JP5544822B2 - Pressure-sensitive adhesive, method for producing resin for pressure-sensitive adhesive, and pressure-sensitive adhesive film - Google Patents

Description

  The present invention relates to a pressure-sensitive adhesive having an antistatic function and a pressure-sensitive adhesive film.

Due to dramatic advances in electronics in recent years, various flat panel displays (FPD) such as liquid crystal displays (LCD), plasma displays (PDP), rear projection displays (RPJ), EL displays, light emitting diode displays, etc.
) Has been used as a display device in various fields. For example, these FPDs
In addition to being used indoors, including personal computer displays and liquid crystal televisions, they are used in vehicles such as car navigation displays.

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, a polarizing film or a retardation film is laminated.
Further, the FPD is not only used as a display device, but may be used as an input device by providing a touch panel function on the surface thereof. Touch panel, protective film,
Antireflection films, ITO vapor-deposited resin films, etc. are 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 sides of a polyethenol polarizer are sandwiched between triacetylcellulose-based or 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, in the inspection process of a laminate in which a polarizing film is attached to a glass surface for a liquid crystal cell, for example, in an LCD manufacturing process, there is air or dust entrainment during lamination,
A polarizing film etc. are peeled off and a new polarizing film etc. are 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 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 polyethenyl alcohol film in the polarizing film has a large dimensional change under high temperature or high temperature and high humidity conditions, for example, a laminate composed of a polarizing film / adhesive layer / glass can be used 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, that is, so-called white spots occur.

In general, a pressure-sensitive adhesive film has a release liner attached to the adhesive layer for the purpose of protecting the adhesive layer. In use, the release liner is peeled off and attached to an adherend. However, there has been a problem that the pressure-sensitive adhesive sheet is charged by static electricity when the release liner is peeled off, and dust and dirt are attached to cause appearance defects. Further, for example, in the LCD manufacturing process, rework is also performed as described above.
However, there are cases where troubles occur in liquid crystals and electronic circuits due to static electricity generated during rework. In addition, it has been pointed out that the same trouble occurs when the polarizing film is charged and attached to the glass surface for a liquid crystal cell due to static electricity generated when the release liner is peeled off as described above. Furthermore, the presence of static electricity has a problem of sucking dust and debris and causing defects due to foreign matters, and an early solution has been desired.

On the other hand, various pressure-sensitive adhesives have been proposed.
For example, in order to impart antistatic performance to the laminated members, the resin is often treated with an antistatic agent. Depending on how the antistatic agent is used, it is roughly divided into surface treatment and internal treatment.

The surface treatment is a treatment of the antistatic agent on the surface of the resin molded product using a technique such as coating, dipping or spraying. A typical example is a water-soluble surfactant, but it has a drawback that its antistatic ability decreases with time.

The internal treatment is a technique of adding an antistatic agent to the polymer during resin molding. Typical antistatic agents in this technique include conductive fine particles and surfactants.

Examples of the conductive fine particles include metal powder, metal oxide fine particles such as ITO and ATO, and carbon (Patent Documents 1 to 3). To impart antistatic ability using these materials, Significant amounts need to be added, and advanced techniques are needed to evenly distribute them. Further, due to the large amount of addition, the original physical properties are greatly affected, and transparency is lost.

Surfactants include anionic, cationic, and nonionic surfactants that are inexpensive and are used for various purposes (Patent Document 4). However, they also have the problem of causing bleeding from the surface of the adhesive layer and contaminating others. In addition, the anionic system lacks compatibility with the resin, uniform dispersion is difficult and heat resistance is low, the cationic system has no problem with antistatic properties, but the thermal stability is low. There were problems such as low compatibility with polymers.

As described above, the pressure-sensitive adhesive containing these surfactants is easily affected by humidity. Under high humidity and below, the cohesive force is reduced by the influence of moisture, and the adhesive layer tends to remain on the adherend. (So-called “glue residue” is likely to occur). Furthermore, these pressure-sensitive adhesives having surfactants and conductive fine particles have poor compatibility, and thus the transparency of the coating film is impaired or coloring is observed. Further, there is a problem that the surfactant or the conductive fine particles migrate to the adherend interface (so-called “bleed”) and the original performance of the pressure-sensitive adhesive such as adhesive force is lowered.

In addition, an antistatic pressure-sensitive adhesive containing an alkali metal salt as an antistatic agent in propenoic acid-based resin, which is used in electronic tape applications, protective film applications, and polarizing plate fixing applications, respectively, is disclosed. (Patent Documents 5 and 6). However, the use of antistatic pressure-sensitive adhesives containing metal ions in materials used in electrical products and electronic components has the potential for contamination associated with bleeding of metal ions, and further resistance to moisture and heat as an adhesive film Decreases.

Also known is a pressure sensitive adhesive comprising a propenoic acid pressure sensitive adhesive containing a propenoic acid resin and a crosslinking agent and a polyether polyol (Patent Document 7) or a polycaprolactone polyol (Patent Document 8). ing.

However, the pressure-sensitive adhesive film using the pressure-sensitive adhesive described in Patent Documents 7 and 8 is contained when it is exposed to a high temperature or a high temperature and high humidity condition for a long time after being attached to an adherend. The polyol that is present is easy to absorb moisture due to its high hydroxyl value, and extremely small bubbles are generated in a streak-like state at the peripheral edge of the optical film. 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 20 inches or more, the luminance of the light source must be set high from the viewpoint of easy viewing. In the pressure-sensitive adhesive optical film using the pressure-sensitive adhesive described in Patent Document 7, white spots were not regarded as a problem in a display device of less than 20 inches. However, there has also been a problem that white spots are conspicuous in a display device using a high-intensity light source used at 20 inches or more.

On the other hand, a pressure-sensitive adhesive obtained by copolymerizing a propenoic acid monomer to which an alkene oxide is added is known for improving the antistatic performance (Patent Documents 9 and 10).

However, when the pressure-sensitive adhesive described in Patent Documents 9 and 10 is produced, the radicals generated from the initiator used cause the ether bond to be decomposed and the polymerization is not stably performed. In order to prepare a copolymer, it is possible only with a very small introduction amount. Therefore, although providing an auxiliary effect of the antistatic function when providing a general pressure-sensitive adhesive, the pressure-sensitive adhesive optical film using the pressure-sensitive adhesive described in Patent Documents 9 and 10 is attached. After sticking to the body, if it is exposed to a heat cycle from low to high temperature under high temperature or high temperature and high humidity conditions for a long time, the oxyacid oligomer produced by decomposition during polymerization is also converted into polyether polyol. As in the case of blending (Patent Document 7), extremely small bubbles are generated in a streak-like state at the peripheral edge of the optical film.
Furthermore, the antistatic effect cannot be obtained only by copolymerizing a propenoic acid monomer to which an alkene oxide is added.

In view of such a situation, the pressure-sensitive adhesive physical properties and optical properties due to the presence of a permanent antistatic effect are suppressed, and it can be used for everything from film labels to electrical and optical applications. A pressure sensitive adhesive was desired.
Furthermore, pressure-sensitive adhesives that have not only antistatic ability but also transparency, solubility in resins and solvents (compatibility), and wet heat resistance have been desired.

Japanese Unexamined Patent Publication No. 01-222141 Japanese Patent Laid-Open No. 05-070760 JP 2005-330409 A JP 04-007350 A Japanese National Patent Publication No. 10-511726 JP 2006-199873 A Japanese Patent Laid-Open No. 06-128539 JP 2002-053835 A JP-A-11-185524 JP-A-12-008013

An object of the present invention is to provide a pressure-sensitive adhesive used for a pressure-sensitive adhesive film having an antistatic function and further having good reworkability, transparency, and heat-and-moisture resistance.

The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems.
That is, the first invention is a copolymer (B) having a side chain (I) having an active hydrogen group at the terminal,
A pressure-sensitive adhesive comprising a reactive compound (C),
The pressure-sensitive adhesive is characterized in that the side chain (I) is formed by a ring-opening reaction between an active hydrogen group of the copolymer (A) and a cyclic amide compound (D).

In the second invention, the copolymer (A) contains an active hydrogen group-containing α, β-unsaturated monomer (a-
The pressure-sensitive adhesive according to the invention is a copolymer of a monomer containing 1).

The third invention relates to the pressure-sensitive adhesive according to any one of the above inventions, wherein the cyclic amide compound (D) is a compound having a heterocyclic ring having 3 to 18 carbon atoms.

The fourth invention relates to the pressure-sensitive adhesive according to any one of the above inventions, wherein the cyclic amide compound (D) is a lactam (d).

The fifth invention is characterized in that the active hydrogen group-containing α, β-unsaturated monomer (a-1) has at least a carboxyl group or an amino group as the active hydrogen group. The present invention relates to the pressure-sensitive adhesive of the invention.

The sixth invention relates to the pressure-sensitive adhesive according to any one of the above inventions, wherein the copolymer (B) has an amine value of 0.1 to 50 mgKOH / g.

The seventh invention relates to the pressure-sensitive adhesive according to the first to sixth inventions, wherein the copolymer (B) has an acid value of 0.1 to 50 mgKOH / g.

In the eighth invention, the copolymer (B) contains an active hydrogen group at the end of the side chain (I) and a sealing compound (
It has a side chain (II) obtained by reacting E), and relates to the pressure-sensitive adhesive according to the sixth invention.

The ninth invention is characterized in that the copolymer (B) has a side chain (II) formed by reacting an active hydrogen group at the terminal of the side chain (I) with a sealing compound (E). The present invention relates to the pressure-sensitive adhesive of the seventh invention.

In the tenth invention, the sealing compound (E) comprises an acid anhydride group-containing compound (e-1), a glycidyl group-containing compound (e-2), an isocyanate group-containing compound (e-3), and an amino group. The pressure-sensitive adhesive according to the eighth invention, wherein the pressure-sensitive adhesive is one or more compounds selected from the group consisting of the containing compound (e-4).

In the eleventh invention, the sealing compound (E) comprises an acid anhydride group-containing compound (e-1), a glycidyl group-containing compound (e-2), an isocyanate group-containing compound (e-3), and an amino group. The pressure-sensitive adhesive according to the ninth aspect of the invention is characterized by comprising the compound (e-4).

The twelfth invention relates to an α, β-unsaturated monomer (a-1) containing an active hydrogen group and α, β-
Copolymerizing the unsaturated monomer (a-2) to obtain a copolymer (A), and
The side chain (I) is obtained by reacting the active hydrogen group in the copolymer (A) with the cyclic amide compound (D).
It is related with the manufacturing method of resin for pressure sensitive adhesives characterized by including the process of producing | generating and obtaining a copolymer (B).

In the thirteenth invention, the end of the side chain (I) is reacted with the sealing compound (E) to produce a side chain (I
The method for producing a resin for a pressure-sensitive adhesive according to the twelfth aspect of the invention, comprising the step of producing I) to obtain a copolymer (B-2).

The fourteenth invention also relates to a pressure-sensitive adhesive comprising the pressure-sensitive adhesive resin obtained by the twelfth or thirteenth invention, and a reactive compound (C).

The fifteenth invention relates to a pressure-sensitive adhesive film formed by forming an adhesive layer made of the pressure-sensitive adhesive of any of the first to eleventh or fourteenth inventions on the base material (F).

The sixteenth invention relates to a laminate in which an adhesive layer made of the pressure-sensitive adhesive of any of the first to eleventh or fourteenth inventions is formed on an optical member.

The seventeenth invention relates to a laminated body in which an optical member, an adhesive layer made of the pressure-sensitive adhesive of any of the first to eleventh or fourteenth inventions, and glass are sequentially laminated.

The pressure-sensitive adhesive of the present invention has an excellent antistatic function, and also has good reworkability, transparency, and wet heat resistance. Therefore, a pressure-sensitive adhesive and a pressure-sensitive adhesive film having the above characteristics can be provided.

The matters necessary for carrying out the present invention are specifically described below.
The pressure-sensitive adhesive of the present invention exhibits permanent antistatic performance without using an antistatic agent. Therefore, the heat resistance and heat-and-moisture resistance under conditions severer than before can be improved, and for example, it can be preferably used for an optical member.
The pressure-sensitive adhesive of the present invention is a copolymer (B) having a side chain (I) having an active hydrogen group at the terminal.
And a reactive compound (C), wherein the side chain (I) is an active hydrogen group of the copolymer (A),
It is formed by a ring-opening reaction with the cyclic amide compound (D).
The pressure-sensitive adhesive having the above structure has many amide bonds in the side chain (I) of the copolymer (B).
A large number of loan pairs derived from amide bonds appear to be pendant to the copolymer. Therefore, for example, when the pressure-sensitive adhesive is used for laminating a polarizing plate in an LCD manufacturing process, the side chain (I) loan pair is oriented near the glass interface of the liquid crystal cell. Shortened and a conductive path is formed. On this conductive path, ionic dissociation occurs due to moisture in the air and the catalyst used when synthesizing the copolymer (B), and the dissociated ions move through the conductive path, so that ionic conduction is easily developed. It is estimated that the pressure-sensitive adhesive can be provided with an antistatic function.

The copolymer (A) used in the present invention contains an active hydrogen group-containing α, β-unsaturated monomer (a-1
) [Hereinafter simply referred to as monomer (a-1)] and α, β-unsaturated monomer (a-2) other than monomer (a-1) [hereinafter simply referred to as monomer ( a-2)]]. Then, the active hydrogen group of the copolymer (A) reacts with the cyclic amide compound (D) to obtain the copolymer (B).

