-unsaturated double bond group-containing compound (a3) having no hydroxyl group or carbonyl group in the molecule, polymerization reactivity, a silane compound (B) having an amino group described later, and a reactive compound (C) So that the compound (a1), the compound (a2), and the compound (a3) are contained in a well-balanced manner in terms of shrinkage in crosslinking and curing, and durability such as heat resistance, moist heat resistance, and water resistance. It is possible to prepare a good copolymer (A) by appropriately blending and polymerizing the monomer mixture, and it is possible to obtain a better pressure-sensitive adhesive.

  The copolymer (A) is a copolymer obtained by copolymerizing the compound (a1), the compound (a2), and the compound (a3), and has a weight average molecular weight (Mw) of the copolymer (A). ) Is 100,000 to 2,000,000 in order to achieve both the coating suitability of the pressure sensitive adhesive and the cohesive strength of the coating film when the copolymer (A) is used as the pressure sensitive adhesive. Preferably, it is 200,000 to 1,800,000, more preferably 400,000 to 1,500,000. If the Mw is less than 100,000, the cohesive force of the copolymer (A) may be insufficient and the adhesive force may be reduced. If it exceeds 2,000,000, the viscosity of the copolymer (A) is high. Therefore, there is a possibility that the coating property of the pressure-sensitive adhesive may deteriorate. When Mw is in the above range, the cohesive force and the like are further improved, so that floating and peeling can be further suppressed, and the stress relaxation property is further improved. In addition, the said weight average molecular weight and number average molecular weight are the values of polystyrene conversion measured by the gel permeation chromatography (GPC) method. Details of the GPC measurement method are described in the Examples.

In the compound (a1), the compound (a2) and the compound (a3), which are monomer units constituting the copolymer (A), the compounds (a1), (a2) and the compounds (a2) constituting the copolymer (A) Monomer mixture of 0.1 to 30% by weight of compound (a1), 0.1 to 30% by weight of compound (a2), and 40 to 99.5% by weight of compound (a3) in a total of 100% by weight of (a3) It is preferable to copolymerize as follows. More preferably, they are the range of 1 to 25 weight% of a compound (a1), 1 to 20 weight% of a compound (a2), and 55 to 98 weight% of a compound (3).
When the compound (a1) and the compound (a2) are each 0.1% by weight or more, a Michael addition reaction or a siloxy group condensation reaction with a silane compound (B) having an amino group described later occurs rapidly, Since it is possible to perform a typical crosslinking reaction, it leads to an improvement in Tg of the crosslinked resin, and an improvement in cohesive force can be expected. Further, when the compound (a1) and the compound (a2) are each 30% by weight or less, the Tg of the crosslinked resin is appropriately controlled and sufficient tackiness (tack) can be secured, which leads to an improvement in adhesive strength. It becomes possible.

  The copolymer (A) is 0.001 to 20 weights with respect to 100 parts by weight of the total monomer mixture of the α, β-unsaturated double bond group-containing compound according to a conventional method. Using a part of the polymerization initiator, it is synthesized by a method such as bulk polymerization, solution polymerization, emulsion polymerization or suspension polymerization. Preferably, it is synthesized by solution polymerization.

  Examples of the polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane 1-carbonitrile) and 2 , 2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2′-azobis (2-methylpropionate) Dimethyl 2,2′-azobisisobutyrate, 1,1′-azobis (1-acetoxy-1-phenylethane), 4,4′-azobis (4-cyanovaleric acid), 2,2′- Examples include azo compounds such as azobis (2-hydroxymethylpropionitrile) and 2,2′-azobis [2- (2-imidazolin-2-yl) propane].

  Also, benzoyl peroxide, tert-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di (2-ethoxyethyl) peroxydicarbonate, tert-butyl peroxy Organic such as 2-ethylhexanoate, tert-butylperoxyneodecanoate, tert-butylperoxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, diacetyl peroxide A peroxide is mentioned.

  In the synthesis, mercaptans such as lauryl mercaptan and n-dodecyl mercaptan, and chain transfer agents such as α-methylstyrene dimer and limonene may be used.

  Among these, from the viewpoint of molecular weight control and molecular weight distribution control, polymerization initiators include 2,2′-azobisisobutyronitrile, dimethyl 2,2′-azobis (2-methylpropionate), dimethyl 2 , 2'-azobisisobutyrate and dibenzoyldioxydan, tert-butyl perbenzoate, tert-butyl peroxypivalate, tert-hexyl peroxypivalate, octanoyl peroxide, lauroyl peroxide, tert-butyl peroxide Oxy-2-ethylhexanoate is preferred.

  When the copolymer (A) is synthesized by a solution polymerization method, examples of the organic solvent that can be used as the solvent include alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, and n-butyl alcohol, and acetone. , Methyl ethyl ketone, methyl-n-propyl ketone, methyl isopropyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, methyl-n-amyl ketone, methyl isoamyl ketone, diethyl ketone, ethyl-n-propyl ketone, ethyl isopropyl ketone, ethyl- Ketones such as n-butyl ketone, ethyl isobutyl ketone, di-n-propyl ketone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, isophorone, methyl acetate, ethyl acetate, acetic acid-n-propyl, isopropyl acetate , Acetate-n-butyl, isobutyl acetate, hexyl acetate, octyl acetate, methyl lactate, propyl lactate, butyl lactate esters, ethylene glycol, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, diethylene glycol Monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether Glycol, glycol ethers such as propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dipropyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl Ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol Glycol acetates such as butyl monobutyl ether acetate and dipropylene glycol monomethyl ether acetate, saturated hydrocarbons such as n-hexane, isohexane, n-nonane, isononane, dodecane, isododecane, 1-hexene, 1-heptene, 1-octene, etc. Unsaturated hydrocarbons, cyclic saturated hydrocarbons such as cyclohexane, cycloheptane, cyclooctane, cyclodecane, decalin, cyclohexene, cycloheptene, cyclooctene, 1,1,3,5,7-cyclooctatetraene, cyclododecene, etc. Cyclic unsaturated hydrocarbons, aromatic hydrocarbons such as benzene, toluene and xylene. These organic solvents may be used alone or in combination of two or more. The amount of the organic solvent may be appropriately determined in consideration of the polymerization conditions, the composition of each component of the α, β-unsaturated double bond group-containing compound, the viscosity and non-volatile content of the copolymer (A) to be obtained. An organic solvent having active hydrogen, such as an alcohol-based organic solvent, which may react with a silane compound (B) having a primary or secondary amino group and a reactive compound (C) described later. Is preferably not used.

  What is necessary is just to set suitably the polymerization conditions at the time of synthesize | combining a copolymer (A) according to a polymerization method, and it is not specifically limited. The polymerization temperature is preferably 20 to 150 ° C, more preferably 40 to 120 ° C. The reaction time may be appropriately set so that the polymerization reaction of each component of the α, β-unsaturated double bond-containing compound is completed.

<Silane compound (B) having primary or secondary amino group>
Next, the silane compound (B) having a primary or secondary amino group will be described.
The silane compound (B) having a primary or secondary amino group is a compound that is referred to as both a silane compound having a primary or secondary amino group in the molecule, and a tertiary amino group. A silane compound having only is not included. The amino group contained in the silane compound (B) forms a chemical bond through an interaction such as a Michael addition reaction with the carbonyl group contained in the copolymer (A). When used, it not only suppresses the scattering of the silane compound (B) during coating drying, but also improves the fixability of the silane compound in the coating film. It becomes easy to demonstrate the characteristics.
Further, the siloxy group contained in the silane compound (B) causes a crosslinking reaction with the hydroxyl group contained in the copolymer (A) or the base material (G) described later, and the pressure-sensitive adhesive and the base material (G) In the meantime, it is possible to develop a strong interaction such as a chemical bond or physical adsorption.

  Examples of the silane compound (B) having a primary or secondary amino group include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, and 3-aminopropylmethyldisilane. Ethoxysilane, 3-aminopropylethyldiethoxysilane, 3-aminopropyldimethylethoxysilane, N- (2-aminomethyl) 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropyltrimethoxy Silane, 3- (2-aminoethylaminopropyl) trimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, 2-aminoethylaminomethyltrimethoxysilane, 3- [2- (2- Aminoethylaminoethylamino) propyl] Methoxysilane, methyltris (2-aminoethoxy) silane, butylaminomethyltrimethoxysilane, 2- (2-aminoethylthioethyl) trimethylsilane, 2- (2-aminoethylthioethyl) methyldiethoxysilane, 3-allyl Aminopropyltrimethoxysilane, 3-cyclohexylaminopropyltrimethoxysilane, 2-cyclohexylaminoethylthiomethyltrimethoxysilane, 3- (N-phenyl) aminopropyltrimethoxysilane, 3-phenylaminopropyltrimethoxysilane, N- [2- (Vinylbenzylamino) ethyl] -3-aminopropyltrimethoxysilane, 2- (2-aminoethylthioethyl) triethoxysilane, 3-piperazinopropylmethyldimethoxysilane, 3-piperazinopropylto Silane, amino-based alkoxysilanes such as 3-ureidopropyltriethoxysilane;