The active hydrogen group of the active hydrogen group-containing α, β-unsaturated monomer (a-1) is preferably a hydroxyl group, a carboxyl group, a sulfonyl group, a phosphonyl group, an amino group, an amide group, a maleimide group, and the like. It is preferable to contain at least one of a group and a carboxyl group. Examples of the monomer (a-1) include compounds having an active hydrogen group among propenoic acid, 2-methylpropenoic acid, propenoic acid derivatives, 2-methylpropenoic acid derivatives, and other alkenyl group-containing compounds. Can do.

It is preferable that 0.01 to 20% by weight of the active hydrogen group-containing α, β-unsaturated monomer (a-1) is contained in 100% by weight of the monomer used for copolymerization of the copolymer (A). Although it can be used outside the above numerical range, it may be difficult to solve the problems of the present invention such as antistatic properties, transparency, and heat and humidity resistance.

The copolymer (A) preferably has a glass transition point (Tg) of −80 to 10 ° C. so that well-balanced adhesive properties (particularly, compatibility between tack and cohesive force) can be obtained, and −60 ~
0 ° C. is more preferable. When the glass transition point is lower than −80 ° C., when used as a pressure-sensitive adhesive tape, the cohesive force of the adhesive layer is lowered, and the floating peeling tends to occur. On the other hand, when the glass transition point exceeds 10 ° C., it is difficult to obtain an adhesive layer having sufficient tack. The copolymer (A
If the Tg of the homopolymer that can be formed from each monomer that is a constituent component of () is known, the Tg of the copolymer (A) is determined based on the Tg of each homopolymer and the constituent ratio of each monomer. Can be obtained theoretically.

The weight average molecular weight (Mw) of the copolymer (A) is 50,000 to 2,000,000.
It is preferable that it is 200,000-1,500,000. Mw is 2
If it exceeds 1,000,000, the fluidity of the copolymer (A) is lowered, and the coating property of the pressure-sensitive adhesive may be deteriorated. On the other hand, when Mw is less than 50,000, the cohesive force of the adhesive layer may be insufficient.

Among the monomer (a-1) or monomer (a-2), as propenoic acid derivative or 2-methylpropenoic acid derivative,
For example, methyl (2-methyl) propenoate [methyl propenoate and methyl 2-methylpropenoate are collectively referred to as “methyl (2-methyl) propenoate”. The same applies hereinafter. ], (2
-Methyl) ethyl propenoate, (2-methyl) propenoate 1-propyl, (2-methyl)
2-propyl propenoate, n-butyl (2-methyl) propenoate, sec-butyl (2-methyl) propenoate, iso-butyl (2-methyl) propenoate, tert-butyl (2-methyl) propenoate, (2-methyl) propenoate n-amyl, (2-methyl) propenoate iso-amyl, (2-methyl) propenoate n-hexyl, (2-methyl) propenoate 2-ethylhexyl, (2-methyl) propene N-octyl acid, iso-octyl (2-methyl) propenoate, n-nonyl (2-methyl) propenoate, iso-nonyl (2-methyl) propenoate, (2-methyl) decylpropenoate, (2- Methyl) dodecyl propenoate, octadecyl (2-methyl) propenoate, lauryl (2-methyl) propenoate, (2-
(2-methyl) propenoic acid alkyl esters such as stearyl (methyl) propenoate;

For example, cyclohexyl (2-methyl) propenoate, benzyl (2-methyl) propenoate, iso-bonyl (2-methyl) propenoate, phenyl (2-methyl) propenoate, (
2-Methyl) propenoic acid 2-phenoxyethyl, (2-methyl) propenoic acid 2-oxo-1
, 2-phenylethyl, (2-methyl) propenoic acid cyclic esters such as 2-oxo-1,2-diphenylethyl;

For example, allyl (2-methyl) propenoate, 1-methylallyl (2-methyl) propenoate, 2-methylallyl (2-methyl) propenoate, 1-butenyl (2-methyl) propenoate, (2-methyl) propene 2-butenyl acid, 3-butenyl (2-methyl) propenoate,
(2-Methyl) propenoic acid 1,3-methyl-3-butenyl, (2-methyl) propenoic acid 2
-Chloroallyl, 3-chloroallyl (2-methyl) propenoate, (2-methyl) propenoic acid-o-allylphenyl, 2- (allyloxy) ethyl (2-methyl) propenoate, (2
-Methyl) allyl lactyl propenoate, citronellyl (2-methyl) propenoate, (2-
It further contains an unsaturated group such as geranyl (methyl) propenoate, rosinyl (2-methyl) propenoate, cinnamyl (2-methyl) propenoate, ethenyl (2-methyl) propenoate (
2-methyl) propenoic acid esters;

For example, (2-methyl) propenoic acid perfluoromethyl, (2-methyl) propenoic acid perfluoroethyl, (2-methyl) propenoic acid perfluoropropyl, (2-methyl) propenoic acid perfluorobutyl, (2-methyl) ) Perfluorooctyl propenoate, (2-
Methyl) trifluoromethyl methyl propenoate, (2-methyl) propenoic acid 2-trifluoromethyl ethyl, (2-methyl) propenoic acid diperfluoromethyl methyl, (2-methyl) acrylic acid 2-perfluoroethyl ethyl, (2-methyl) propenoic acid 2-perfluoromethyl-2-perfluoroethylmethyl, (2-methyl) propenoic acid triperfluoromethylmethyl, (2-methyl) propenoic acid 2-perfluoroethyl-2-perfluoro Butylethyl, 2-perfluorohexylethyl (2-methyl) propenoate, 2-perfluorodecylethyl (2-methyl) propenoate, 2-perfluorohexadecylethyl (2-methyl) propenoate, (2-methyl ) Propenoic acid-2,6-dibromo-4-butylphenyl, (2-methyl) pro Phosphate-2,4,6 tribromophenoxyethyl, (2-
Halogen-containing (2-methyl) propenoic acid alkyl esters such as (methyl) propenoic acid-2,4,6-tribromophenolethene oxide adduct (ethene oxide addition moles: 4 to 12);

For example, 2-hydroxyethyl (2-methyl) propenoate, 1-hydroxypropyl (2-methyl) propenoate, 2-hydroxypropyl (2-methyl) propenoate, 2-methoxyethyl (2-methyl) propenoate, (2-methyl) propenoic acid 2-ethoxyethyl,
Hydroxyl groups or (2-methyl) propenoic acid esters such as 2-hydroxybutyl (2-methyl) propenoate and 4-hydroxybutyl (2-methyl) propenoate;

For example, (2-methyl) propenoic acid glycidyl, (2-methyl) propenoic acid (3,4-
(2-Methyl) propenoic acid esters containing oxygen atoms such as epoxycyclohexyl) methyl, (2-methyl) propenoic acid (3-methyl-3-oxetanyl) methyl, (2-methyl) propenoic acid tetrahydrofurfuryl, etc. ;

For example, 3- (2-methylpropane-2-enoyloxypropyl) trimethoxysilane, 3- (2-methylpropane-2-enoyloxypropyl) triethoxysilane, 3
-(2-methylpropane-2-enoyloxypropyl) triisopropoxysilane, 3
-(2-methylpropane-2-enoyloxypropyl) methyldimethoxysilane, 3-
(2-methylpropane-2-enoyloxypropyl) methyldiethoxysilane, 3- (
(2-methyl) propenoic acid esters containing alkoxysilyl groups such as propan-2-enoyloxypropyl) trimethoxysilane;

For example, N-methylaminoethyl (2-methyl) propenoate, N-tributylaminoethyl (2-methyl) propenoate, N, N-dimethylaminoethyl (2-methyl) propenoate, (2-methyl) propenoic acid N, N-diethylaminoethyl, (2-methyl) propenoic imide, (2-methyl) propenoic acid morpholinoethyl, (2-methyl) propenoic acid pentamethylpiperidinyl, (2-methyl) propenoic acid tetramethylpiperidin Nitrogen-containing (2-methyl) propenoates such as amino groups such as nyl;

For example, 2- [2′-hydroxy-5 ′-(2-methyl) propane-2-enoyloxyethylphenyl] -2H-benzotriazole, 2- [2′-hydroxy-5 ′-(2-methyl) Propane-2-enoyloxyethylphenyl] -5-chloro-2H-benzotriazole, 2- [2'-hydroxy-5 '-(2-methyl) propan-2-enoyloxypropylphenyl] -2H-benzo Triazole, 2- [2′-hydroxy-5 ′-(2-methyl) propane-2-enoyloxypropylphenyl] -5-chloro-2H-benzotriazole, 2- [2′-hydroxy-3′-tert -Butyl-5 '-(2-methyl) propane-2-enoyloxyethylphenyl] -2H-benzotriazole, (2-methyl)
Propenoic acid-3- (2H-1,23-benzotriazol-2-yl) -4-hydroxyphenethyl, 2- (2'-hydroxy-3'-tert-butyl-5 '-(2-methyl) propane- Benzotriazole-based (2-methyl) propenoic acid derivatives such as 2-enoyloxyethylphenyl) -5-chloro-2H-benzotriazole;

For example, 2-hydroxy-4- [2- (2-methyl) propane-2-enoyloxy] ethoxydiphenylmethanone, 2-hydroxy-4- [2-((2-methyl) propane-2
-Enoyloxy) butoxydiphenylmethanone, 2,2'-dihydroxy-4- [2- (
2-Methyl) propane-2-enoyloxy] ethoxydiphenylmethanone, 2-hydroxy-4- [2- (2-methyl) propane-2-enoyloxy] ethoxy-4 ′-(2-
Diphenylmethanone-based (2-methyl) propenoic acid derivatives such as hydroxyethoxy) diphenylmethanone;

For example, 2,4-diphenyl-6- [2-hydroxy-4- (2- (2-methyl) propane-2-enoyloxyethoxy)]-S-triazine, 2,4-bis (2-methylphenyl) ) -6- [2-hydroxy-4- (2- (2-methyl) propane-2-enoyloxyethoxy)]-S-triazine, 2,4-bis (2-methoxyphenyl) -6- [ 2-Hydroxy-4- (2- (2-methyl) propane-2-enoyloxyethoxy)]-S-
Triazine, 2,4-bis (2-ethylphenyl) -6- [2-hydroxy-4- (2- (
2-methyl) propane-2-enoyloxyethoxy)]-S-triazine, 2,4-bis (2-ethoxyphenyl) -6- [2-hydroxy-4- (2- (2-methyl) propane- 2-Enoyloxyethoxy)]-S-triazine, 2,4-bis (2,4-dimethoxyphenyl) -6- [2-hydroxy-4- (2- (2-methyl) propan-2-enoyl Oxyethoxy)]-S-triazine, 2,4-bis (2,4-dimethylphenyl) -6- [
2-hydroxy-4- (2- (2-methyl) propane-2-enoyloxyethoxy)]
-S-triazine, 2,4-bis (2,4-diethoxylphenyl) -6- [2-hydroxy-4- (2- (2-methyl) propane-2-enoyloxyethoxy)]-S- Triazine, 2,4-bis (2,4-diethylphenyl) -6- [2-hydroxy-4- (2- (
(2-methyl) propan-2-enoyloxyethoxy)]-S-triazine, 2,4-diamino-6-methacryloyloxyethyl-s-triazine and other triazine-based (2-methyl) propenoic acid derivatives;

For example, alkene oxide-containing (2-methyl) propenoic acid derivatives such as an oxirane adduct of (2-methyl) propenoic acid;

For example, (2-methyl) propenoic acid phosphooxyethyl, (2-methyl) propenoic acid phosphooxypropyl, (2-methyl) propenoic acid phosphooxybutyl, (2-methyl) propenoic acid-3-chloro- 2-acid phosphooxyethyl, 2
-Methyl) propenoic acid-3-chloro-2-acid phosphooxypropyl, 2-methyl)
Propenoic acid-3-chloro-2-acid phosphooxybutyl, (2-methyl) propenoic acid phosphooxyethene oxide (ethene oxide addition moles: 4 to 10), (
(2-Methyl) propenoic acid acid phosphooxypropene oxide (propene oxide addition mole number: 4 to 10) and other (2-methyl) propenoic acid esters containing a phosphonyl group;

For example, (2-methyl) propenoic acid sulfomethyl, (2-methyl) propenoic acid 2-sulfoethyl, (2-methyl) propenoic acid 2-sulfopropyl, (2-methyl) propenoic acid 3
-Sulfopropyl, 2-sulfobutyl (2-methyl) propenoate, 4-sulfobutyl (2-methyl) propenoate, 2-sulfobutyl (2-methyl) propenoate, 6-sulfohexyl (2-methyl) propenoate, 2-methyl) sulfooctyl propenoate, sulfodecyl (2-methyl) propenoate, sulfolauryl (2-methyl) propenoate, (2-methyl)
Sulfonyl group-containing (2-methyl) propenoic acid alkyl esters such as propenoic acid sulfostearyl, (2-methyl) propenoic acid sulfophenoxyethyl, (2-methyl) propenoic acid sulfocyclohexyl-containing (2- Methyl) propenoic acid cyclic esters;