  For example, 1,1,3,3-tetramethyldisilazane, hexamethyldisilazane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, 1,3-bis (chloromethyl) -1 , 1,3,3, -tetramethyldisilazane, 1,1,3,3,5,5-hexamethylcyclotrisilazane, 1,1,3,3,5,5,7,7-octamethylcyclo Silazane silylamines such as tetrasilazane;

  For example, trimethylsilyldimethylamine, trimethylsilyldiethylamine, allylaminotrimethylsilane, isopropylaminomethyltrimethylsilane, allyloxy-2-aminoethylaminomethyldimethylsilane, allylaminotrimethylsilane, 2-aminoethylaminomethyltrimethylsilane, bis (ethylamino) Dimethylsilane, bis (butylamino) dimethylsilane, 3- (2-aminoethylaminopropyl) tris (trimethylsiloxy) silane, 3-butylaminopropylmethylsilane, methyltris (cyclohexylamino) silane, 1,3-bis (3 -Aminopropyl) tetramethyldisiloxane, 1,3-bis (2-aminoethylaminomethyl) -1,1,3,3-tetramethyldisiloxane, 3- (2-a Noethylaminopropyl) heptaethyltrisiloxane, heptamethyl-3- (3-piperazinopropyl) trisiloxane, 3-aminophenoxydimethylvinylsilane, 4-aminophenoxydimethylvinylsilane, 2-aminoethylaminomethyldimethylphenylsilane, ani Linotrimethylsilane, dianilinodidiphenylsilane, dianilinodimethylsilane, 3-benzylaminopropyltrimethoxysilane, 1,4-bis (3-aminopropyldimethylsilyl) benzene, 2- (2-piperazinoethylthioethyl) ) Trimethylsilane, dibutylmethyl-3- (4-piperidylmethylaminopropyl) silane, dimethylphenylpiperazinomethylsilane, butyldimethyl-3-piperazinopropylsilane, 3-piperazinopropyl Lis (trimethylsiloxy) silane, heptamethyl-3- [3- (4-piperazinomethylaminopropyl)] trisiloxane, 3- [3- (4-cyclohexylcarbamoylpiperazino) propyl] heptamethyltrisiloxane, N Examples thereof include silylamines having a silylamino group such as-(3-trimethoxysilylpropyl) -p-nitrobenzeneamide.

In addition, a silane compound having a primary or secondary amino group obtained by co-condensation reaction with the above amino-based alkoxysilanes or silylamines and a silane compound (D) described later also has an amino group. Included in (B).
The silane compound (B) having an amino group exemplified here may be used alone, or a plurality of compounds may be used in combination. The amine value of the silane compound having a secondary amino group is preferably 100 to 600 mgKOH / g, and more preferably 200 to 500 mgKOH / g.
When a pressure-sensitive adhesive film is prepared using a pressure-sensitive adhesive compounded with the silane compound (B), and this adhesive film is laminated on the substrate (G) described later, the silane compound (B) has an amino group. By doing so, the polarity of the silane compound is increased, so that the intermolecular affinity with the copolymer (A) is reduced, and it becomes easy to move to the interface with the base material (G). At this time, it becomes easy to form a silyl ether bond by reacting with the polar group (especially hydroxyl group) on the surface of the base material (G) or adhering water, and interaction with the base material (G) surface such as chemical bond or physical adsorption. Improves adhesion. At the time of migration, the amino group or siloxy group contained in the silane compound (B) undergoes a Michael addition reaction with the carbonyl group contained in the copolymer (A) or a condensation reaction with the hydroxyl group. Even in this case, it is considered that not only the scattering of the silane compound (B) can be prevented, but also the cohesive strength of the crosslinked coating film is improved through the crosslinking reaction.
When the amine value is 100 mgKOH / g or more, the silane compound (B) easily moves to the interface with the substrate (G), and the adhesion is improved. On the other hand, if it is 600 mgKOH / g or less, there is no generation of aggregates due to the self-condensation reaction of the silane compound (B), and the Michael addition reaction with the carbonyl group in the copolymer (A) proceeds effectively. It is possible to improve the cohesive strength of the crosslinked coating film. Therefore, when it is within this range, it is possible to enhance the effect of suppressing floating and peeling when exposed to a high temperature atmosphere or a high temperature and high humidity atmosphere.

  As described above, the silane compound (B) having a primary or secondary amino group is used in a range where the primary or secondary amine value (hereinafter referred to as primary or secondary amine value) is in the range of 100 to 600 mgKOH / g. In addition to forming an effective cross-linking reaction, it effectively aligns at the interface between the pressure-sensitive adhesive and various substrates, improving adhesion, heat resistance, moist heat resistance, and water resistance. Solvent resistance, mechanical strength, electrical insulation, dimensional stability, etc. are significantly improved.

  Here, a method for measuring the primary or secondary amine value of the silane compound (B) having a primary or secondary amino group will be described.

The primary or secondary amine value of the silane compound (B) having a primary or secondary amino group was calculated by the following method.
Primary / secondary amine value = total amine value (ASTM D2074) -tertiary amine value (ASTM D2073)

Here, the total amine value means the number of mg of potassium hydroxide equivalent to hydrochloric acid required for neutralizing the primary, secondary and tertiary amines contained in 1 g of a sample. According to the method specified in ASTM D2074, about 1 g of a sample is weighed, and 30 mL of neutral ethanol [neutralized bromcresol green (BCG)] is added and dissolved.
Next, it titrates with a 0.2N ethanolic hydrochloric acid solution (titer: F1). The titration end point is judged from potentiometric titration (automatic potentiometric titrator “GT-100” manufactured by Mitsubishi Chemical Corporation), and the total amine value is calculated from the obtained end point.
The total amine value was determined by the following formula. The total amine value is a numerical value of the dry state of the sample (unit: mgKOH / g).
Total amine value (mgKOH / g) = (a1 × 0.2 × 56.108 × F1 / S1) / nonvolatile content concentration (%)
However, S1: Sample collection amount (g)
a1: Consumption of 0.2N ethanolic hydrochloric acid solution (ml)
F1: Potency of 0.2N ethanolic hydrochloric acid solution

The tertiary amine value means the number of mg of potassium hydroxide equivalent to perchloric acid required to neutralize the tertiary amine contained in 1 g of a sample. According to the method prescribed in ASTM D2073, about 1 g of a sample is weighed, 20 mL of an acetic anhydride / acetic acid mixed solution (9/1) is added and dissolved, and left at room temperature for 3 hours. Next, 30 mL of acetic acid is added and titrated with a 0.1N-perchloric acid / acetic acid solution (titer: F2). A blank test is performed as described above. The titration end point is determined from potentiometric titration (Mitsubishi Chemical Corporation automatic potentiometric titrator “GT-100”) as in the previous period, and the tertiary amine value is calculated from the obtained end point. The tertiary amine value is a numerical value of the dry state of the sample (unit: mgKOH / g).
Tertiary amine value (mgKOH / g) = {(a2-b2) × F2 × 0.1 × 56.108 / S2} / nonvolatile content concentration (%)
However, S2: Sample collection amount (g)
a2: Consumption of 0.1N-perchloric acid / acetic acid solution (ml)
b2: Consumption of 0.1N-perchloric acid / acetic acid solution in the blank test (ml)
F2: 0.1N-perchloric acid / acetic acid solution titer

  As the silane compound (B) having a primary or secondary amino group, in particular, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropylethyldiethoxysilane, 3-aminopropyldimethylethoxysilane, 2-cyclohexylaminoethylthiomethyltrimethoxysilane, 3- (N- Phenyl) aminopropyltrimethoxysilane, trimethylsilyldimethylamine, trimethylsilyldiethylamine, 1,1,3,3-tetramethyldisilazane, hexamethyldisilazane are preferably used.

  The pressure-sensitive adhesive of the present invention preferably contains 0.1 to 30 parts by weight of the silane compound (B) with respect to 100 parts by weight of the copolymer (A), and 0.5 to 20 parts by weight. It is more preferable to contain. If it is 0.1 parts by weight or more, an effective crosslinking reaction with the carbonyl group in the copolymer (A) is performed, so that heat resistance and heat-and-moisture resistance are improved. Since the siloxy group contained in the compound (B) is oriented on the substrate surface, the coating film can be prevented from floating, peeling off or foaming in a harsh environment and suitable for adhesion to the substrate (G). is there.

<Reactive compound (C) having at least one functional group in the molecule capable of reacting with a hydroxyl group in the copolymer (A)>
Next, the reactive compound (C) having at least one functional group capable of reacting with a hydroxyl group in the copolymer (A) in the molecule will be described.
In one embodiment of the pressure-sensitive adhesive of the present invention, the pressure-sensitive adhesive is a reaction having one or more functional groups in the molecule that can react with a hydroxyl group in the copolymer (A) in addition to the above essential components. The compound (C) may also be included.
The reactive compound (C) has a role of cross-linking with the hydroxyl group of the copolymer (A), improving the cross-linking molecular weight of the pressure-sensitive adhesive, and further improving the cohesive force. In addition, the reactive compound (C) can be expected to improve the interaction such as chemical bonding and physical adsorption with the surface of the substrate (G) described later. For example, for a base material subjected to a physical treatment such as corona discharge treatment or a chemical treatment modified with an acid or the like, the reactive functional group in the reactive compound (C) is chemically reacted with the base material. It is also possible to develop a strong interaction between the copolymer (A) and the substrate.