Further, metal salts and ammonium salts of the sulfonyl group-containing (2-methyl) propenoic acid alkyl esters, (2-methyl) propenoyloxydimethylethylammonium ethyl sulfate, (2-methyl) propenoylaminopropyltrimethylammonium Metal salts and ammonium salts of sulfonyl group-containing (2-methyl) propenoic acid alkyl esters such as sulfate and (2-methyl) propenoylaminopropyltriethylammonium sulfate, and sulfonyl group-containing (2-methyl) propenoic acid cyclic esters Metal salts and ammonium salts, (2-methyl) propenoic acid sulfobenzyl, (2-methyl) propenoyloxyethyldimethylbenzylammonium p-toluenesulfonate, (2
Metal salts of (2-methyl) propenoic acid cyclic esters containing a sulfonyl group such as -methyl) propenoyloxyethyltrimethylammonium-p-toluenesulfonate and (2-methyl) propenoylaminopropyltrimethylammonium-p-toluenesulfonate And ammonium salts;

For example, as a bifunctional monomer, di (2-methyl) propenoic acid ethene oxide, di (
2-methyl) propenoic acid triethene oxide, di (2-methyl) propenoic acid tetraethene oxide, di (2-methyl) propenoic acid polyethene oxide, di (2-methyl) propenoic acid propene oxide, di (2-methyl) ) Dipropene oxide propenoate, di (
2-Methyl) propenoic acid tripropene oxide, di (2-methyl) propenoic acid polypropene oxide, di (2-methyl) propenoic acid butene oxide, di (2-methyl) propenoic acid pentane oxide, di (2-methyl) 2,2-dimethylpropyl propenoate, di (2-methyl) propenoic acid hydroxypivalyl hydroxypivalate (common name: Manda), di (2-methyl) propenoic acid hydroxypivalyl hydroxypivalate dicaprolactonate, di (2 -Methyl) propenoic acid 1,6-hexanediol, di (2-methyl) propenoic acid 1,2-hexanediol, di (2-methyl) propenoic acid 1,5-hexanedioldi, di (2-methyl) propene Acid 2,5-hexanediol, di (2-methyl) propenoic acid 1,7-heptanediol, (2-methyl) propenoic acid 1,8-octanediol, di (2-methyl) propenoic acid 1,2-octanediol, di (2-methyl) propenoic acid 1,
9-nonanediol di, di (2-methyl) propenoic acid 1,2-decanediol, di (2-
Methyl) propenoic acid 1,10-decanediol, di (2-methyl) propenoic acid 1,2-decanediol, di (2-methyl) propenoic acid 1,12-dodecanediol, di (2-methyl) propenoic acid 1 , 2-dodecanediol, di (2-methyl) propenoic acid 1,14-tetradecanediol, di (2-methyl) propenoic acid 1,2-tetradecanediol, di (2
-Methyl) propenoic acid 1,16-hexadecanediol, di (2-methyl) propenoic acid 1
, 2-hexadecanediol, di (2-methyl) propenoate 2-methyl-2,4-pentanediol, di (2-methyl) propenoate 3-methyl-1,5-pentanediol, di (
2-methyl) propenoic acid 2-methyl-2-propyl-1,3-propanediol, di (2
-Methyl) propenoic acid 2,4-dimethyl-2,4-pentanediol, di (2-methyl)
2,2-diethyl-1,3-propanediol of propenoic acid, 2,2,4-trimethyl-1,3-pentanediol of di (2-methyl) propenoic acid, dimethylol di (2-methyl) propenoate Octane, 2-ethyl-1,3-hexanediol di (2-methyl) propenoate,
Di (2-methyl) propenoic acid 2,5-dimethyl-2,5-hexanediol, di (2-methyl) propenoic acid 2-methyl-1,8-octanediol, di (2-methyl) propenoic acid 2- Butyl-2-ethyl-1,3-propanediol, di (2-methyl) propenoic acid 2,
4-diethyl-1,5-pentanediol, di (2-methyl) propenoic acid 1,2-hexanediol, di (2-methyl) propenoic acid 1,5-hexanediol, di (2-methyl)
2,5-hexanediol propenoate, 1,7-heptanediol di (2-methyl) propenoate, 1,8-octanediol di (2-methyl) propenoate, di (2-methyl) propenoate 1,2 -Octanediol, di (2-methyl) propenoic acid 1,9-nonanediol, di (2-methyl) propenoic acid 1,2-decanediol, di (2-methyl) propenoic acid 1
, 10-decanediol, di (2-methyl) propenoic acid 1,2-decanediol, di (2
-Methyl) propenoic acid 1,12-dodecanediol, di (2-methyl) propenoic acid 1,2
-Dodecanediol, di (2-methyl) propenoic acid 1,14-tetradecanediol, di (2-methyl) propenoic acid 1,2-tetradecanediol, di (2-methyl) propenoic acid 1,16-hexadecanediol, di (2-methyl) propenoic acid 1,2-hexadecanediol, di (2-methyl) propenoic acid 2-methyl-2,4-pentane, di (2-methyl) propenoic acid 3-methyl-1,5-pentane Diol, di (2-methyl) propenoic acid 2-
Methyl-2-propyl-1,3-propanediol, di (2-methyl) propenoic acid 2,4
-Dimethyl-2,4-pentanediol, 2,2-diethyl-1,3-propanediol di (2-methyl) propenoate, 2,2,4-trimethyl-1 di (2-methyl) propenoate
, 3-pentanediol, dimethyloloctane di (2-methyl) propenoate, di (2-
Methyl) propenoate 2-ethyl-1,3-hexanediol, di (2-methyl) propenoate 2,5-dimethyl-2,5-hexanediol, di (2-methyl) propenoate 2-butyl-2- Ethyl-1,3-propanediol, di (2-methyl) propenoic acid 2,4-diethyl-1,5-pentanediol, di (2-methyl) propenoic acid 1,1,1-trishydroxymethylethane, di (2-Methyl) propenoic acid tricyclodecane dimethylol, di (
2-methyl) propenoic acid tricyclodecane dimethylol dicaprolactonate, di (2-
Methyl) -2,2-bis (hydroxyphenyl) propane tetraethene oxide adduct, di (2-methyl) propenoic acid 2,2-bis (hydroxyphenyl) methane tetraethene oxide adduct, di (2-methyl) ) Tetraethene oxide adduct of propenoic acid-4,4′-sulfonyldiphenol, di (2-methyl) propenoic acid-water-added 2,2-bis (
Hydroxyphenyl) propane tetraethene oxide adduct, di (2-methyl) propenoic acid-water addition 2,2-bis (hydroxyphenyl) methane tetraethene oxide adduct, di (2-methyl) propenoic acid-water addition 2,2-bis (hydroxyphenyl) propane,
Di (2-methyl) propenoic acid-water-added 2,2-bis (hydroxyphenyl) methane, di (2
-Methyl) propenoic acid-2,2-bis (hydroxyphenyl) propane tetraethylene oxide adduct-dicaprolactonate, di (2-methyl) propenoic acid-2,2-bis (
(2-methyl) propenoic acid-based bifunctional derivatives such as hydroxyphenyl) methane tetraethene oxide adduct-dicaprolactonate;

Tri (2-methyl) propenoic acid glycerin and tri (2-methyl) as trifunctional monomers
Trimethylolpropane propenoate, trimethylolpropane tri (2-methyl) propenoate tricaprolactonate, trimethylolethane tri (2-methyl) propenoate, trimethylolhexane tri (2-methyl) propenoate, tri (2- Methyl) propenoic acid trimethyloloctane, tri (2-methyl) propenoic acid pentaerythritol, tri (2
-Methyl) propenoic acid 1,1,1-trishydroxymethylethane, tri (2-methyl)
Trifunctional (2-methyl) propenoic acid esters such as propenoic acid 1,1,1-trishydroxymethylpropane;

Tetra (2-methyl) propenoic acid pentaerythritol as a tetrafunctional or higher monomer
Tetra (2-methyl) propenoic acid pentaerythritol tetracaprolactonate, tetra (2-methyl) propenoic acid diglycerin, tetra (2-methyl) propenoic acid ditrimethylolpropane, tetra (2-methyl) propenoic acid ditrimethylolpropane Tetracaprolactonate, tetra (2-methyl) propenoic acid ditrimethylolethane, tetra (2
-Methyl) propenoic acid ditrimethylolbutane, tetra (2-methyl) propenoic acid ditrimethylolhexane, tetra (2-methyl) propenoic acid ditrimethyloloctane, tetra (2-methyl) propenoic acid dipentaerythritol, hexa (2-methyl) ) Dipentaerythritol propenoate, tripentaerythritol hexa (2-methyl) propenoate,
Polyfunctional (2-methyl) propenoic acid ester such as hepta (2-methyl) propenoic acid tripentaerythritol, octa (2-methyl) propenoic acid tripentaerythritol, hepta (2-methyl) propenoic acid dipentaerythritol polyalkene oxide Kind;

For example, di (2-methyl) propenoic acid ethane 1,2-diol, di (2-methyl) propenoic acid, 2,2′-oxyethane-1-ol, di (2-methyl) propenoic acid 3,6-di Oxaoctane-1,8-diol, di (2-methyl) propenoic acid 3,6,9-trioxaundecane-1,11-diol, di (2-methyl) propenoic acid 3,6,9,12-tetra Oxatetradecane-1,14-diol, 2-ethyl-2- (hydroxymethyl) propane-1,3-diol tri (2-methyl) propenoate, 2,2-bis (hydroxy) tri (2-methyl) propenoate Methyl) propane-1,3-diol, di (2-methyl)
1,1,1-trishydroxymethylethane propenoic acid, 1,1,1-trishydroxymethylethane tri (2-methyl) propenoic acid, 1,1,1 tri (2-methyl) propenoic acid
-Polyfunctional (2-methyl) propenoates such as trishydroxymethylpropane.

Examples of the alkenyl group-containing compound include ethenylbenzene, α-isopropenylbenzene, β-isopropenylbenzene, 1-methylethenylbenzene, 2-methylethenylbenzene, 3-methylethenylbenzene, 1-butylethenyl. Tenylbenzene, 1-chloro-
Aromatic ethenyl monomers such as 4-isopropenylbenzene;

For example, ethenyl phenyl pentyl ether, ethenyl phenyl hexyl ether, ethenyl phenyl heptyl ether, ethenyl phenyl octyl ether, ethenyl phenyl nonyl ether, ethenyl phenyl decyl ether, ethenyl phenyl undecyl ether, ethenyl phenyl dodecyl ether Ethenyl phenyl tridecyl ether, ethenyl phenyl tetradecyl ether, ethenyl phenyl pentadecyl ether, ethenyl phenyl hexadecyl ether, ethenyl phenyl heptadecyl ether, ethenyl phenyl octadecyl ether, ethenyl phenyl nonadecyl ether, Tenenylphenyl eicosyl ether, ethenylphenyl henecosyl ether, ethenylphenyl docosyl ether, ethenylphenyl Butyl butyl ether, ethenyl phenyl methyl pentyl ether, ethenyl phenyl methyl hexyl ether, ethenyl phenyl methyl heptyl ether, ethenyl phenyl methyl octyl ether, ethenyl phenyl methyl nonyl ether, ethenyl phenyl methyl decyl ether, ethenyl phenyl methyl ether Decyl ether, ethenyl phenyl methyl dodecyl ether, ethenyl phenyl methyl tridecyl ether, ethenyl phenyl methyl tetradecyl ether, ethenyl phenyl methyl pentadecyl ether, ethenyl phenyl methyl hexadecyl ether, ethenyl phenyl methyl heptadecyl ether, Ethenyl phenyl methyl octadecyl ether, ethenyl phenyl methyl nonadecyl ether, ethenyl phenyl methyl Lee waist ether, ethenyl phenylmethyl hen eicosyl ether, aromatic ethenyl ether monomer having a long-chain alkyl groups such as ethenyl phenylmethyl docosyl 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 phenylmethyl nonyl ether, isopropenyl phenyl methyl decyl ether, isopropenyl phenyl methyl undecyl ether, isopropenyl phenyl methyl dodecyl ether, isopropenyl phenyl methyl tridecyl ether, isopropenyl phenyl methyl tetradecyl ether, isopropenyl phenyl methyl penta Decyl ether, isopropenyl phenylmethyl hexadecyl ether, isopropenyl phenyl methyl heptadecyl ether, isopropenyl phenyl methyl octadecyl ether,
Isopropenyl phenyl monomers having a long chain alkyl group such as isopropenyl phenylmethyl nonadecyl ether, isopropenyl phenyl methyl eicosyl ether, isopropenyl phenyl methyl heneicosyl ether, isopropenyl phenyl methyl docosyl ether;

Hexyl 4-ethenylbenzenecarboxylate, octyl 4-ethenylbenzenecarboxylate, nonyl 4-ethenylbenzenecarboxylate, decyl 4-ethenylbenzenecarboxylate, 4
-Ethenylbenzenecarboxylate dodecyl, 4-ethenylbenzenecarboxylate tetradecyl, 4-ethenylbenzenecarboxylate hexadecyl, 4-ethenylbenzenecarboxylate octadecyl, 4-ethenylbenzenecarboxylate eicosyl, 4-ethenylbenzenecarboxylate Docosyl acid, hexyl 4-isopropenylbenzenecarboxylate, octyl 4-isopropenylbenzenecarboxylate, nonyl 4-isopropenylbenzenecarboxylate, decyl 4-isopropenylbenzenecarboxylate, dodecyl 4-isopropenylbenzenecarboxylate, 4
Long chain alkyl groups such as tetradecyl isopropenylbenzenecarboxylate, hexadecyl 4-isopropenylbenzenecarboxylate, octadecyl 4-isopropenylbenzenecarboxylate, eicosyl 4-isopropenylbenzenecarboxylate, docosyl 4-isopropenylbenzenecarboxylate, etc. Having an ethenylbenzenecarboxylic acid ester-based monomer or an isopropenylbenzenecarboxylic acid ester-based monomer;

For example, tetra (ethene oxide) ethenyl phenyl ether, methyl tetra (ethene oxide) ethenyl phenyl ether, ethyl tetra (ethene oxide) ethenyl phenyl ether, propyl tetra (ethene oxide) ethenyl phenyl ether, n
-Butyltetra (ethene oxide) ethenylphenyl ether, n-pentyltetra (
Ethene oxide) ethenyl phenyl ether, tetra (propene oxide) ethenyl phenyl ether, methyl tetra (propene oxide) ethenyl phenyl ether, ethyl tetra (propene oxide) ethenyl phenyl ether, propoxy tetra (propene oxide) ethenyl phenyl ether, n-Butyltetra (propene oxide)
Ethenyl phenyl ether, n-pentoxytetra (propene oxide) ethenyl phenyl ether, poly (ethene oxide) ethenyl phenyl ether, methyl poly (ethene oxide) ethenyl phenyl ether, ethyl poly (ethene oxide) ethenyl phenyl ether, poly (Propene oxide) ethenyl phenyl ether, methyl poly (
Propene oxide) ethenyl phenyl ether, ethyl poly (propene oxide) ethenyl phenyl ether, poly (ethene oxide) ethenyl benzyl ether, methyl poly (ethene oxide) ethenyl benzyl ether, ethyl poly (ethene oxide)
Ethenyl benzyl ether, poly (propene oxide) ethenyl benzyl ether, methyl poly (propene oxide) ethenyl benzyl ether, ethyl poly (propene oxide) ethenyl benzyl ether, poly (ethene oxide) ethenyl phenyl ethyl ether, methyl poly (ethene oxide) ) Ethenyl phenyl ethyl ether, ethyl poly (ethene oxide) ethenyl phenyl ethyl ether, poly (oxypropylene)
An ethenylbenzene monomer having a long-chain polyalkene oxide moiety such as vinylphenyl ethyl ether, methyl poly (propene oxide) ethenyl phenyl ethyl ether, ethyl poly (propene oxide) ethenyl phenyl ethyl ether;

For example, poly (ethene oxide) isopropenyl phenyl ether, methyl poly (ethene oxide) isopropenyl phenyl ether, ethyl poly (ethene oxide) isopropenyl phenyl ether, poly (propene oxide) isopropenyl phenyl ether, methyl poly (propene oxide) isopropenyl phenyl Ether, ethyl poly (propene oxide) isopropenyl phenyl ether, poly (ethene oxide)
Polyalkene oxide moieties such as isopropenyl benzyl ether, methyl poly (ethene oxide) isopropenyl benzyl ether, ethyl poly (ethene oxide) isopropenyl benzyl ether, poly (propene oxide) isopropenyl benzyl ether, methyl poly (propene oxide) isopropenyl benzyl ether Isopropenyl monomers having

For example, mono long chain alkyl ester of dicarboxylic acid such as ethenylphenylnonyl butanedioate, ethenylphenylmethyldecyl hexahydrobenzene-1,2-dicarboxylate, ethenylphenylethyldodecyl benzene-1,4-dicarboxylate Monomer;

For example, butanedioic acid ethenyl phenyl poly (ethene oxide), hexahydrobenzene-1,2-dicarboxylic acid ethenyl phenyl methyl poly (ethene oxide), benzene-1,4-dicarboxylic acid ethenyl phenyl ethyl poly (ethene oxide) ) Monocarboxylic acid esters of dicarboxylic acids such as 4-ethenylbenzenecarboxylate methyl poly (ethene oxide), 4-ethenylbenzenecarboxylate ethyl poly (ethene oxide), 4-isopropenylbenzenecarboxylate methyl poly (propene oxide), 4
An ethenyl benzene carboxylic acid ester-based or isopropenyl benzene carboxylic acid ester-based monomer having a polyalkene oxide moiety such as ethyl isopropenyl benzene carboxylate poly (propene oxide);

For example, fluorine-containing ethenyl monomers such as perfluoroethene, perfluoropropene, perfluoro (propyl ethenyl ether), ethenylidene fluoride;

For example, triethyloxysilyl group-containing ethenyl monomers such as ethenyltrimethoxysilane and ethenyltriethoxysilane;

For example, ethenyl ethanoate, ethenyl propanoate, ethenyl pivalate, ethenyl benzenecarboxylate, ethenyl 3-phenyl-2-propenoate, diallyl cis-butenedioate, diallyl 2-methylidene succinate, (E) -but-2- Ethenyl ethenyl, (Z) -octadeca-9-ethenyl enoate, (9Z, 12Z, 15Z) -octadec-9,12,15
-Ethenyl ester monomers such as ethenyl trienoate;

For example, 2-propenenitrile, 2-methyl-2-propenenitrile, (2-methyl)
Nitrile group-containing ethenyl monomers such as 2-cyanoethyl propenoate;

For example, ethenylbenzene-containing sulfonic acid compounds such as ethenylbenzenesulfonic acid, ethenylsulfonic acid, allylsulfonic acid, allyloxybenzenesulfonic acid, methallylsulfonic acid, methallyloxybenzenesulfonic acid, vinylsulfuric acid, etc. Ammonium sulfonate, monomethylammonium ethenylbenzenesulfonate, dimethylammonium ethenylbenzenesulfonate, trimethylammonium ethenylbenzenesulfonate,
Ethenylbenzenesulfonate tetramethylammonium, ethenylbenzenesulfonate ethylammonium, ethenylbenzenesulfonate diethylammonium, ethenylbenzenesulfonate triethylammonium, ethenylbenzenesulfonate tetraethylammonium, ethenylbenzenesulfonate propylammonium Ethenylbenzene sulfones containing alkenyl groups such as dipropylammonium ethenylbenzenesulfonate, tripropylammonium ethenylbenzenesulfonate, butylammonium ethenylbenzenesulfonate, pentylammonium ethenylbenzenesulfonate or hexylammonium ethenylbenzenesulfonate Ammonium salts of acids, sodium ethenylbenzenesulfonate, ethenylbenzenesulfone Metal salts of alkenyl group-containing ethenylbenzene sulfonates such as potassium acid, lithium ethenylbenzenesulfonate, magnesium ethenylbenzenesulfonate, zinc ethenylbenzenesulfonate, iron ethenylbenzenesulfonate, ammonium ethenylsulfonate, Metal salts and ammonium salts of ethenyl sulfonic acid containing alkenyl group such as sodium ethenyl sulfonate, potassium ethenyl sulfonate, ammonium ethenyl sulfonate, sodium ethenyl sulfonate, potassium alkenyl alkenyl group containing allyl sulfonic acid, sodium Metal salts and ammonium salts such as ethenyl alkyl sulfosuccinate, ammonium ethenyloxybenzenesulfonate, sodium ethenyloxybenzenesulfonate, ethenyloxybenze Metal salts and ammonium salts of alkenyl group-containing methallyl sulfonic acids such as potassium alkenyl alkenyl group-containing ethenyloxybenzene sulfonic acid metal salts and ammonium salts, ammonium methallyl sulfonate, sodium methallyl sulfonate, potassium methallyl sulfonate Salts, ammonium methallyloxybenzenesulfonate, sodium methallyloxybenzenesulfonate, potassium alkenyl group-containing methallyloxybenzenesulfonate metal salts and ammonium salts, (2-methyl) 2-propenamide Sulfonic acid [2-propenamide sulfonic acid and 2-methyl-2-propenamide sulfonic acid are combined to form “(2-
Methyl) 2-propenamide sulfonic acid ". The same applies hereinafter. ], Tert-butyl- (2-methyl) 2-propenamidesulfonic acid, (2-methyl) 2-propenamide-
Alkenyl group-containing amide sulfonic acids such as 2-methyl-1-propanesulfonic acid

For example, unsaturated carboxylic acids such as 2-carboxyethyl propenoate, 2-methylidene succinic acid, cis-butenedioic acid, trans-butenedioic acid, penta-2-enedioic acid, 2-methylfumaric acid;

For example, unsaturated carboxylic acid anhydrides such as 2,5-dihydrofuran-2,5-dione, 3-methylidenetetrahydrofuran-2,5-dione, 3-methyl-2,5-dihydrofuran-2,5-dione, etc. Things;

For example, monoalkyl esters and dialkyl esters of the above unsaturated carboxylic acids;

For example, glycidyl group-containing ethenyl esters such as glycidyl cinnamate, allyl glycidyl ether, ethenylcyclohexene monooxirane, 1,3-butadiene monooxirane;

For example, 2-propenamide, 2-methylprop-2-enoylamide, N, N-dimethyl-2-propenamide, N, N-diethyl-2-propenamide, N-methoxymethyl-2-propenamide, N-ethoxy Methyl (2-methyl) propenamide, N- (n
-, Iso-) butoxymethyl (2-methyl) propenamide, N-methoxyethyl (2
-Methyl) propenamide, N-ethoxyethyl (2-methyl) propenamide, N- (
n-, iso-) butoxyethyl (2-methyl) propenamide, N- [3- (N ′, N
'-Dimethylamino) propyl] -2-propenamide, N-isopropyl-2-propenamide, N-ethenylmethaneamide, N-ethenylacetamide, N-ethenyl-α-
Aliphatic amide group-containing ethenyl monomers such as methylthioacetamide and N-ethenylformamide;

For example, cyclic amide group-containing ethenyl monomers such as 4-propenoylmorpholine, N-ethenyl-2-pyrrolidone, N-ethenyl-2-azehan-2-one;

For example, 2-ethenylpyridine, 4-ethenylpyridine, 2-ethenylpiperazine, 2
-Ethenylpyrimidine, N-ethenylimidazole, 4-ethenylpiperazine, ethenyloxazole, N-ethenylcarbazole, N-ethenylindole, N-ethenylpyrrolidene, methylethenylimidazolium chloride, 2,4 -Diamino-6-ethenyl-s
-Triazine, 2-ethenylpyrrole, 1-benzyl-2-ethenyl-1H-pyrrole
2- (1-pyrrolyl) ethyl vinyl ether, 1- (4-vinylphenyl) -1H-pyrrole-2,5-dione, 2-ethenylthiophene, 2- (2-nitroethenyl) thiophene, 5-formyl-2 -Ethenylthiophene, 3-bromo-4- (1-iodo-2-
Perfluorobutyl-ethenyl) thiophene, 3-bromo-4- (1-bromo-2-pentafluorosulfanyl-ethenyl) -thiophene, 5- [4- [2- [4-diphenylaminophenyl-phenyl] -ethenyl] Nitrogen-containing complexes such as -phenyl] -thiophene-2-carbaldehyde, bis (2-diphenylethenyl) thiophene, 4- [2- (4-diphenylamino-phenyl) -ethenyl] -benzaldehyde, and diethenylethylurea Ring ethenyl monomers;

For example, maleimide derivatives such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide;

For example, N-methylitaconimide, N-ethylitaconimide, N-butylitaconimide, N-octylitaconimide, N-2-ethylhexylitaconimide, N-cyclohexylitaconimide, N-laurylitaconimide, N- Prop-2-enoyloxymethylene succinimide, N-prop-2-enoyl-6-oxyhexamethylene succinimide, N-prop-2-enoyl-8-oxyoctamethylene succinimide, N-2-methylprop-2-enoyl Imide derivatives other than maleimide derivatives such as oxymethylene succinimide, N-2-methylprop-2-enoyl-6-oxyhexamethylene succinimide, N-2-methylprop-2-enoyl-8-oxyoctamethylene succinimide;

For example, ethene, propene, 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 mixtures thereof;

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

Examples include chloroethene, 1,1-dichloroethene, allyl chloride, allyl alcohol, and the like, but are not particularly limited thereto.

Further, for example, an α, β-unsaturated compound having a copolymerizable α, β-unsaturated double bond obtained by reacting the above-mentioned glycidyl group-containing ethenyl ester with a fatty acid, the above-mentioned halogenation Copolymerizable α obtained by reacting alkylethenylbenzenes with at least one alcoholic hydroxyl group-containing compound selected from long-chain alcohols, poly (ethene oxide), and / or poly (ethene oxide) monoalkyl ethers .Alpha.,. Beta.-unsaturated compounds having .beta.-unsaturated double bonds are also included in monomer (a-1) or monomer (a-2).

In addition, for example, a copolymer of the above monomer (a-1) or monomer (a-2), which has a high molecular weight type having an α, β-unsaturated double bond at the end of the copolymer These polymerizable copolymers, so-called macromonomers, are also included.

These may be used alone or in combination of two or more, and are not particularly limited.