  Examples of the reactive compound (C) include an isocyanate compound (c1), a carbodiimide compound (c2), an aziridine compound (c3), a metal chelate compound (c4), and an epoxy compound (c5). A compound having two or more functional groups capable of reacting with the hydroxyl group in the coalescence (A) is preferably used, has high reactivity with the hydroxyl group, and is excellent in improving the adhesiveness of the pressure-sensitive adhesive after the crosslinking reaction. Therefore, the isocyanate compound (c1) is preferably used.

  Of the reactive compounds (C), the isocyanate compound (c1) may be any compound having at least one isocyanate group in the molecule, and examples thereof include monofunctional isocyanates and polyfunctional isocyanates. The polyfunctional isocyanate is classified into aromatic polyisocyanate, aliphatic polyisocyanate, araliphatic polyisocyanate, and alicyclic polyisocyanate.

  Examples of the monofunctional isocyanate include methyl isocyanate, ethyl isocyanate, propyl isocyanate, butyl isocyanate, octyl isocyanate, decyl isocyanate, octadecyl isocyanate, stearyl isocyanate, cyclohexyl isocyanate, phenyl isocyanate, benzyl isocyanate, p-chlorophenyl isocyanate, and p-nitrophenyl. Isocyanate, 2-chloroethyl isocyanate, 2,4-dichlorophenyl isocyanate, 3-chloro-4-methylphenyl isocyanate, trichloroacetyl isocyanate, chlorosulfonyl isocyanate, (R)-(+)-α-methylbenzyl isocyanate, (S) -(-)-Α-methylbenzyl isocyanate, (R)-( -)-1- (1-naphthyl) ethyl isocyanate, (R)-(+)-1-phenylethyl isocyanate, (S)-(-)-1-phenylethyl isocyanate, p-toluenesulfonyl isocyanate, and the like. .

  Among the polyfunctional isocyanates, aliphatic polyisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (also known as HDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1, Examples include 3-butylene diisocyanate, dodecamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate.

  Examples of the aromatic polyisocyanate include 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate (also known as 2,4-TDI), 2, 6-tolylene diisocyanate (also known as 2,6-TDI), 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4′-diphenyl ether diisocyanate, 4,4 ', 4 "-triphenylmethane triisocyanate, 1,3-phenylene bismethylene diisocyanate (alias: m-XDI), 1,4-phenylene bismethylene diisocyanate (alias: p-XDI), 2,2 '-Diphenylmethane diisocyanate (alias: 2, 2-MDI), 4,4'-diphenylmethane diisocyanate (also known as 4,4-MDI), 1,3-naphthalenediyl diisocyanate (also known as 1,3-NDI), 1,5-naphthalenediyl diisocyanate (also known as 1) , 5-NDI).

  Examples of the araliphatic polyisocyanate include ω, ω′-diisocyanate-1,3-dimethylbenzene, ω, ω′-diisocyanate-1,4-dimethylbenzene, ω, ω′-diisocyanate-1,4-diethylbenzene, , 4-tetramethylxylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate, and the like.

  As alicyclic polyisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (also known as IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, Mention may be made of methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), 1,4-bis (isocyanatomethyl) cyclohexane, norbornene diisocyanate and the like.

  Further, as part of the isocyanate compound (c1) component, adducts of the above-mentioned polyfunctional isocyanates with polyols such as 2-methylpentane-2,4-diol and trimethylolpropane, trimers having an isocyanurate ring, etc. Can also be used. Polyphenylmethane polyisocyanate (also known as PAPI), and these polyisocyanate-modified products can also be used. As the polyisocyanate-modified product, a carbodiimide group, a uretdione group, a uretonimine group, a burette group reacted with water, a group of isocyanurate groups, or a modified product having two or more of these groups can be used. A reaction product of a polyol and a diisocyanate can also be used as a compound having at least two isocyanate groups. Moreover, the isocyanate compound (c1) can also use the blocked isocyanate which blocked the isocyanate group using the blocking agent.

  When the isocyanate compound (c1) is used, a known catalyst can be used as necessary for promoting the reaction between the hydroxyl group of the copolymer (A) and the isocyanate group. For example, a tertiary amine compound, an organometallic compound, etc. are mentioned, and they may be used alone or in combination.

  Examples of tertiary amine compounds include triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, diazabicycloundecene (also known as DBU), and these may be used alone or in combination. You can also

Examples of organometallic compounds include tin compounds and non-tin compounds.
Examples of the tin compound include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (also known as DBTDL), dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide. , Tributyltin acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate, tin 2-ethylhexanoate and the like.
Examples of non-tin compounds include titanium compounds such as dibutyltitanium dichloride, tetrabutyltitanate, and butoxytitanium trichloride, lead compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate, and lead naphthenate. -Iron-based such as iron ethylhexanoate, iron 2,4-pentadionate, cobalt-based such as cobalt benzoate, cobalt 2-ethylhexanoate, zinc-based such as zinc naphthenate, zinc 2-ethylhexanoate, Examples thereof include zirconium naphthenate.

  Among the above catalysts, diazabicycloundecene (alias: DBU), dibutyltin dilaurate (alias: DBTDL), tin 2-ethylhexanoate and the like are preferable in terms of reactivity and hygiene.

  As the isocyanate compound (c1), particularly in terms of crosslinking reactivity, adducts of diisocyanates such as HDI, TDI, MDI, and IPDI with trimethylolpropane, burettes reacted with water, and 3 added to isocyanurate rings. A monomer is preferably used.

  Among the reactive compounds (C), as the carbodiimide compound (c2), a compound having two or more carbodiimide groups (—N═C═N—) in the molecule is preferably used, and a known polycarbodiimide is used. it can. Moreover, as the carbodiimide compound, polycarbodiimide produced by decarboxylation condensation reaction of diisocyanate in the presence of a carbodiimidization catalyst can also be used.

Examples of such compounds include those obtained by subjecting the following diisocyanates to a decarboxylation condensation reaction. As the diisocyanate, 4,4′-diphenylmethane diisocyanate, 3,3′-dimethoxy-4,4′-diphenylmethane diisocyanate, 3,3′-dimethyl-4,4′-diphenylmethane diisocyanate, 4,4′-diphenyl ether diisocyanate, 3,3′-dimethyl-4,4′-diphenyl ether diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1-methoxyphenyl-2,4-diisocyanate, isophorone diisocyanate, 4,4′- One of dicyclohexylmethane diisocyanate, tetramethylxylylene diisocyanate, or a mixture thereof can be used.
As the carbodiimidization catalyst, 1-phenyl-2-phospholene-1-oxide, 3-methyl-2-phospholene-1-oxide, 1-ethyl-3-methyl-2-phospholene-1-oxide, 1-ethyl- Phosphorene oxides such as 2-phospholene-1-oxide or their 3-phospholene isomers can be used.

  As such a polycarbodiimide, a carbodilite series manufactured by Nisshinbo Co., Ltd. may be mentioned as a commercial product. Among these, Carbodilite V-01, 03, 05, 07, 09 is preferable because of its excellent compatibility with organic solvents.

  Among the reactive compounds (C), examples of the aziridine compound (c3) include N, N′-diphenylmethane-4,4′-bis (1-aziridinecarboxite), N, N′-toluene-2,4. -Bis (1-aziridinecarboxite), bisisophthaloyl-1- (2-methylaziridine), tri-1-aziridinylphosphine oxide, N, N'-hexamethylene-1,6-bis (1- Aziridinecarboxite), 2-methylpentane-2,4-diol-tri-β-aziridinylpropionate, 2,2-bis (hydroxymethyl) 1,3-propanediol-tri-β-aziridinyl Propionate, tris-2,4,6- (1-aziridinyl) -1,3,5-triazine, 2-methylpentane-2,4-diol tris [3- (1- Aziridinyl) propionate], 2-methylpentane-2,4-diol tris [3- (1-aziridinyl) butyrate], 2-methylpentane-2,4-diol tris [3- (1- (2-methyl) aziridinyl] ) Propionate], 2-methylpentane-2,4-diol tris [3- (1-aziridinyl) -2-methylpropionate], 2,2-bis (hydroxymethyl) 1,3-propanediol tetra [3 -(1-aziridinyl) propionate], diphenylmethane-4,4-bis-N, N'-ethyleneurea, 1,6-hexamethylenebis-N, N'-ethyleneurea, 2,4,6- (triethylene Imino) -Syn-triazine, bis [1- (2-ethyl) aziridinyl] benzene-1,3-carboxylic acid amide, and the like. It is.

  Among the reactive compounds (C), as the metal chelate compound (c4), for example, polyvalent metals such as aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium and zirconium, Examples thereof include coordination compounds with 2,4-pentadione and ethyl-3-oxobutanoate.

  Among the reactive compounds (C), examples of the epoxy compound (c5) include bisphenol A-epichlorohydrin type epoxy resins, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, and glycerin. Triglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, diglycidylaniline, N, N, N ′, N′-tetraglycidyl-m-xylylenediamine, 1,3-bis ( N, N′-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′-tetraglycidylaminophenylmethane and the like.

  The reactive compound (C) exemplified here may be used alone or in combination with a plurality of compounds, and is not particularly limited thereto. In view of crosslinking reactivity with the hydroxyl group contained in the polymer (A), the isocyanate compound (c1) is preferably used. Moreover, it is also possible to use together an isocyanate compound (c1), a carbodiimide compound (c2), an aziridine compound (c3), a metal chelate compound (c4), or an epoxy compound (c5).

  The pressure-sensitive adhesive of the present invention preferably contains 0.1 to 50 parts by weight of the reactive compound (C) with respect to 100 parts by weight of the copolymer (A). If it is 0.1 parts by weight or more, the heat resistance and heat-and-moisture resistance are improved, and if it is 50 parts by weight or less, the coating film can be prevented from floating, peeling or foaming in a harsh environment. Suitable for adhesion and adhesion to (G).

<Silane compound (D) having no primary or secondary amino group>
Next, the silane compound (D) having no primary or secondary amino group will be described.
In one embodiment of the pressure-sensitive adhesive of the present invention, the pressure-sensitive adhesive contains a silane compound (D) having no primary or secondary amino group (also referred to as a primary or secondary amino group) in addition to the above components. ) In combination with the above silane compound (B), a self-condensation reaction between the silane compounds and a polar group on the surface of the base material (G) promote an interaction such as a chemical bond or physical adsorption. The adhesive strength of the pressure adhesive can be improved. In particular, since the interaction is high on the surface of an inorganic material such as glass, a metal foil, a metal vapor deposition film, a metal plate, or an inorganic filler-containing film, it is easy to improve the adhesive strength.

  As the silane compound (D) having no primary or secondary amino group, a known silane compound can be used. For example, alkyl alkoxysilane, aryl alkoxysilane, carbamate alkoxysilane, vinyl alkoxysilane. , Alkoxysilanes having an alkoxyl group such as halogen-based alkoxysilanes, (meth) acryloyl-based alkoxysilanes, mercapto-based alkoxysilanes, imidazole-based alkoxysilanes, isocyanate-based alkoxysilanes, epoxy-based alkoxysilanes, or hydrogen atoms on silicon atoms , Alkylsilanes, aryl groups, or halogens, and organic silanes having reactivity by reacting directly or silylamines having a tertiary amino group.

  For example, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltriacetoxysilane, methyltris (methoxyethoxy) silane, methyltris (methoxypropoxy) silane, Ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltriisopropoxysilane, butyltrimethoxysilane, butyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxy Silane, octyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, silane Chlorotrimethoxysilane, cyclohexyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiisopropoxysilane, dimethyldiacetoxysilane, dimethylbis (methoxyethoxy) silane, dimethylbis (methoxypropoxy) silane, diethyldimethoxysilane , Diethyldiethoxysilane, diethyldiisopropoxysilane, diethyldiacetoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, methylethyldiisopropoxysilane, methylethyldiacetoxysilane, methylpropyldimethoxysilane, methylpropyldiethoxy Alkyl alkoxysilanes such as silane, methylpropyldiisopropoxysilane, methylpropyldiacetoxysilane, etc. ;

  For example, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriisopropoxysilane, phenyltriacetoxysilane, tolyltrimethoxysilane, tolyltriethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldiisopropoxysilane, diphenyldi Aryl alkoxysilanes such as acetoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, methylphenyldiisopropoxysilane, methylphenyldiacetoxysilane;

For example, (3-carbamateethyl) propyltriethoxysilane, (3-carbamateethyl) propyltrimethoxysilane, (3-carbamateethyl) propyltripropoxysilane, (3-carbamatepropyl) propyltriethoxysilane, (3-carbamatepropyl ) Propyltrimethoxysilane, (3-carbamatepropyl) propyltripropoxysilane, (3-carbamatebutyl) propyltriethoxysilane, (3-carbamatebutyl) propyltrimethoxysilane, (3-carbamatebutyl) propyltripropoxysilane, (3-carbamatebutyl) butyltripropoxysilane, (3-carbamatebutyl) propylmethyldiethoxysilane, (3-carbamatepentyl) propyltriethoxysilane (3-carbamate hexyl) propyl triethoxysilane, (3-carbamate octyl) pentyl riboxysilane, (3-carbamateethyl) propylsilyltrichloride, (3-carbamateethyl) propyltrimethylsilane, (3-carbamateethyl) propyl Carbamate alkoxysilanes such as dimethylsilane, 3-carbamateethyl) propyltributylsilane, (3-carbamateethyl) ethyl-p-xylenetriethoxysilane, (3-carbamateethyl) -p-phenylenetriethoxysilane;

  For example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltriacetoxysilane, vinyltris (methoxyethoxy) silane, vinyltris (methoxypropoxy) silane, allyltrimethoxysilane, allyltriethoxysilane, divinyldimethoxysilane , Divinyldiethoxysilane, divinyldiisopropoxysilane, divinyldiacetoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, methylvinyldiisopropoxysilane, methylvinyldiacetoxysilane, diallyldimethoxysilane, diallyldiethoxysilane, Diallyldiisopropoxysilane, methylallyldimethoxysilane, methylallyldiethoxysilane, methylallyldiisopropoxy Vinyl alkoxysilanes such as silane and methylallyldiacetoxysilane;

  For example, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, 3-chloropropylmethyldiethoxysilane, 3,3,3-trifluoropropyltrimethoxy Halogen-based alkoxysilanes such as silane, 3,3,3-trifluoropropyltriethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, 3,3,3-trifluoropropylmethyldimethoxysilane Kind;

  For example, 3-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ- (Meth) acryloyl alkoxysilanes such as acryloxypropylmethyldimethoxysilane;

  For example, mercapto-based alkoxysilanes such as 3-mercaptopropyltrimethoxylane, 3-mercaptopropyltriethoxysilane, and γ-mercaptopropylmethyldiethoxysilane;

  For example, imidazole alkoxysilanes such as 3- (2-imidazolin-1-yl) propyltrimethoxysilane and 3- (2-imidazolin-1-yl) propyltriethoxysilane;

  For example, isocyanate-based alkoxysilanes such as 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropyltripropoxysilane;

  For example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- ( 3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, epoxy-based alkoxysilanes such as 2- (3,4-epoxycyclohexyl) ethylmethyldiethoxysilane;

  For example, methylsilane, ethylsilane, dimethylsilane, diethylsilane, diethylmethylsilane, butyldimethylsilane, di-t-butylmethylsilane, triethylsilane, trihexylsilane, butyldimethylsilane, cyclohexyldimethylsilane, n-hexylsilane, n- Octylsilane, tri-n-octylsilane, tripropylsilane, triisopropylsilane, triisobutylsilane, trihexylsilane, n-octadecylsilane, phenylsilane, methylphenylsilane, dimethylphenylsilane, methylphenylvinylsilane, dimethylbenzylsilane, Diphenylsilane, triphenylsilane, (phenylethynyl) dimethylsilane, methyldichlorosilane, ethyldichlorosilane, dimethylchlorosilane, bis ( -Chloroethoxy) methylsilane, tris (2-chloroethoxy) silane, n-hexyldichlorosilane, diisopropylchlorosilane, dichlorosilane, di-t-butylchlorosilane, trichlorosilane, chloromethylsilane, methylphenylchlorosilane, phenyldichlorosilane, diphenyl Chlorosilane, chloroisopropylsilane, dichloromethylsilane, dichloroethylsilane, methyldimethoxysilane, dimethoxymethylsilane, methyldiethoxysilane, dimethylethoxysilane, diethoxysilane, trimethoxysilane, triethoxysilane, tripentyloxysilane, tris ( Trimethylsiloxy) silane, methylphenylethenylsilane, allyldimethylsilane, 1,1,2-trimethyldisilane, 1,1,2, -Tetraphenyldisilane, 1,1,3,3-tetramethyldisilazane, 1,4-bis (dimethylsilyl) benzene, methyltris (dimethylsiloxy) silane, tris (trimethylsiloxy) silane, phenyltris (dimethylsiloxy) silane , Tetrakis (dimethylsiloxy) silane, tetramethyldisilazane, diacetoxymethylsilane, tetrakis (dimethylsilyl) silane, allyldimethylsilane, mercaptodimethylsilane, cyclopropanesilane, tris (trimethylsilyl) silane, 1,1,4,4 -Tetramethyldisilylethene, cyclohexanesilane, pentamethyldisiloxane, tetramethylcyclotetrasiloxane, 1,3-diphenyl-1,3-dimethyldisiloxane, pentamethyldisiloxane, 1,1,3 , 3-tetramethyldisiloxane, 1,1,3,3-tetraisopropyldisiloxane, 1,1,3,3-tetrakis (trimethylsiloxy) disiloxane, 1,2-bis (dimethylsilyl) benzene, 1, 1,3,3,5,5-hexamethyltrisiloxane, 1,1,3,3,5,5,7,7-octamethyltetrasiloxane, 1,1,1,3,5,5,5- Heptamethyltrisiloxane, 1,1,3,3,5,5-heptamethyltrisiloxane, 1,1,1,3,5,7,7,7-octamethyltetrasiloxane, 1,3,5,7 -Silyl with tetramethylcyclotetrasiloxane, 1,3,5,7,9-pentamethylcyclopentasiloxane, α, ω-bis (hydrodiene) polydimethylsiloxane or long-chain dimethylsiloxane oligomer Oily or waxy organosilanes with bases;