The cyclic amide compound (D) is an aminocarboxylic acid condensate obtained by dehydration condensation of an amino group and a carboxyl group of an aminocarboxylic acid within a molecule or between molecules to form a heterocyclic structure having 3 to 18 carbon atoms. preferable. The aminocarboxylic acid condensate is not limited as long as it can form a ring by dehydration reaction of aminocarboxylic acid, and may be a dimer or a multimer of trimer or higher. As the aminocarboxylic acid, aliphatic, alicyclic, aromatic and heterocyclic compounds can be used. However, an aminocarboxylic acid condensate having a heterocyclic structure having less than 3 carbon atoms or 19 or more carbon atoms is not preferable because the ring-opening reactivity is lowered.

Examples of the aminocarboxylic acid include aminoethanoic acid, 2-aminopropanoic acid, 3-aminopropanoic acid, 2-aminobutanoic acid, 4-aminobutanoic acid, 2-aminopentanoic acid, 5
-Aminopentanoic acid, 6-aminohexanoic acid, 8-aminooctanoic acid, 10-aminodecanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, (2R, 3S) -2-amino-3-methylpentanoic acid, (2R, 3S) -2-amino-3-hydroxybutanoic acid, 2
-Amino-5-guanidinopentanoic acid, 2-amino-3-carbamoylpropanoic acid, 2-
Aminobutanedioic acid, 2-amino-3-sulfanylpropanoic acid, 2,2'-diamino-3
, 3'-Disulfanediyldipropanoic acid, 2-aminopentanedioic acid, 2-amino-4-
Carbamoylbutanoic acid, 2-amino-3- (1H-imidazol-4-yl) propanoic acid, 2-amino-4-sulfanylbutanoic acid, 2-amino-4-hydroxybutanoic acid, (2
R, 3R) -2-amino-3-methylpentanoic acid, 2-amino-4-methylpentanoic acid,
2,6-diaminohexanoic acid, 2-amino-4- (methylsulfanyl) butanoic acid, 2,
5-diaminopentanoic acid, 2-amino-3-phenylpropanoic acid, pyrrolidine-2-carboxylic acid, 2-amino-3-hydroxypropanoic acid, (2R, 3S) -2-amino-3-hydroxybutanoic acid, 2 -Amino-3- (1H-indol-3-yl) propanoic acid, 2-
Amino-3- (4-hydroxyphenyl) propanoic acid, 2-amino-3-methylbutanoic acid, 2-amino-2-methylbutanoic acid, 2-methylalanine, (R) -2-amino-2-methyloctanoic acid, 2-phenylglycine, β-aminobenzenepropanoic acid, paraaminomethylbenzenecarboxylic acid, 4-chloro-β-ethyl-L-phenylalanine, α- (1-
Naphthyl) phenylalanine, o-methyl-L-serine, 3-sulfo-L-alanine, L
-Methionine S, S-dioxide, 3-amino-4-oxobutanoic acid, 2-aminobenzenecarboxylic acid, 3-aminobenzenecarboxylic acid, 3,5-di-tert-butyl-2-aminobenzenecarboxylic acid, 3- Aminobenzenecarboxylic acid, 3,4-diaminosibenzenecarboxylic acid, 4-amino-3-phenylbenzenecarboxylic acid, 4-amino-3-methoxybenzenecarboxylic acid, 4-amino-3,5-dimethoxybenzenecarboxylic acid, 4'-amino-4-carboxybiphenyl, 6-amino-2-naphthalenecarboxylic acid, 3-amino-
2-naphthalenecarboxylic acid, 5-amino-1-naphthalenecarboxylic acid, ω-aminoundecanoic acid, aminododecanoic acid, oxamic acid, 3-carbamoylpropanoic acid, 3-bromo-2-carbamoylbenzoic acid, D-glucal- 1-amido acid, 2'-methoxysuccinanilide acid, etc. are mentioned.

These aminocarboxylic acids may be organic compounds having a carboxyl group and an amino group in one molecule, and are not limited to the above examples.

Among the above aminocarboxylic acid condensates, lactam (d) is preferred. Specifically, for example, β-propiolactam, β-butyrolactam, β-propiolactam, γ-butyrolactam, δ-pentanelactam, γ-valerolactam, δ-valerolactam, ε-caprolactam, γ-caprolactam, δ-caprolactam, γ-heptanolactam, γ-octanolactam, δ-octanolactam, ε-octanolactam, δ-nonalactam, dodecane-12-lactam, benzoylcaprolactam, octanoylcaprolactam, 3, 5, 5-trimethylhexanoylcaprolactam, nonanoylcaprolactam, decanoylcaprolactam, undecenoylcaprolactam, benzoylvalerolactam,
Octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam, 1-methyloctahydro-2
H-azonin-2-one, 3-octyl-N- (2-ethylhexyl) valerolactam,
4-octyl-N- (2-ethylhexyl) valerolactam, 3-octyl-N- (2-
Ethylhexyl) caprolactam, 5-octyl-N- (2-ethylhexyl) caprolactam, 4-methyl-2-azetidinone, 1,4-diphenyl-2-azetidinone, 3,
3-dimethyl-1-ethyl-4-phenyl-2-azetinone, 3-azabicyclo [3,2
, 2] nonanone-2, 2-azabicyclo [3,2,2] nonanone-3, α-bromo-α-fluoro-β-lactam, α-hydroxy-α-trifluoromethyl-γ-lactam, 1-
Benzyl-3-hydroxy-3-trifluoromethyl-6,7-dihydroxy-2,4 (
3H, 5H) -dione, 3-hydroxy-1-phenyl-3-trifluoromethyl-6,
7-dihydroxy-2,4 (3H, 5H) -dione, 3-hydroxy-1-phenethyl-
3-trifluoromethyl-6,7-dihydroxy-2,4 (3H, 5H) -dione, 1-
Benzhydryl-3-hydroxy-3-trifluoromethyl-6,7-dihydroxy-2
, 4 (3H, 5H) -dione, 1-benzyl-3-hydroxy-6,6-dimethyl-3-
And trifluoromethyl-6,7-dihydroxy-2,4 (3H, 5H) -dione.

Among the lactones, those having an amide ring in the range of 3 to 18 carbon atoms from the side chain (I) length formed by the ring-opening reaction and the reactivity with the active hydrogen group. Specifically, butyrolactam, valerolactam, and caprolactam are particularly preferable.

In the present invention, the active hydrogen group of the copolymer (B) is preferably at least a carboxyl group or an amino group in consideration of the reactivity with the reactive compound (C). The above-mentioned carboxyl group and amino group containing the copolymer (B) are the active hydrogen group containing α,
It originates from the active hydrogen group generated after the ring-opening addition reaction of the cyclic amide (D) to the active hydrogen group of the β unsaturated monomer (a-1) and the active hydrogen group contained in the copolymer (A).

In the present invention, the amine value of the copolymer (B) is preferably from 0.1 to 50 mgKOH / g, more preferably from 0.5 to 30 mgKOH / g.
On the other hand, the acid value of the copolymer (B) is preferably from 0.1 to 50 mgKOH / g, and preferably from 0.5 to 40
mgKOH / g is more preferred.

If the amine value or acid value is lower than 0.1 mgKOH / g, the reactivity of the reactive compound (C) with respect to the amino group or carboxyl group is poor, the crosslinking density of the pressure-sensitive adhesive is lowered, and the cohesive force is insufficient. There is a fear. When the amine value or acid value is higher than 50 mgKOH / g,
There is a possibility that the pot life of the pressure-sensitive adhesive containing the reactive compound (C) may be shortened.

And when a copolymer (B) has both a carboxyl group and an amino group, Comprising: When the reactive compound (C) which can react with a carboxyl group is used, 0.1-10 mgKOH / g
Is preferable, and 0.1-8 mgKOH / g is more preferable.
When the reactive compound (C) capable of reacting with an amino group is used, 0.5 to 10 mgK
OH / g is preferred.

In the cross-linking reaction between the copolymer (B) and the reactive compound (C) in the present invention, a part of the terminal of the side chain (I) of the copolymer (B) is sealed for adjusting the cross-linking density. It is also preferred to adjust the crosslinking density by reacting compound (E) to produce side chain (II). The side chain (II
) Is referred to as copolymer (B-2).

The sealing compound (E) used in the present invention must have a functional group capable of reacting with the terminal active hydrogen group of the side chain (I). Specifically, an acid anhydride group-containing compound (e-
1), a glycidyl group-containing compound (e-2), an isocyanate group-containing compound (e-3), an amino group-containing compound (e-4), and the like. Moreover, sealing compound (E) may be used independently or may be used in combination of 2 or more type.

Examples of the acid anhydride-containing compound (e-1) used in the present invention include a molecular weight of 90 to 500.
Any known dicarboxylic acid compound anhydrides and derivatives, including those having a trifunctional or higher polycarboxylic acid acid anhydride ring, any of aliphatic compounds, aromatic compounds and alicyclic compounds good.

Examples of the aliphatic dicarboxylic acid include ethanedioic acid, propanedioic acid, butanedioic acid, hexanedioic acid, decanedioic acid, nonanedioic acid, octanedioic acid, (Z) -but-2-enedioic acid, chloro (Z) -but-2-enedioic acid, (E) -but-2-enedioic acid, dodecanedioic acid, heptanedioic acid, 2-methyl- (Z) -but-2-enedioic acid, pentanedioic acid Acid, 2-methylidenebutanedioic acid, tetrahydrofuran-2,5-dione, 2,5-dihydrofuran-2,5-dione, and the like, and anhydrides of these aliphatic dicarboxylic acids can be used. Further, derivatives of tetrahydrofuran-2,5-dione (methyltetrahydrofuran-2,5-dione, 2,2-
Dimethyltetrahydrofuran-2,5-dione, butyltetrahydrofuran-2,5-dione, isobutyltetrahydrofuran-2,5-dione, hexyl succinic anhydride, octyl succinic anhydride, dodecenyltetrahydrofuran-2,5-dione, phenyl Tetrahydrofuran-2,5-dione, etc.), tetrahydropyran-2,6-dione derivatives (tetrahydropyran-2,6-dione, 3-allyltetrahydropyran-2,6-dione, 2,
4-dimethyltetrahydropyran-2,6-dione, 2,4-diethyltetrahydropyran-2,6-dione, butyltetrahydropyran-2,6-dione, hexyltetrahydropyran-2,6-dione, etc.), 2, Derivatives of 5-dihydrofuran-2,5-dione (2
-Methyl 2,5-dihydrofuran-2,5-dione, 2,3-dimethyl 2,5-dihydrofuran-2,5-dione, butyl 2,5-dihydrofuran-2,5-dione, pentyl 2
, 5-dihydrofuran-2,5-dione, hexyl 2,5-dihydrofuran-2,5-dione, octyl 2,5-dihydrofuran-2,5-dione, decyl 2,5-dihydrofuran-2, 5-dione, dodecyl 2,5-dihydrofuran-2,5-dione, 2,3-dichloro 2,5-dihydrofuran-2,5-dione, phenyl 2,5-dihydrofuran-2,
Anhydride derivatives such as 5-dione, 2,3-diphenyl 2,5-dihydrofuran-2,5-dione, etc.) can also be used.

Examples of the aromatic dicarboxylic acid include benzene-1,2-dicarboxylic acid and benzene-
1,3-dicarboxylic acid, benzene-1,4-dicarboxylic acid, 2,5-dimethylbenzene
1,4-dicarboxylic acid, 4,4-biphenyldicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, bicyclo [2,2,1] hept-2-enedicarboxylic acid, diphenylmethane-4 , 4'-dicarboxylic acid, phenyl-2,3-dihydro-1
H-indenedicarboxylic acid and the like, and anhydrides of these aromatic dicarboxylic acids can be used. In addition, 1,3-dihydroisobenzofuran-1,3-dione, 4-methyl-1,3-
Examples include dihydroisobenzofuran-1,3-dione, and hexahydro-1,3-dione.
Dihydroisobenzofuran-1,3-dione derivative ((3-methyl-hexahydro-1
, 3-Dihydroisobenzofuran-1,3-dione, 4-methyl-hexahydro-1,3
-Dihydroisobenzofuran-1,3-dione), derivatives of tetrahydro-1,3-dihydroisobenzofuran-1,3-dione (1,2,3,6-tetrahydro-1,3-dihydroisobenzofuran-1, 3-dione, 3-methyl-1,2,3,6-tetrahydro-
1,3-dihydroisobenzofuran-1,3-dione, 4-methyl-1,2,3,6-tetrahydro-1,3-dihydroisobenzofuran-1,3-dione, methylbutenyl-1
, 2,3,6-tetrahydro-1,3-dihydroisobenzofuran-1,3-dione, etc.)
1,3-dihydroisobenzofuran-1,3-dione derivatives such as can also be used.

Examples of the alicyclic dicarboxylic acid include dimer acid, 1,4-cyclohexyl dicarboxylic acid, 1,3-cyclohexyl dicarboxylic acid, 1,2-cyclohexyl dicarboxylic acid, c
Examples thereof include is-4-cyclohexene-1,2-dicarboxylic acid, and anhydrides of these alicyclic dicarboxylic acids can be used.

Furthermore, 4,5,6,7,8,8-hexachloro-3a, 4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione, 1,4,5,6,7, 7-hexachloro-5-norbornene-2,3-dicarboxylic anhydride, biphenyldicarboxylic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, endomethylene-1,2,3,6
-Tetrahydro-1,3-dihydroisobenzofuran-1,3-dione, methyl-3,6
-Endomethylene-1,2,3,6-tetrahydro-1,3-dihydroisobenzofuran-1,3-dione, 1,2-cyclohexanedicarboxylic anhydride, 1-cyclopentene-
1,2-dicarboxylic acid anhydride, methylcyclohexene dicarboxylic acid anhydride, 1,8-naphthalenedicarboxylic acid anhydride, octahydro-1,3-dioxo-4,5-isobenzofurandicarboxylic acid anhydride and the like.

As what has an anhydride ring of polycarboxylic acid more than trifunctional, 1,3-dihydro-1,3-dioxo-5-isobenzofurancarboxylic acid is mentioned, for example. Examples of the trifunctional or more polycarboxylic acids having two or more anhydride rings include 1, 2, 3, 4
-Butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride,
1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylethanoic dianhydride, 2,3,5,6-tetracarboxycyclohexane dianhydride, 2,3 , 5,6-tetracarboxynorbornane dianhydride, 3,5,6-tricarboxynorbornane-2-ethanoic acid dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 5- (2 , 5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo [2,2,2] -oct-7-ene-2,3,5,6- Tetracarboxylic dianhydride, pyromellitic anhydride, 1
, 2,4,5-benzenetetracarboxylic dianhydride, ethene oxide di-1,3-dihydro-1,3-dioxo-5-isobenzofurancarboxylic acid ester, propene oxide di-1,3-dihydro-1 , 3-dioxo-5-isobenzofurancarboxylic acid ester, butene oxide di-1,3-dihydro-1,3-dioxo-5-isobenzofurancarboxylic acid ester, 3,3 ′, 4,4′-benzophenone tetracarboxylic acid Acid dianhydride, 2
, 2 ′, 3,3′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenylsulfonetetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenylsulfonetetracarboxylic Acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2
, 3,6,7-naphthalenetetracarboxylic dianhydride, naphthalene-1,8: 4,5-tetracarboxylic dianhydride, 4,4 ′-(hexafluoropropylidene) diphthalic anhydride, 3, 3 ', 4,4'-biphenyl ether tetracarboxylic dianhydride, 3,3', 4
4'-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3 ', 4,4'-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4 , 4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4′-bis (3 4-dicarboxyphenoxy) diphenylpropane dianhydride,
3,3 ′, 4,4′-perfluoroisopropylidenediphthalic dianhydride, 3,3 ′, 4
, 4'-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) Dianhydride, bis (triphenylbenzenedicarboxylic acid) -4,4'-diphenyl ether dianhydride, bis (triphenylbenzenedicarboxylic acid) -4,4'-diphenylmethane dianhydride, 9,9-bis [4- (3,4-Dicarboxyphenoxy) phenyl] fluorene anhydride, ethene oxide bis (anhydrotrimellitate), 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenebutanedioic acid diacid Anhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-6-methyl-1-naphthalenebutanedioic acid diacid Water, 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride, bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic anhydride, methyl nadic anhydride, Allylbicyclo [2.2.1] hept-5-ene-2
, 3-dicarboxylic anhydride, methallylbicyclo [2.2.1] hept-5-ene-2,3
-Dicarboxylic anhydride, allylmethylbicyclo [2.2.1] hept-5-ene-2,3
A dicarboxylic acid anhydride, methallylmethylbicyclo [2.2.1] hept-5-ene-2,
3-dicarboxylic anhydride etc. are mentioned.

Each of these acid anhydrides may be used alone or in combination of two or more.
-1). Use of a cyclic anhydride-containing compound having one anhydride ring is preferable because a pressure-sensitive adhesive excellent in adhesiveness, heat resistance, moist heat resistance and transparency can be obtained.

As the glycidyl group-containing compound (e-2) used in the present invention, a compound containing a known monofunctional glycidyl group can be used. For example, methyl glycidyl ether, butyl glycidyl ether, hexyl glycidyl ether, 2-ethyl-hexyl glycidyl ether, octyl glycidyl ether, decyl glycidyl ether, dodecyl glycidyl ether, stearyl glycidyl ether, methoxyethene oxide glycidyl ether (ethene oxide addition moles: 2-10), ethoxyethene oxide glycidyl ether (ethene oxide addition mole number: 2-10), butoxyethene oxide glycidyl ether (ethene oxide addition mole number: 2-10), dodecaoxyethene oxide glycidyl ether (ethene oxide addition mole) Number: 2 to 10), Methoxypropene oxide glycidyl ether (Propene oxide addition mole number: 2 to 10) Ethoxypropene oxide glycidyl ether (propene oxide addition mole number: 2 to 10), butoxy propene oxide glycidyl ether (propene oxide addition mole number: 2 to 10)
, Dodecaoxypropene oxide glycidyl ether (propene oxide addition mole number: 2 to 10), phenoxyethene oxide glycidyl ether (ethene oxide addition mole number: 2 to 10), phenoxypropene oxide glycidyl ether (propene oxide addition mole number: 2 to 2) 10) Cresyl glycidyl ether, benzyl glycidyl ether, phenyl glycidyl ether, (S) -2-glycidyl triphenyl ether, se
c-Ributylphenol monoglycidyl ether, p-tert-butylphenyl glycidyl ether, dibromophenyl glycidyl ether, 3-nitrobenzenesulfonic acid (
S) glycidyl ethers such as glycidyl ether, metaparacresyl glycidyl ether, allyl glycidyl ether;
For example, butanoic acid glycidyl ester, butanoic acid 2-methylglycidyl ester, hexanoic acid glycidyl ester, 2-ethyl-hexanoic acid glycidyl ester, octanoic acid glycidyl ester, decanoic acid glycidyl ester, dodecanoic acid glycidyl ester, hexadecanoic acid glycidyl ester, octadecane Glycidyl esters such as acid glycidyl ester, (2-methyl) propenoic acid glycidyl, itaconic acid monoglycidyl ester, butenetricarboxylic acid diglycidyl ester, butenetricarboxylic acid monoglycidyl ester;
For example, cycloaliphatic glycidyl esters such as cyclohexene oxide and ethenylcyclohexene oxide;
Other examples include glycidyl esters such as ethenylbenzene oxide and epichlorohydrin.

As the isocyanate group-containing compound (e-3) used in the present invention, a compound containing a known monofunctional isocyanate group can be used. For example, 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, 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, etc. are mentioned.

The isocyanate group-containing compound (e-3) used in the present invention can be used alone or in combination of two or more.

As the amino group-containing compound (e-4) used in the present invention, a known compound containing a primary amino group can be used. For example, methylamine, ethylamine, propylamine, isopropylamine, butylamine, isobutylamine, t-butylamine, pentylamine, isopentylamine, hexylamine, heptylamine, octylamine, 2-ethylhexylamine, diisobutylamine, nonylamine, decylamine, Undecylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine,
Eicosylamine, docosylamine, amylamine, 2-methyl-3-pentylamine,
3-isobutoxypropylamine, 3-methoxypropylamine, 3-propoxypropylamine, 3-butoxypropylamine, 3- (2-ethylhexyloxy) propylamine, 3-decyloxypropylamine, laurylamine, myristylamine, cetylamine , Coconutamine, stearylamine, oleylamine, 3-lauryloxypropylamine, 3-myristyloxypropylamine, beef tallow amine, polyoxypropenamine, polyoxyetheneamine, 2-aminoethanol, 6-aminocapronitrile, rosinamine Aliphatic amines such as

For example, cyclohexylamine, aniline, benzylamine, phenethylamine, p-
Methoxyphenethylamine, 1-phenylethylamine, 1- (4-methylphenyl) ethylamine, 1- (3-methoxyphenyl) ethylamine, 2- (phenylmethoxy) cyclopentanamine, 1- (1-naphthyl) ethylamine, 1- ( 2-naphthyl) ethylamine, 5-aminoindane, 1-aminotetralin, 1-methyl-3-phenylpropylamine, 1-amino-3-phenoxy-2-propanol, o-toluidine, 2-ethylaniline, 2-fluoroaniline O-anisidine, m-toluidine, m-anisidine, m-phenetidine, p-toluidine, 2,3-dimethylaniline, 1-aminopiperidine, N-amino-4-pipecholine, N-aminoethylpiperidine, N-amino Ethyl-2
-Pipecoline, N-aminoethyl-4-pipecoline, N-aminopropylpiperidine, N
-Aminopropyl-2-pipecoline, N-aminopropyl-4-pipecoline, N-aminobutylpiperidine, 4-aminomethyl-1-butylpiperidine, N-aminohexylpiperidine, N-aminoethylmorpholine, N-aminopropylmorpholine N-aminobutylmorpholine, N-aminohexylmorpholine, 3-amino-1-benzylpyrrolidine,
1-benzyl-2-methyl-3-aminopyrrolidine, 1-amino-4-methylpiperazine, furfurylamine, aminopyrazine, 2-aminomethylpyrazine, 2-aminoethylpyrazine, pyrazineamide, 5-methylpyrazineamide, 2 -Amino-3,5-dibromopyrazine, picolinamide, isonicotinamide, 2-aminonicotinic acid, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-amino-3-methylpyridine, 2
-Aminomethylpyridine, 3-aminomethylpyridine, 4-aminomethylpyridine, 2-
Amino-4-methylpyridine, 2-amino-6-methylpyridine, 2-amino-4-ethylpyridine, 2-amino-4-propylpyridine, 2-amino-3-nitropyridine, 2
-Amino-5-nitropyridine, 3-amino-2-chloropyridine, 4-amino-2-chloropyridine, 2-amino-5-chloropyridine, 2-amino-3,5-dichloropyridine, 3-amino- 2,6-dichloropyridine, 3-amino-2-chloro-4-picoline,
2-amino-3,5-dichloro-6-methylpyridine, 2-amino-5-chloro-3-methylpyridine, 3-amino-3,5-dichloro-4-methylpyridine, 4-amino-3,
Examples include amines having an alicyclic, aromatic or heterocyclic ring structure such as 5-dichloro-4,6-dimethylpyridine and 3-aminoethyl-6-chloropyridine.

In the present invention, the side chain (II) is formed when the terminal active hydrogen group of the side chain (I) is an amino group, the sealing compound (E) is an acid anhydride group-containing compound (e-1), glycidyl Group-containing compound (e-2
) Or an isocyanate group-containing compound (e-3), which is preferably a monofunctional compound. When the terminal active hydrogen group of the side chain (I) is a carboxyl group, the sealing compound (E
) Is preferably an acid anhydride group-containing compound (e-1), a glycidyl group-containing compound (e-2), an isocyanate group-containing compound (e-3), or an amino group-containing compound (e-4). .

In the present invention, by changing the structure of the side chain (II) of the copolymer (B-2) depending on the type of the sealing compound (E) to be used, various functions are imparted when used in a pressure-sensitive adhesive. be able to.
For example, in the case of using a glycidyl group-containing compound, the secondary hydroxyl group to be formed can improve the adhesiveness, for example, the adhesive force to glass is improved. Moreover, when an isocyanate group containing compound is used, heat resistance and heat-and-moisture resistance improve by the urethane bond to form. Furthermore, when an acid anhydride group-containing compound or an amino group-containing compound is used, the antistatic function can be improved by the amide bond or acid-base bond formed.

Next, a method for producing a pressure-sensitive adhesive resin will be described.
In the present invention, the pressure-sensitive adhesive resin production method can be produced by the following two-stage process, preferably a three-stage process.
Step 1 for copolymerization of monomer (a-1) and monomer (a-2) to obtain copolymer (A)
,and,
The side chain (I) is obtained by reacting the active hydrogen group in the copolymer (A) with the cyclic amide compound (D).
The production process of the two-step process of the process 2 which produces | generates and obtains a copolymer (B) is mentioned.
If necessary, the active hydrogen group of the side chain (I) in the copolymer (B) and the sealing compound (E
) To form a side chain (II) to obtain a copolymer (B-2).

First, a monomer (a-1) and a monomer (a-2) are copolymerized in advance to obtain a copolymer (A).
Step 1 for obtaining the above will be described.

The copolymer (A) in the present invention is 0.001 to 5 parts by weight with respect to a total of 100 parts by weight of various monomers (a-1) and monomers (a-2) as described above. The polymerization initiator is synthesized by a method such as bulk polymerization, solution polymerization, emulsion polymerization, 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) and dimethyl 2,2′-azobis (2
-Methyl propionate), 4,4'-azobis (4-cyanovaleric acid) and 2,2 '
-Azobis (2-hydroxymethylpropionitrile), 2,2'-azobis [2- (2
-Imidazolin-2-yl) propane] and the like.

Also, benzoyl peroxide, tert-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di (2-ethoxyethyl) peroxydicarbonate, tert-butyl peroxy 2-ethylhexanoate, tert-butylperoxyneodecanoate and te
Examples thereof include organic peroxides such as rt-butyl peroxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, and diacetyl peroxide.

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.

Next, Step 2 in which the active hydrogen group in the copolymer (A) and the cyclic amide compound (D) are reacted to produce the side chain (I) to obtain the copolymer (B) will be described.

In step 2, the active hydrogen group in the copolymer (A) obtained in step 1 and a cyclic amide (D
) And ring-opening addition to produce side chain (I) to obtain copolymer (B).
The copolymer (B) has a side chain (I), which improves adhesion to the adherend when used as a pressure-sensitive adhesive, and forms at the end of the side chain (I). Since the reaction between the active hydrogen group and the crosslinking agent proceeds efficiently and the cohesive force is improved, there is an advantage that a tough crosslinked structure can be formed.