  For example, bis (dimethylamino) methylsilane, bis (dimethylamino) dimethylsilane, bis (dimethylamino) methylvinylsilane, dimethylaminotrimethylsilane, diethylaminodiethylsilane, tris (dimethylamino) silane, tris (trimethylsilyl) amine, methyltris (dimethyl) Amino) silane, methyltris (N, N-dimethylaminoxy) silane, tetrakis (dimethylamino) silane, phenyltris (dimethylamino) silane, bis (dimethylamino) diphenylsilane, benzylidene-3-ethoxydimethylsilylpropylamine, 3 -Trimethylsilylphenyl N, N-dimethyl carbonate, 4-trimethylsilylphenyl N, N-dimethyl carbonate, trimethylsilylmethyl N, N-dimethyl Dithiocarbonate, methyl N-cyclohexyl-N-trimethylsilyl carbonate, isobutyl N-butyl-N-trimethylsilylmethyl carbonate, methylsilatrane, phenylsilatrane, N-methyl-N-trimethylsilylacetamide, 3-dimethylaminopropyldiethoxymethylsilane Silylamines having a tertiary amino group, such as N, N′-bis (trimethylsilyl) -1,1,3,3-tetramethyl-3-vinylsiloxane;

  For example, 1-trimethylsilylimidazole, 2- (dimethylsilyl) pyridine, methyltris (1H-imidazol-1-yl) silane, 1-trimethylsilyl-1,2,4-triazole, 1-trimethylsilylpyrrole, 1-trimethylsilylpyrrolidine, heptamethyl -3- (3-pyrrolidinopropyl) trisiloxane, piperidinomethyltrimethylsilane, dimethylpiperidinomethylvinylsilane, 2-piperidinoethyltrimethylsilane, 2-piperidinoethylmethyldimethoxysilane, 3-piperidi Nopropylmethyldimethoxysilane, 3-piperidinopropyltrimethoxysilane, dimethylphenyl-2-piperidinoethoxysilane, allyldimethylpiperidinomethylsilane, 3-piperidinopropyltrimethylsilane, di Toxi-2-piperidinoethoxyvinylsilane, 3-methylpiperidinomethylpentamethyldisiloxane, 3- (4-methylpiperidinopropyl) pentamethyldisiloxane, pentamethylpiperidinomethyldisiloxane, heptamethyl-3 -(2-piperidinoethyl) trisiloxane, 3-piperidinopropyltris (trimethylsiloxy) silane, 3- (4-methylpiperazinopropyl) trimethylsilane, 3-morpholinopropyltrimethoxysilane, heptamethyl-3- ( Silylamines having a nitrogen atom-containing heterocycle such as 3-morpholinopropyl) trisiloxane, bis (trimethylsilyl) uracil, N-trimethylsilylmethylphthalimide, N- (3-dimethoxymethylsilylpropyl) succinimide;

  For example, dimethyloctadecyl-3-trimethoxysilylpropylammonium chloride, N, O-bis (trimethylsilyl) trifluoroacetamide, N, N′-bis (trimethylsilyl) -N-phenylurea, N, N′-bis (trimethylsilyl) Examples thereof include silylamines having a nitrogen atom and not having a primary or secondary amino group, such as urea and N, N′-diphenyl-N-trimethylsilylurea.

  In addition, as the silane compound (D), a commercially available product can be used, and an oligomeric silane obtained by oligomerizing a mixture of two or more silanes by hydrolysis and condensation can also be used. The silane compound (D) may be used alone or in combination of two or more. In particular, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-mercaptopropyltrimethoxy in terms of improving adhesion to the substrate surface. Lan, 3-mercaptopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3- (2- Imidazolin-1-yl) propyltriethoxysilane and 3-isocyanatopropyltriethoxysilane are preferably used.

  The pressure-sensitive adhesive of the present invention preferably contains 0.1 to 10 parts by weight of the silane compound (D) with respect to 100 parts by weight of the copolymer (A). If it is 0.1 parts by weight or more, the heat resistance and heat-and-moisture resistance are improved, and if it is 10 parts by weight or less, the coating film can be prevented from floating, peeling or foaming in a harsh environment. Suitable for adhesion and adhesion to (G).

<Other components (E)>
In one embodiment of the pressure-sensitive adhesive of the present invention, other components (E) are appropriately added to the pressure-sensitive adhesive in addition to the essential components as long as the effects of the present invention are not impaired. Is also possible.
As other components (E), for example, polymerization curing shrinkage reduction, thermal expansion coefficient reduction, dimensional stability improvement, elastic modulus improvement, viscosity adjustment, thermal conductivity improvement, strength improvement, toughness improvement, coloring improvement, etc. From the viewpoint, an organic or inorganic filler can be blended. Such fillers may be composed of materials such as polymers, ceramics, metals, metal oxides, metal salts, and dyes and pigments. Moreover, about the shape, it is not specifically limited, For example, a particulate form, fibrous form, etc. may be sufficient. In addition, when blending the above polymer-based materials, flexibility imparting agent, plasticizer, flame retardant, storage stabilizer, antioxidant, ultraviolet absorber, thixotropy imparting agent, dispersion stabilizer, fluidity imparting It is also possible to dissolve, semi-dissolve or micro-disperse in pressure sensitive adhesives as polymer blends or polymer alloys rather than as independent fillers such as adhesives, tackifiers, antistatic agents and antifoaming agents. .

<Pressure sensitive adhesive>
Next, the pressure sensitive adhesive will be described.
The pressure-sensitive adhesive of the present invention is a pressure-sensitive adhesive containing a copolymer (A) having a weight average molecular weight of 100,000 to 2,000,000 and a silane compound (B) having a primary or secondary amino group. It is an agent, and the copolymer (A) is characterized by containing the compounds (a1), (a2) and (a3) as monomer units constituting the copolymer (A). Accordingly, the reactive compound (C), the silane compound (D), or other component (E) is appropriately blended.

  It is preferable that the viscosity of the pressure-sensitive adhesive of the present invention is appropriately adjusted according to the usage form. The pressure-sensitive adhesive of the present invention substantially contains an organic solvent, and a solvent may be additionally used as necessary to adjust the viscosity. For example, as a solvent, organic solvents such as methanol, ethanol, isopropyl alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl acetate, ethyl acetate, butyl acetate, cyclohexane, toluene, xylene, and other hydrocarbon solvents as described above, or water are used. Can be used. By using such a solvent, the viscosity of the pressure-sensitive adhesive can be easily adjusted. However, it is preferable not to use a solvent having active hydrogen that can react with the silane compound (B), the reactive compound (C), or the silane compound (D), for example, an alcohol solvent. Further, the viscosity can be lowered by heating the pressure-sensitive adhesive without using an additional solvent.

Using the pressure-sensitive adhesive of the present invention, a pressure-sensitive adhesive layer typically having a film thickness of 0.5 to 300 μm is formed. Furthermore, 1-100 micrometers is more preferable. When the film thickness is in the above range, a sufficient adhesive force can be obtained.
Accordingly, from the viewpoint of coating film formation, the viscosity of the pressure-sensitive adhesive is in the range of 500 to 8,000 mPa · s, preferably 1,000 to 5 when measured with a B-type viscometer at 25 ° C. , Preferably in the range of 1,000 mPa · s. When the viscosity is 8,000 mPa · s or less, a thin film of 0.5 to 300 μm can be easily formed on the base material (G) by coating, and optical properties such as transmittance can be easily improved. It is. On the other hand, when the viscosity is 500 mPa · s or more, it is easy to control the thickness of the resin layer formed from the pressure-sensitive adhesive. In the present embodiment, the film thickness, viscosity, or nonvolatile content concentration of the adhesive layer is set according to the use of the laminate.

<Pressure-sensitive adhesive film>
Next, the pressure sensitive adhesive film will be described.
The pressure-sensitive adhesive film of the present invention is obtained by forming a pressure-sensitive adhesive layer made of the above-mentioned pressure-sensitive adhesive on a substrate (G) described later. As a method for producing a pressure-sensitive adhesive film, for example, a pressure-sensitive adhesive is applied to the release-treated surface of a sheet-like substrate (also referred to as a release liner) whose surface has been subjected to a release treatment, and then the substrate (G) is bonded. Or a method in which the pressure-sensitive adhesive is directly applied to the substrate (G) and dried, and the release treatment surface of the release liner is bonded to the surface of the adhesive layer.

  As the substrate (G), it is preferable to use a sheet-like substrate. Specific examples of the sheet-like substrate include cellophane, various plastic sheets, and paper sheets. Of these, the use of various transparent plastic sheets is preferred. Further, the substrate (G) may have a single layer structure, or may have a multilayer structure formed by laminating a plurality of substrates, and is a sheet-like substrate having any structure. Can also be suitably used. When constituting the laminate of the present invention, it is preferable to form a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive of the present invention on at least one surface of various plastic sheets. Further, a sheet-like substrate (also referred to as a release liner) whose surface has been subjected to a release treatment can be used.