The ring-opening addition of the cyclic amide (D) may be a single addition of only one molecule or a side chain (I
The ring may be subjected to multiple ring-opening additions such as further ring-opening addition of the cyclic amide (D) to the active hydrogen group generated at the terminal of When the ring-opening addition is multiplexed in this way, the side chain (I) can be made longer. As a result, the side chain (I) can move more flexibly, so that the active hydrogen group at the end of the side chain (I) can react with the crosslinking agent more efficiently. Further, since the side chain (I) has a plurality of amide bonds, there is an advantage that the affinity with the adherend is further increased.

The cyclic amide (D) is preferably reacted in an amount of 0.2 to 100 mol, more preferably 0.5 to 80 mol, with respect to 1 mol of the active hydrogen group in the copolymer (A). 8
It is more preferable to make it react -60 mol, and it is especially preferable to make it react 1.5-40 mol. If it deviates from the above range, both tack and cohesion may not be satisfied when used in a pressure sensitive adhesive.
The ring-opening addition reaction of the cyclic amide (D) to the active hydrogen group in the copolymer (A) is 50-2.
It is preferable to carry out in the range of 00 ° C. More preferably, it is the range of 70-150 degreeC. 5
When the temperature is lower than 0 ° C, the reaction hardly occurs, and when the temperature is higher than 200 ° C, the copolymer (A
) Is not preferred because the ring-opening addition reaction is unlikely to occur in the active hydrogen group, and homopolymerization is likely to occur.
The copolymer (B) thus obtained has an acid value or amine value of 0.1 to 30 mgKOH.
/ G is preferable, and a range of 0.5 to 30 mgKOH / g is more preferable.

Next, the active hydrogen group of the side chain (I) in the copolymer (B) and the sealing compound (E) are reacted to produce the side chain (II), and the copolymer (B-2) is obtained. The obtaining step 3 will be described.

In step 3, the side chain (II) is produced by reacting the end of the side chain (I) of the copolymer (B) with the sealing compound (E). Various specific functions can be imparted by the side-chain structural changes that occur at this time.
Moreover, the ratio of the side chain (I) which has an active hydrogen group from the whole side chain which a copolymer (B-2) has can also be reduced by producing | generating side chain (II). This is because the active hydrogen group at the end of the side chain (I) is necessary for the reaction with the cross-linking agent. . Specifically, when an amino group or a carboxyl group is present more than necessary at the end of the side chain (I), the physical properties may be deteriorated.
Further, by using the sealing compound (E), it is possible to simultaneously seal an amino group and a carboxyl group that exist other than the terminal of the side chain (I) of the copolymer (B). Therefore, it is preferable that the terminal of side chain (II) does not have an active hydrogen group. However, depending on the desired physical properties, the end of the side chain (II) may have a functional group other than an amino group and a carboxyl group.

By the sealing reaction as described above, the side chain of the copolymer (B-2) has a side chain capable of crosslinking reaction having an active hydrogen group, and a side having no active hydrogen group (sealed). There is a chain.
That is, the copolymer (B-2) of the present invention has a side chain (side chain I) having a crosslinkable functional group,
A plurality of side chains including a side chain (side chain II) having no active hydrogen group such as an amino group and a carboxyl group (side chain II) are branched from the main chain of the copolymer, and a sealing compound ( Since the structure of the end of the side chain varies depending on the type of E), various properties such as adhesion and durability can be imparted when used in a pressure-sensitive adhesive.

In the present invention, it is preferable to appropriately use a catalyst in the reaction for forming the side chain (I) and the reaction for forming the side chain (II). Catalysts include ammonia, amines, quaternary ammonium salts, quaternary phosphonium salts, alkali metal hydroxides, alkaline earth metal hydroxides, Lewis acids, tin, lead, titanium, iron, zinc, zirconium, Examples include organometallic compounds containing cobalt and the like, metal halides, and the like.

Examples of amines include triethylamine, pyridine, phenylamine, morpholine, N-methylmorpholine, pyrrolidine, piperidine, N-methylpiperidine, cyclohexylamine, n-butylamine, dimethyloxazoline, imidazole, N-methylimidazole, N, N. -Dimethylethanolamine, N, N-diethylethanolamine,
N, N-dimethylisopropanolamine, N-methyldiethanolamine and the like can be mentioned.

Examples of the quaternary ammonium salts include tetramethylammonium bromide, tetramethylammonium chloride, tetramethylammonium fluoride trihydrate, tetramethylammonium hexafluorophosphate, tetramethylammonium hydrogen phthalate, tetramethylammonium hydroxide pentahydrate. Tetramethylammonium hydroxide, tetramethylammonium iodide, tetramethylammonium nitrate, tetramethylammonium perchlorate, tetramethylammonium tetrafluoroborate, tetramethylammonium tribromide,
Phenyltrimethylammonium bromide, tetraethylammonium bromide, tetraethylammonium chloride, tetraethylammonium fluoride trihydrate, tetraethylammonium hydroxide, tetraethylammonium iodide, tetraethylammonium perchlorate, tetraethylammonium tetrafluoroborate, tetraethylammonium-p-toluenesulfonate, Tetrapropylammonium bromide, tetrapropylammonium chloride, tetrapropylammonium iodide, tetrapropylammonium hydroxide, tetrapropylammonium perchlorate, tetra-n-propylammonium hydrogensulfate,
Tetra-n-propylammonium pearlate (VII), tetrabutylammonium bromide, tetrabutylammonium tribromide, tetrabutylammonium chloride, tetrabutylammonium iodide, tetrabutylammonium hydroxide, tetrabutylammonium hexafluorophosphate, tetrabutyl Ammonium hydrogen sulfate, tetrabutylammonium nitrate, tetrabutylammonium tetrahydroborate, tetrabutylammonium tetrafluoroborate, tetrabutylammonium cyanotrihydroborate, tetrabutylammonium difluorotriphenylstannate, tetrabutylammonium fluoride trihydrate,
Tetrabutylammonium tetrathiophenate (IV), tetrabutylammonium fluoride hydrate, tetra-n-butylammonium dihydrogen trifluoride, tetra-n-butylammonium trifluoromethanesulfonate, tributylammonium bis (2,3-dimercapto- 2-butenedinyllate-S, S ′) nicolate, tetra-n-heptylammonium bromide, tetra-n-heptylammonium chloride, tetra-n-heptylammonium iodide, tetra-n-hexylammonium benzoate, tetra-n -Hexylammonium bromide, tetra-n-hexylammonium chloride, tetra-n-hexylammonium iodide, tetra-n-hexylammonium Examples include perchlorate, tetraoctyl ammonium bromide, and tetraoctadecyl ammonium bromide.

Examples of quaternary phosphonium salts include benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, ethyltriphenylphosphonium bromide, ethyltriphenylphosphonium iodide, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, tetrabutylphosphonium tetrafluoroborate, Tetrabutylphosphonium hexafluorophosphate, tetrabutylphosphonium tetraphenylborate, tetrabutylphosphonium benzotriazolate, tetrabutylphosphonium bis (1,2-benzenedithiolate) nicolate (III), tetrabutylphosphonium bis (4-methyl-1) , 2-Benzenedithiolate) Nicolate (
III), tetrabutylphosphonium bis (4,5-mercapto-1,3-dithiol-
2-thionate-S ⁴ , S ⁵ ) Nicolate (III) and the like.

Examples of the alkali metal or alkaline earth metal hydroxide include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide;
And alkaline earth metal hydroxides such as magnesium hydroxide, calcium hydroxide, strontium hydroxide and barium hydroxide.

Examples of organic tin compounds include dibutyltin dichloride, dibutyltin oxide,
Dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (DBTD)
L), dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide,
Examples thereof include tributyltin oxide, tributyltin acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate, and tin 2-ethylhexanoate.

Examples of organic zirconium compounds include zirconium ethanoate, zirconium benzenecarboxylate, zirconium naphthenate, and the like.

Examples of the organic titanium compounds include dibutyltitanium dichloride, tetrabutyltitanate, tetrabutoxytitanate, tetraethyltitanate, tetraisopropyltitanate, butoxytitanium trichloride, and the like.

Examples of the organic lead compounds include lead ethanoate, (Z) -octadeca-9-enoate lead,
Examples include lead 2-ethylhexanoate, lead benzenecarboxylate, and lead naphthenate.

Examples of organic iron compounds include iron 2-ethylhexanoate and iron acetylacetonate.

Examples of the organic cobalt compounds include cobalt ethanoate, cobalt benzenecarboxylate, and cobalt 2-ethylhexanoate.

Examples of the organic zinc compounds include zinc ethanoate, zinc ethanedioate, zinc naphthenate, and zinc 2-ethylhexanoate.

Examples of metal halides include stannous chloride, stannous bromide, stannous iodide, and the like.

Furthermore, Lewis acids such as boron trifluoride, manganese ethanoate, germanium oxide, antimony trioxide, aluminum trichloride, zinc chloride, titanium chloride and the like can be mentioned. These catalysts may be used alone or in combination of two or more. The amount of the catalyst used is preferably 0.0001 to 10 parts by weight with respect to a total of 100 parts by weight of the copolymer (B) and the sealing compound (E), and the range of 0.0001 to 1 part by weight is used. More preferred. If the amount exceeds 10 parts by weight, the product may be colored, or the catalyst that has not been deactivated may adversely affect the adhesive properties.

It is preferable that the pressure sensitive adhesive of this invention contains the resin for pressure sensitive adhesives obtained by the above-mentioned manufacturing method, and the reactive compound (C) mentioned above.

The reactive compound (C) used in the present invention is a compound having a functional group capable of reacting with a hydroxyl group, a carboxyl group, an amino group, an amide group, a maleimide group, etc., which the pressure-sensitive adhesive resin has. Examples of such compounds include polyisocyanate compounds, oxirane compounds, amine compounds, aziridine compounds, carbodiimide compounds, oxazoline compounds, melamine compounds, and metal chelate compounds. These compounds have 2 functional groups in the molecule.
It is necessary to have more than one.

When the active hydrogen group of the pressure-sensitive adhesive resin is a carboxyl group, the reactive compound (C)
Examples thereof include polyisocyanate compounds, oxirane compounds, amino compounds, aziridine compounds, oxazoline compounds, melamine compounds, and metal chelate compounds. When the active hydrogen group is an amino group, examples of the reactive compound (C) include polyisocyanate compounds. Among these, a polyisocyanate compound is particularly preferably used because it is excellent in the adhesion of the resin composition after the crosslinking reaction and the adhesion to the coating layer.

For example, examples of the polyisocyanate compound include aromatic polyisocyanate, aliphatic polyisocyanate, araliphatic polyisocyanate, and alicyclic polyisocyanate.

Examples of the aromatic polyisocyanate include 1,3-phenylene diisocyanate,
4,4'-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4
'-Diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-
Tolylene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4 ', 4 "-Triphenylmethane triisocyanate etc. can be mentioned.

Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HMDI), pentamethylene diisocyanate, 1,2-propene diisocyanate, 2,3-butene diisocyanate, 1,3-butene diisocyanate, and dodeca. Methylene diisocyanate, 2, 4,
4-trimethylhexamethylene diisocyanate and the like can be mentioned.

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

Examples of the alicyclic polyisocyanate include 3-isocyanate methyl-3,5,5.
-Trimethylcyclohexyl isocyanate (IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4, 4'-methylenebis (cyclohexyl isocyanate), 1,4-bis (isocyanatemethyl) cyclohexane and the like can be mentioned.

The polyisocyanate 2-methyl-2- (hydroxymethyl) propane-1,
A 3-diol, a trimer having an isocyanurate ring, or the like can also be used in combination. Polyphenylmethane polyisocyanate (PAPI), naphthylene diisocyanate, and these polyisocyanate modified products can be used. As polyisocyanate modified products,
A modified product having a carbodiimide group, a uretdione group, a uretoimine group, a burette group reacted with water, or an isocyanurate group, or two or more of these groups can be used. A reaction product of a polyol and a diisocyanate can also be used as a polyisocyanate.

Among these polyisocyanate compounds, 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (also known as isophorone diisocyanate), xylylene diisocyanate, 4,4 ′ Use of a non-yellowing or hard yellowing polyisocyanate compound such as methylenebis (cyclohexyl isocyanate) (also known as hydrogenated MDI) is particularly preferred from the viewpoint of weather resistance, heat resistance, and heat and humidity resistance.

When a polyisocyanate compound is used as the reactive compound (C), a known catalyst can be used as necessary to accelerate the reaction. For example, a tertiary amine compound, an organometallic compound, etc. are mentioned, and it is possible to use a single compound or plural compounds.

Examples of the tertiary amine compound include triethylamine, triethenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, diazabicycloundecene (DBU) and the like. it can.

Examples of organometallic compounds include tin compounds and non-tin compounds.
Examples of tin compounds include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (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 the non-tin compounds include titanium compounds such as dibutyltitanium dichloride, tetrabutyltitanate, butoxytitanium trichloride, (Z) -octadeca-9-leadate, 2-ethylhexanoate, lead benzenecarboxylate, naphthene. Lead type such as lead acid, 2
-Iron series such as iron ethylhexanoate and iron acetylacetonate, cobalt series such as cobalt benzenecarboxylate and cobalt 2-ethylhexate, zinc series such as zinc naphthenate and zinc 2-ethylhexanoate, zirconium naphthenate, etc. Can be mentioned.
Among the above catalysts, dibutyltin dilaurate (DBTDL), tin 2-ethylhexanoate and the like are preferable in terms of reactivity and hygiene.