  The various plastic sheets are also referred to as various plastic films, and it is preferable to use various transparent plastic films (also referred to as transparent film (H)). Specific examples of the transparent film (H) include, for example, a polyvinyl alcohol film (also referred to as PVA film), a polytriacetyl cellulose film (also referred to as TAC film), a polypropylene film (also referred to as PP film), and a polyethylene film (PE film). Polyolefin resin film such as polycycloolefin film (also referred to as COP film), ethylene-vinyl acetate copolymer film (also referred to as EVA film), polyethylene terephthalate film (also referred to as PET film) and polybutylene terephthalate Films of polyester resin such as film (also referred to as PBT film), film of polycarbonate resin (also referred to as PC film), film of polynorbornene resin Film, polyarylate resin film, polyacrylate resin film, polyphenylene sulfide resin film (also referred to as PPS film), polystyrene resin film (also referred to as PST film), polyamide resin film (PA film) Also a polyimide resin film (also referred to as a PI film), an oxirane resin film, and the like. Among these substrates, it is particularly preferable to use a sheet-like substrate such as a PVA film, a TAC film, a COP film, a polyester resin film, or a PC film as the transparent film (H).

  In addition, the transparent film (H) has a surface with physical treatment such as corona discharge, plasma treatment, flame treatment, etc., chemical treatment that modifies the film surface with acid or alkali, etc. Films with a substantial increase in surface area of the substrate, or metal oxides such as silicon, aluminum, magnesium, calcium, potassium, tin, sodium, boron, titanium, lead, zirconium, yttrium on the surface, or non-metallic inorganic oxides For the pressure-sensitive adhesive, such as a plastic film on which is vapor-deposited, one that has been subjected to an easy adhesion treatment or one that has been provided with functionality for each application can be suitably used.

  In the present invention, for the purpose of optical use, an optical film (I) in which a transparent film (H) is used as a substrate (G) and an adhesive layer made of a pressure-sensitive adhesive is formed on the transparent film (H). It is also possible. Here, with the optical film (I), the transparent film (H) can be used as it is as the optical film (I), and the transparent film itself having a special function is used. Is also possible. Here, the special function is intended to have optical functions such as light transmission light diffusion, light collection, refraction, scattering, and HAZE. These transparent films (H) can be used alone or in combination of several kinds when used as the optical film (I). In the present invention, an optical layered body can be formed by forming an adhesive layer made of the pressure-sensitive adhesive on at least one surface of the optical film (I), and the display is laminated on a liquid crystal cell or the like. It can also be used for applications.

Examples of the optical film (I) used in the present invention include a polarizing film, a retardation film, an elliptically polarizing film, an antireflection film, and a brightness enhancement film.
For example, a polarizing film is also called a polarizing plate, and a polycycloolefin film that is a polynorbornene film, a polyacrylate resin film, a polycarbonate film, or a polyester film on one or both surfaces of a polyvinyl alcohol polarizer. A multilayer structure film in which films such as films are laminated. In the case of a polarizing film, even when left in a high-temperature atmosphere and a high-temperature and high-humidity atmosphere, the adhesive layer according to the present invention has good stress relaxation properties, so that light leakage caused by warping of the polarizing film can be suppressed.

  After applying a pressure-sensitive adhesive to the release liner or optical film (I) by an appropriate method according to a conventional method, if the pressure-sensitive adhesive contains a liquid medium such as an organic solvent or water, heating, etc. If the liquid medium is removed by the method or if the pressure-sensitive adhesive does not contain the liquid medium to be volatilized, the adhesive layer in the molten state is cooled and solidified to adhere onto the release liner or optical film. A layer can be formed. When an adhesive layer is formed on the release liner, the adhesive layer surface and the optical film (I) are bonded together, and the adhesive layer is transferred onto the optical film (I) to adhere to the optical film (I). A layer can be formed.

  The method for applying the pressure-sensitive adhesive of the present invention is not particularly limited. For example, various well-known methods such as Mayer bar, applicator, brush, spray, roller, gravure coater, die coater, kiss coater, lip coater, comma coater, blade coater, knife coater, reverse coater, spin coater, dip coater, etc. Can be applied. Moreover, it can select without particular restriction | limiting also about forms, such as thin film coating or thick film coating.

  The optical laminate of the present invention is obtained by sequentially laminating a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive of the present invention and glass using the optical film (I) as a base material (G). Here, the optical film (I) is preferably a polarizing film. The glass may be the glass surface of a liquid crystal cell.

  The pressure-sensitive adhesive sheet of the present invention has been described by taking a polarizing film as an example of the optical film (I). However, it is not limited to the polarizing film, and it should be easily understood that a laminated body that can be suitably used in optical applications can be configured in other embodiments using other various substrates. For example, it can be preferably used for various electronics-related members such as liquid crystal displays, plasma displays, touch panels, electrode peripheral members, glass members such as protective films, building materials and vehicle window glass, but plastics such as polyolefin, ABS, polyacryl, cardboard It can also be used for metals such as wood, plywood, stainless steel and aluminum.

  Specific examples of the present invention will be described below together with comparative examples, but the present invention is not limited to the following examples. In the following examples and comparative examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively, unless otherwise specified.

<Production of copolymer (A)>
(Synthesis Example 1)
A polymerization tank, a stirrer, a thermometer, a reflux condenser, a dropping apparatus, a polymerization tank and a dropping apparatus of a polymerization reaction apparatus equipped with a nitrogen introducing tube, the following monomers {α, β-unsaturated having one or more hydroxyl groups: Double bond group-containing compound (a1), α, β-unsaturated double bond group-containing compound (a2) having one or more carbonyl groups, and α, β-unsaturated double having no hydroxyl group and carbonyl group The bonding group-containing compound (a3)}, the polymerization initiator, and the organic solvent were charged at the following ratios.

[Polymerization tank]
N-butyl acrylate (a3-1) 38 parts methyl acrylate (a3-2) 20 parts 2-hydroxyethyl acrylate (a1-1) 1 part N- (1,1-dimethyl-3-oxobutyl) acrylamide ( a2-1) 2 parts Acetone (organic solvent) 33 parts V-65 (polymerization initiator) 0.05 parts [Drip device]
N-butyl acrylate (a3-1) 38 parts 2-hydroxyethyl acrylate (a1-1) 1 part Acetone (organic solvent) 33 parts V-65 (polymerization initiator) 0.05 parts

After replacing the air in the polymerization tank with nitrogen gas, the polymerization was started by heating to 60 ° C. with stirring in a nitrogen atmosphere. The mixture of the α, β-unsaturated double bond group-containing compound, the polymerization initiator, and the organic solvent was dropped from the dropping device over about 2 hours at the reflux temperature. After completion of the dropwise addition, the mixture was further aged for 6 hours with stirring, 160 parts of ethyl acetate was added, and the mixture was cooled to room temperature to obtain a copolymer (A) solution having a nonvolatile concentration of about 30%.
This solution is colorless and transparent, has a nonvolatile content concentration of 30.5% by weight, a solution viscosity of 6,000 mPa · s (23 ° C.), and the copolymer (A) has a glass transition temperature of −35 ° C. and a weight average. The molecular weight was 1,200,000.

<Synthesis Examples 2 to 25>
(A2) and (a3-2) are all charged in the polymerization tank, and (a1), (a3-1), the organic solvent, and the polymerization initiator are half the amount in the polymerization tank and the dropping device. A copolymer solution was synthesized in the same manner as in Synthesis Example 1 except that each change was made. The solution appearance, nonvolatile content concentration (NV), solution viscosity (Vis), weight average molecular weight (Mw) and glass transition temperature (Tg) of the obtained copolymer were determined according to the following methods, and the results are shown in Table 1. It was.

<< Solution appearance >>
The solution appearance of the copolymer obtained in each synthesis example was observed and evaluated visually.

<< Non-volatile content (NV) >>
About 1 g of the copolymer solution obtained in each synthesis example was weighed into a metal container, dried in an oven at 150 ° C. for 20 minutes, the residue was weighed, and the remaining rate was calculated, and the non-volatile concentration ( Solid unit) (unit:%).

<< Solution viscosity (Vis) >>
As described above, the copolymer solution obtained in each synthesis example was measured with a B-type viscometer (TV-22 manufactured by Toki Sangyo Co., Ltd.) at 25 ° C., and about 1.2 ml was used as a measurement sample, and the rotation speed was The solution viscosity (mPa · s) was measured under conditions of 5 to 100 rpm and 1 minute rotation.

《Average molecular weight》
For the measurement of the number average molecular weight (Mn) and the weight average molecular weight (Mw), GPC (gel permeation chromatography) manufactured by Showa Denko KK was used. The number average molecular weight (Mn) and the weight average molecular weight (Mw) were determined in terms of polystyrene as a standard substance.
Device name: Showa Denko GPC (Gel Permeation Chromatography) “Shodex GPC System-21”
Column: Tosoh GMHXL: 4 Tosoh HXL-H: 1 In series.
Mobile phase solvent: Tetrahydrofuran Flow rate: 1.0 ml / min Column temperature: 40 ° C

<< Glass transition temperature (Tg) >>
An “SSC5200 disk station” (manufactured by Seiko Instruments Inc.) was connected to a robot DSC (differential scanning calorimeter, “RDC220” manufactured by Seiko Instruments Inc.) and used for measurement.
About 10 mg of a sample is put in an aluminum pan, weighed and set in a differential scanning calorimeter, and kept for 5 minutes at a temperature of 100 ° C. using the same type of aluminum pan without a sample as a reference. It was rapidly cooled to 120 ° C. Thereafter, the temperature was increased at a rate of temperature increase of 10 ° C./min, and the glass transition temperature (Tg, unit: ° C.) was determined from the obtained DSC chart.

Illustrative compounds are specifically shown in Table 1 below. In Table 1, a blank means no blending.
Compound (a1-1)
2HEA: 2-hydroxyethyl acrylate, 4HBA: 4-hydroxybutyl acrylate compound (a1-2)
HPPA: 2-hydroxy-3-phenoxypropyl acrylate / compound (a2-1)
DAAM: N- (1,1-dimethyl-3-oxobutyl) acrylamide, AAEM: 2-oxobutanoylethyl methacrylate / compound (a2-2)
PAV: vinyl propionate / compound (a2-3)
CEA: 2-carboxyethyl acrylate compound (a3-1)
BA: n-butyl acrylate, 2EHA: 2-ethylhexyl acrylate, LMA: lauryl methacrylate / compound (a3-2-1)
NMEA: N-methylaminoethyl acrylate / compound (a3-2-2)
MA: methyl acrylate, MMA: methyl methacrylate, PHEA: phenoxyethyl acrylate, AA: acrylic acid / polymerization initiator V65: 2,2′-azobis (2,4-dimethylvaleronitrile) [Wako Pure Chemical Industries, Ltd. “V65”], PBO: t-butyl peroxy-2-ethylhexanoate [“Perbutyl O” manufactured by NOF Corporation]
Organic solvent Ace: acetone, MEK: methyl ethyl ketone, MeAc: methyl acetate, EAc: ethyl acetate In the column of organic solvent in Table 1, the notation “Ace / EAc” is “organic solvent during copolymer polymerization” / Dilution solvent "means that the organic solvent at the time of copolymer polymerization used Ace, and the dilution solvent used EAc.

Using the copolymers obtained in the synthesis examples shown in Table 1, pressure-sensitive adhesives were prepared by the following methods.
(Examples 1-62, Comparative Examples 1-10)
The silane compound (B) having an amino group is an essential component for 100 parts of the copolymer (A) obtained in each synthesis example, and can react with the hydroxyl group in the copolymer (A) as necessary. Reactive compounds (C) having one or more functional groups in the molecule, silane compounds (D) having no primary or secondary amino groups, and other components (E) are listed in Table 2 in the weight ratio ( Part) and an additional solvent such as ethyl acetate was added to adjust the non-volatile content concentration to about 30% to obtain a pressure-sensitive adhesive. The obtained pressure-sensitive adhesive was applied to each substrate, dried, and bonded to create a pressure-sensitive adhesive film, and evaluated by the following methods. The results are shown in Table 2.

<Stability of solution over time>
The pressure-sensitive adhesive was evaluated in three stages for changes in viscosity, appearance changes such as separation of solution layers and generation of precipitates. The viscosity of the pressure-sensitive adhesive was 25 ° C. using a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd.) immediately after the pressure-sensitive adhesive was prepared and stored at 5, 25, and 40 ° C. for 1 month. The measurement was performed under the conditions of 12 rpm and 1 minute rotation, and changes in appearance such as changes in viscosity and separation of solution layers and generation of precipitates were evaluated in three stages. In the case of “○” or “△” evaluation, there is no problem in actual use.
○: No separation of solution layer or generation of precipitates, viscosity increase rate up to 1 month is less than 50%, good.
Δ: No separation of solution layer or generation of precipitate, viscosity increase rate up to one month is 50% or more and less than 100%, usable.
X: Gelation occurs within one month, the rate of increase in viscosity is 100% or more, or separation of the solution layer or generation of precipitates occurs. Bad.
Here, the viscosity increase rate was calculated by the following method.
Viscosity increase rate = 100 × {(viscosity after storage for one month) − (viscosity immediately after adjustment)} / (viscosity immediately after adjustment)

<Evaluation of coatability>
The pressure-sensitive adhesive was used as a base material on a polyethylene terephthalate film (Therapy MF: manufactured by Toray Film Processing Co., Ltd.) (hereinafter referred to as “release liner”) having a thickness of 38 μm, and the thickness after drying was reduced. The adhesive layer was formed by coating to 25 μm and drying with hot air at 100 ° C. for 2 minutes. Next, a 100 μm thick polyethylene terephthalate film (PET film) was bonded to the coated surface to prepare a pressure-sensitive adhesive film. And the state of the adhesive layer surface (coating surface) after peeling a peeling film was observed visually, and it evaluated in three steps. In the case of “○” or “△” evaluation, there is no problem in actual use.
○: A smooth coated surface was obtained. Good.
Δ: Some repelling and foaming are observed at the end of the coated surface. Can be used practically.
×: Repelling, foaming and streaking were observed on the coated surface. Bad.

<Measurement of peel strength>
The pressure-sensitive adhesive film was cut to a width of 25 mm, the release liner was peeled off, and the exposed adhesive layer was attached to a non-alkali glass plate having a thickness of 100 μm using a laminator in an environment of 23 ° C. and a relative humidity of 50%. . Then, it hold | maintained for 20 minutes in the autoclave of conditions of 50 degreeC and 5 atmospheres, and obtained the measurement sample. The measurement sample was allowed to stand at 23 ° C. for 1 day, and was then peeled at a peeling speed of 300 mm / min and a peeling angle using a tensile tester (“Tensilon” manufactured by Orientec Co., Ltd.) in an environment of 23 ° C. and 50% relative humidity. The peel strength was measured under the condition of 180 degrees (measurement of peel strength one day after bonding). Moreover, after leaving the said measurement sample to stand at 23 degreeC for 14 days, peeling strength was measured by the same method (peeling strength measurement after 14 days of bonding). This peel strength was evaluated as an adhesive strength in three stages. In the case of “○” or “△” evaluation, there is no problem in actual use.
○: Peel strength is 8.0 (N / 25 mm) or more and less than 12.0 (N / 25 mm). Good.
Δ: Peel strength is 5.0 (N / 25 mm) or more and less than 8.0 (N / 25 mm), or peel strength is 12.0 (N / 25 mm) or more and less than 15.0 (N / 25 mm). Can be used practically.
X: Peel strength is less than 5.0 (N / 25 mm), or 15.0 (N / 25 mm) or more. Bad.

<< Evaluation of optical characteristics >>
The pressure-sensitive adhesive was applied on the release liner so that the thickness after drying was 25 μm, and dried with hot air at 100 ° C. for 2 minutes to form a pressure-sensitive adhesive layer. Next, a separately prepared release liner was bonded to the adhesive layer to prepare a sample in which the adhesive layer was sandwiched between the release liners.
Next, both release liners were removed, the appearance of the pressure-sensitive adhesive layer alone was visually determined, and HAZE was measured by “NDH-300A (Nippon Denshoku Industries Co., Ltd.)”. In the case of “○” or “△” evaluation, there is no problem in actual use.
○: No cloudiness or the like is observed, and HAZE: less than 0.5. Good.
Δ: No cloudiness or the like is observed, but HAZE: 0.5 or more and less than 2, and can be used without any practical problem.
X: Cloudiness is observed or HAZE: 2 or more. Bad.

<< Evaluation of workability >>
The pressure-sensitive adhesive film was cut into a width of 100 mm and a length of 100 mm, 30 sheets of this were stacked, and the adhesive layer protruded from the edge of the adhesive film when pressed at 40 ° C.-60 Kg / cm ² for 1 hour. The state was evaluated in three stages as follows. In the case of “○” or “△” evaluation, there is no problem in actual use.
○: No protruding adhesive layer is observed. Good.
Δ: Protrusion of the adhesive layer of less than 0.3 mm is observed, but can be used practically.
X: Protrusion of the adhesive layer of 0.3 mm or more is observed. Bad.

<Evaluation of foaming peeling resistance>
The pressure-sensitive adhesive film is cut into a width of 100 mm and a length of 100 mm, the release liner is peeled off, and bonded and fixed to a polycarbonate (PC) plate, and a pressure of 0.5 MPa is applied at 50 ° C. for 20 minutes. A test piece (optical laminate) having a layer structure of “polyester film / pressure-sensitive adhesive layer / PC plate” held in an autoclave was produced. Using the test piece, a heat treatment (heat resistance test) was performed in an oven at 80 ° C. for 24 hours. After this heat resistance test, the adhesion interface (the interface between the pressure-sensitive adhesive layer and the PC plate) of the test piece was visually observed and evaluated in three stages. In the case of “○” or “△” evaluation, there is no problem in actual use.
○: No bubbles or floats are observed, and it is good.
Δ: Fine bubbles and floats are slightly observed at the end, but can be used practically.
X: Bubbles and floats were observed over the entire surface. Bad.

<Evaluation of light leakage>
The pressure-sensitive adhesive was dried on a 38 μm-thick polyethylene terephthalate film (Therapy MF: manufactured by Toray Film Processing Co., Ltd.) (hereinafter referred to as “release liner”) as a base material. Was applied to a thickness of 25 μm and dried with hot air at 100 ° C. for 2 minutes to form a pressure-sensitive adhesive layer. Next, both surfaces of a polyvinyl alcohol (PVA) polarizing film (HLC2-5618: manufactured by SANRITZ) are sandwiched between the adhesive layers as an optical film (I) with a triacetyl cellulose film (hereinafter referred to as “TAC film”). One side of a polarizing film with a laminated structure is bonded, and then aged for one week under conditions of a temperature of 35 ° C. and a relative humidity of 55%, and an optical structure having a configuration of “release liner / pressure-sensitive adhesive layer / TAC film / PVA / TAC film” A pressure-sensitive adhesive film (also referred to as a polarizing film adhesive sheet) was obtained.
It cut | judged to 80 mm x 150 mm so that the axial direction of the absorption axis of said polarizing film adhesive sheet may become an angle of 45 degrees with respect to a long side. Next, the release liner is peeled off, and the exposed pressure-sensitive adhesive layer is arranged on both surfaces of a non-alkali glass plate having a thickness of 0.4 mm so that the axial directions of the respective absorption axes are orthogonal to each other in a 50 ° C. atmosphere. After applying pressure of 5 kg / cm ² and holding it in an autoclave for 20 minutes, leaving it in an atmosphere of 80 ° C. for 500 hours, returning it to room temperature, and checking for light leakage from the four corners or peripheral edges It observed visually and evaluated in three steps as light leakage. In the case of “○” or “△” evaluation, there is no problem in actual use.
○: No light leakage is observed. Good.
Δ: Light leakage is slightly noticeable, but can be used practically.
X: Light leakage is very remarkable. Bad.

<< Evaluation of removability (reworkability) >>
The polarizing film adhesive sheet is cut into a size of 25 mm × 150 mm, the release liner is peeled off, and is attached to a float glass plate with a thickness of 1.1 mm using a laminator, and placed in an autoclave at 50 ° C. and 5 atm. It was held for 20 minutes to obtain an optical laminate of a polarizing film adhesive sheet and a glass plate.
The polarizing film of this laminated body was peeled off at a speed of 300 mm / min in the direction of 180 °, and the fogging of the glass surface after peeling was visually observed and evaluated in three stages. In the case of “○” or “△” evaluation, there is no problem in actual use.
○: No cloudiness and no problem in practical use. Very good.
Δ: Some cloudiness is observed, but there is no practical problem. Good.
X: Transfer of the pressure-sensitive adhesive is recognized over the entire surface, and is not practical.

<< Evaluation of durability (heat resistance, heat and humidity resistance) >>
The release liner of the polarizing film adhesive sheet is peeled off, and the exposed pressure-sensitive adhesive layer is subjected to a pressure of 5 kg / cm ² in a 50 ° C. atmosphere on one side of a non-alkali glass plate having a thickness of 0.4 mm and autoclaved for 20 minutes. After being held and bonded together, it was left in an atmosphere at 80 ° C. for 500 hours (heat resistance test). Similarly, the sample was left in a constant temperature and humidity chamber at 60 ° C. and 90% relative humidity for 500 hours (moisture and heat resistance test).
After standing, the temperature was returned to room temperature, and the state of the polarizing film adhesive sheet floating / peeling, foaming and cracking was visually observed and evaluated in three stages. In the case of “○” or “△” evaluation, there is no problem in actual use.
Foaming is a state in which relatively large bubbles are generated at the interface (other than the peripheral edge) between the pressure-sensitive adhesive layer and the glass.
The floating / peeling is a state where the polarizing film adhesive sheet is lifted from the glass and peeled off.
The crack is a state in which fine bubbles having a diameter of 1 mm or less are generated in a streak-like manner at the peripheral edge of the polarizing film adhesive sheet.
Each evaluation standard is as follows.
○: No foaming, floating / peeling or cracking occurs. Good.
Δ: Minor occurrence of foaming, floating, peeling or cracking of 0.5 mm or less is observed, but it can be used practically.
X: Remarkable generation | occurrence | production, such as foaming, a float, peeling, a crack, is recognized over the whole surface. Cannot be used practically.

The materials used in the examples are shown below. In Table 2, a blank means no blending.
・ Copolymer (A)
Copolymer / compound (B) obtained in each synthesis example shown in Table 1
MAS: 3-aminopropyltrimethoxysilane (amine value: 313 mgKOH / g), PAS: 3- (N-phenyl) aminopropyltrimethoxysilane (amine value: 439 mgKOH / g), MCHS: methyltris (cyclohexylamino) silane ( Amine value: 166 mgKOH / g), MTAS: methyltris (2-aminoethoxy) silane (amine value: 754 mgKOH / g)
・ Compound (C)
TDI / TMP: trimethylolpropane adduct of tolylene diisocyanate, XDI / TMP: trimethylolpropane adduct of xylylene diisocyanate, V05: carbodiimide [“Carbodilite V-05” manufactured by Nisshinbo Co., Ltd.], HBAP : 2,2′-bishydroxymethylbutanol tris [3- (1-aziridinyl) propionate], ALAA: aluminum tris (acetylacetonate), TGXA: N, N, N ′, N′-tetraglycidyl-m-xyl Range amine compound (D)
HTS: hexyltrimethoxysilane, EPS: 3-glycidoxypropyltrimethoxysilane, EAS: diethylaminotrimethylsilane and other components (E)
AO50: Phenol-based antioxidant [Adeka "Adekastab AO-50"]

As described above, the pressure-sensitive adhesive of the present invention has the solution stability over time, the coating property in Examples 1, 2, 11 to 13, 18 to 24, 29 to 31, 35 to 45, and 54 to 62. In any of peel strength, optical properties, workability, foam peeling resistance, light leakage, reworkability, heat resistance, and heat and humidity resistance, the “△” evaluation (practical level) is 2 or less out of 13 items. , And others are all “Excellent” (good level), so it can be seen that they are excellent.
Moreover, in Examples 3 to 10, 14 to 17, and 25 to 28, the “△” evaluation (practical level) of each evaluation is 3 to 13 out of 13 items, and the “×” evaluation (defective level) is. Since there is no one, it can be used practically without any problem.
On the other hand, in Comparative Examples 1 to 10, any one of solution aging stability, coating property, peel strength, optical properties, workability, foam peeling resistance, light leakage property, rework property, heat resistance, and wet heat resistance It turns out that is extremely inferior.

  Since the pressure-sensitive adhesive according to the present invention has excellent adhesive strength, it can be used in the construction field (eg, exterior, interior, equipment, etc.), electrical equipment field (eg, home appliances, kitchen equipment, air conditioning, etc.), and transport equipment field. It can also be used in various industrial fields other than the optical field, such as the ship field, automobiles, etc., the furniture field, and the sundries field.

Claims (9)

A pressure-sensitive adhesive containing a copolymer (A) having a weight average molecular weight of 100,000 to 2,000,000 and a silane compound (B) having a primary or secondary amino group, A) is a pressure-sensitive adhesive containing the following compounds (a1), (a2) and (a3) as monomers constituting the copolymer (A).
Α, β-unsaturated double bond group-containing compound (a1) having one or more hydroxyl groups
Α, β-unsaturated double bond group-containing compound having one or more carbonyl groups (a2)
Α, β-unsaturated double bond group-containing compound having no hydroxyl group or carbonyl group (a3)
(However, the compound (a2) does not have a hydroxyl group) In a total of 100% by weight of the compounds (a1), (a2) and (a3) constituting the copolymer (A),
0.1 to 30% by weight of compound (a1),
0.1 to 30% by weight of compound (a2),
Compound (a3) is 40 to 99.8% by weight,
The pressure-sensitive adhesive according to claim 1, wherein   The pressure-sensitive adhesive according to claim 1 or 2, wherein the silane compound (B) having a primary or secondary amino group has a primary or secondary amine value of 100 to 600 mgKOH / g.   Compound (a3) is an α, β-unsaturated double bond group-containing compound (a3−) having an alkyl group having 2 to 20 carbon atoms and having a homopolymer having a glass transition temperature of −80 to 0 ° C. The pressure-sensitive adhesive according to claim 1, comprising 1).   Furthermore, the pressure sensitive adhesive in any one of Claims 1-4 containing the reactive compound (C) which has one or more functional groups which can react with the hydroxyl group in a copolymer (A).   A pressure-sensitive adhesive film comprising an adhesive layer containing the pressure-sensitive adhesive according to any one of claims 1 to 5 laminated on at least one surface of a substrate (G).   The pressure-sensitive adhesive film according to claim 6, wherein the substrate (G) is a transparent film (H).   The pressure-sensitive adhesive film according to claim 7, wherein the transparent film (H) is an optical film (I).   An optical laminate comprising an optical film (I), an adhesive layer containing the pressure-sensitive adhesive according to any one of claims 1 to 5, and glass.