Among reactive compounds (C), examples of oxirane compounds include 2,2-bis (hydroxyphenyl) propane, 2-chloromethyloxirane type oxirane resins and 2,2-bis (hydroxyphenyl) methane type, 2,2-bis (4-hydroxyphenyl) ethane type, 2,2-bis (4-hydroxyphenyl) butane type, 4,4′-sulfonyldiphenol type, 1,1-dichloro-2,2-bis ( 4-hydroxyphenyl) ethene, 1,3
-Bis [2- (4-hydroxyphenyl) -2-propyl] benzene type, 2,2-bis (
4-hydroxy-3-methylphenyl) propane type, 2,2-bis (4-hydroxy-3)
-Methylphenyl) methane type, 2,2-bis (4-hydroxy-3-methylphenyl) hexafluoropropane type, 2,2-bis (4-hydroxy-3,5-dimethylphenyl)
Propane type, 2,2-bis (4-hydroxycyclohexyl) propane type, 2,2-bis (2-hydroxy-5-biphenylyl) propane type and copolymerized oxirane resins, phenol novolac type, Orthocresol novolac type, para tertiary butylphenol novolak type, paraoctylphenol novolak type, nonylphenol novolak type and co-condensation type oxirane resins, ethene oxide diglycidyl ether, polyethene oxide diglycidyl ether, glycerin diglycidyl ether, glycerin tri Glycidyl ether, 1,6-hexanediol diglycidyl ether, 2-methylpentane-2,4-diol triglycidyl ether, diglycidylphenylamine, N, N, N ′, N′— Tetraglycidyl-m-xylylenediamine, 1,3-
Bis (N, N′-diglycidylaminomethyl) cyclohexane and the like can be mentioned.

Of the reactive compounds (C), as an example of an amine compound, a primary amino group is preferably 2
An aliphatic polyamine (which may contain an aromatic ring in its skeleton) is a polyamine having two or more primary amino groups that are not directly bonded to the aromatic ring because it is a polyamine having at least one and has a good curing speed. preferable.
Examples of aliphatic polyamines include 2,5-dimethyl-2,5-hexamethylenediamine,
Mensendiamine, 1,4-bis (2-amino-2-methylpropyl) piperazine, polypropene oxide in which amino groups are bonded to propylene branched carbons at both ends of the molecule (propene oxide diamine, propene skeleton triamine, etc. ), Ethenediamine, propenediamine, butenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethenehexamine, hexamethylenediamine, trimethylhexamethylenediamine, N-aminoethylpiperazine, 1,2-diaminopropane, iminobis Polyether skeleton diamines such as propylamine, methyliminobispropylamine, ethene oxide skeleton diamine, etc., with methylene groups bonded to them, 1,5-diamino-2-methylpentane, Xylylenediamine (MXDA), polyamidoamine, isophoronediamine, 1,3-bisaminomethylcyclohexane, 1-cyclohexylamino-3-aminopropane, 3-aminomethyl-3,3,5-trimethyl-cyclohexylamine, norbornane skeleton And dimethyleneamine.
Among these, since the curing rate is particularly high, 1,3-bisaminomethylcyclohexane, dimethyleneamine having a norbornane skeleton, metaxylylenediamine, H ₂ N (CH ₂ C
H ₂ O) ₂ (CH ₂ ) ₂ NH ₂ (a diamine having an ethene oxide skeleton), a diamine having a propene oxide skeleton, a triamine having a propene oxide skeleton, and a polyamidoamine are usefully used.

Ketimines, which are the reaction products of these polyamines and ketones, are also included in the amino compounds. From the viewpoints of stability, adjustment of reactivity, and overcoatability, 1-phenylethanone or 1-phenylethanone
Obtained from phenylethane-1-one and 1,3-bisaminomethylcyclohexane; Obtained from 1-phenylethanone or 1-phenylethane-1-one and dimethyleneamine (NBDA) having a norbornane skeleton Obtained from 1-phenylethanone or 1-phenylethan-1-one and metaxylylenediamine; 1-phenylethanone or 1-phenylethan-1-one and an ethene oxide skeleton or propene oxide skeleton Those obtained from Jeffamine, EDR148, Jeffamine D230, Jeffamine D400, etc., which are diamines, or Jeffamine T403, which is a triamine having a propene oxide skeleton, can also be used.

Among the reactive compounds (C), examples of the aziridine compound 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, tetramethylolmethane-tri-β-aziridinylpropionate, 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′-bishydroxymethylbutanol tris [3- (1 -Aziridinyl) propionate], pentaerythritol tetra [3- (1-aziridinyl) propionate], diphenylmethane-4,4
-Bis-N, N'-ethyleneurea, 1,6-hexamethylenebis-N, N'-ethyleneurea, 2,4,6- (triethyleneimino) -Syn-triazine, bis [1- (2-
Ethyl) aziridinyl] benzene-1,3-carboxylic acid amide and the like.

Among the reactive compounds (C), carbodiimide compounds include carbodiimide groups (—N
A compound having two or more = C = N-) in the molecule is preferably used, and a known polycarbodiimide can be used.

Moreover, as a carbodiimide compound, the high molecular weight polycarbodiimide produced | generated by carrying out the decarboxylation condensation reaction of diisocyanate in 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'-dicyclohexylmethane diisocyanate, one of tetramethylxylylene diisocyanate, or these Mixtures can be used.

Examples of the carbodiimidization catalyst include 1-phenyl-2-phospholene-1-oxide, 3-
Methyl-2-phospholene-1-oxide, 1-ethyl-3-methyl-2-phospholene-1
Phosphorene oxides such as -oxide, 1-ethyl-2-phospholene-1-oxide, or their 3-phospholene isomers can be used. An example of such a high molecular weight polycarbodiimide is a carbodilite series manufactured by Nisshinbo Industries, Ltd.

Among the reactive compounds (C), as the oxazoline compound, a compound having two or more oxazoline groups in the molecule is preferably used. Specifically, 2′-methylenebis (2-oxazoline), 2,2′- Ethenebis (2-oxazoline), 2,2'-ethenebis (4-
Methyl-2-oxazoline), 2,2'-propenebis (2-oxazoline), 2,2 '
-Tetramethylenebis (2-oxazoline), 2,2'-hexamethylenebis (2-oxazoline), 2,2'-octamethylenebis (2-oxazoline), 2,2'-p-phenylenebis (2- Oxazoline), 2,2'-p-phenylenebis (4,4'-dimethyl-2-oxazoline), 2,2'-p-phenylenebis (4-methyl-2-oxazoline), 2,2'-p -Phenylenebis (4-phenyl-2-oxazoline), 2,2'-m
-Phenylenebis (2-oxazoline), 2,2'-m-phenylenebis (4-methyl-
2-oxazoline), 2,2'-m-phenylenebis (4,4'-dimethyl-2-oxazoline), 2,2'-m-phenylenebis (4-phenylenebis-2-oxazoline),
2,2'-o-phenylenebis (2-oxazoline), 2,2'-o-phenylenebis (
4-methyl-2-oxazoline), 2,2'-bis (2-oxazoline), 2,2'-bis (4-methyl-2-oxazoline), 2,2'-bis (4-ethyl-2-) Oxazoline), 2,2'-bis (4-phenyl-2-oxazoline) and the like. Alternatively, ethenyl monomers such as 2-isopropenyl-2-oxazoline and 2-isopropenyl-4,4-dimethyl-2-oxazoline, and other monomers that can be copolymerized with these ethenyl monomers. It may be a copolymer with a monomer.

Among the reactive compounds (C), the melamine compound is a compound having a triazine ring in the molecule, such as melamine, benzoguanamine, cyclohexanecarboguanamine, methylguanamine, ethenylguanamine, hexamethoxymethylmelamine, tetramethoxymethylbenzoguanamine, etc. Is mentioned. These low-condensates, alkyl etherified formaldehyde resins and aminoplast resins may also be used.

Among the reactive compounds (C), examples of the metal chelate compounds include aluminum, iron, copper, zinc, tin, titanium, titanium, nickel, antimony, magnesium, vanadium, chromium, zirconium and other polyvalent metals such as acetylacetone and Examples thereof include compounds coordinated to ethyl acetoethanoate.

  These reactive compounds (C) can be used alone or in combination.

Further, the reactive compound (C) is 0.001 with respect to 100 parts by weight of the pressure-sensitive adhesive resin.
It is preferable to use -50 weight part, and it is more preferable to use 0.01-30 weight part.
When the usage-amount of a reactive compound (C) exceeds 50 weight part, there exists a possibility that the adhesiveness of a pressure sensitive adhesive film may fall. On the other hand, when the amount is less than 0.001 part by weight, a sufficient cross-linked structure cannot be obtained, so that the cohesive force of the adhesive layer is lowered, and the heat resistance and heat and humidity resistance may be lowered.

The pressure-sensitive adhesive of the present invention preferably contains an organic solvent. In addition, various resins, softeners, dyes, pigments, antioxidants, tackifiers, silane coupling agents, plasticizers, fillers, antistatic agents, antiaging agents, etc., as long as the effects of the present invention are not impaired. May be blended.

In the pressure-sensitive adhesive film of the present invention, an adhesive layer made of the above-mentioned pressure-sensitive adhesive is formed on the substrate (F). As a method for producing a pressure-sensitive adhesive film, for example, a method in which a pressure-sensitive adhesive is applied to a release treatment surface of a release liner, dried, and a base material (F) is bonded, or a pressure-sensitive type is applied to the base material (F). Examples include a method in which an adhesive is applied and dried, and the release treatment surface of the release liner is bonded to the surface of the adhesive layer.

Examples of the substrate (F) include sheet-like substrates such as cellophane, various plastic sheets, and paper. Moreover, a base material can also be used independently, The thing in the multilayer state formed by laminating | stacking a several base material can also be used. Further, a sheet-like base material whose surface is peeled can also be used.

Various plastic sheets are also referred to as various plastic films, such as polyethenol film (also referred to as PEA film), triacetyl cellulose film (also referred to as TAC film), polypropene (also referred to as PP film), polyethene (also referred to as PE film), poly Polyolefin resin films such as cycloolefin (also referred to as COP film), ethene-ethanoic acid ethenyl copolymer (also referred to as EVA film), polyethene terephthalate (also referred to as PET film), polybutene terephthalate (also referred to as PBT film), etc. Polyester resin film, polycarbonate resin film (also called PC film), polynorbornene resin film, polyarylate resin film , Propenoic acid resin film, polyphenylene sulfide resin film (also referred to as PPS film), polyethenylbenzene resin film (also referred to as PST film), ethenyl resin film, polyamide resin film (also referred to as PA film) ), A polyimide resin film (also referred to as a PI film), an oxirane resin film, and the like. Among these substrates, in particular P
It is preferable to use a sheet-like substrate such as an EA film, a TAC film, a polyolefin resin film, a polyester resin film, or a PC film as the optical film.

Moreover, in this invention, it is also preferable to set it as the optical adhesive film which used the optical film for the base material (F) and formed the contact bonding layer which consists of a pressure sensitive adhesive on the said optical film. The optical adhesive film can also be used for display applications such as laminating on a liquid crystal cell or the like.

Examples of the optical film used in the present invention include a polarizing film, a retardation film, an elliptically polarizing film, an antireflection film, and a brightness enhancement film.
The polarizing film is also called a polarizing plate, and is a multilayer structure film in which both sides of a polyethenol polarizer are sandwiched between two triacetylcellulose protective films and two cycloolefin films.

After applying a pressure-sensitive adhesive to a release liner or optical film 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, the liquid is heated by a method such as heating. When the medium is removed or when the pressure-sensitive adhesive does not contain a liquid medium that should be volatilized, the molten resin layer is cooled and solidified to form an adhesive layer on the release liner or optical film can do.
The thickness of the adhesive layer is preferably 0.1 μm to 200 μm, preferably 0.1 μm to 100 μm.
More preferably, it is μm. If the thickness is less than 0.1 μm, sufficient adhesive strength may not be obtained, and if the thickness exceeds 200 μm, characteristics such as adhesive strength are often not improved further.

As a method for applying the pressure-sensitive adhesive of the present invention, Mayer bar, applicator, brush, spray, roller, gravure coater, die coater, lip coater, comma coater, knife coater, reverse coater, spin coater, etc. are used. It is preferable.

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

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.

(Synthesis Example 1)
<Production of copolymer (A) (step 1)>
A polymerization tank, a stirrer, a thermometer, a reflux condenser, a dropping device, a polymerization reactor equipped with a nitrogen introduction tube, and a dropping device, the following monomers (active hydrogen group-containing α, β-unsaturated monomer) (A-1),
And α, β-unsaturated monomer (a-2)), a polymerization initiator, and a solvent were respectively charged in the following ratios.

[Polymerization tank]
N-butyl propenoate (a-2) 29.5 parts methyl propenoate (a-2) 15 parts propenoic acid (a-1) 5 parts 2-hydroxyethyl 2-methylpropenoate (a-1) 0.5 Part Methyl ethanoate 30 parts 2,2'-Azobisisobutyronitrile 0.05 part [Drip device]
N-butyl propenoate (a-2) 45 parts propenoic acid (a-1) 5 parts ethyl ethanoate 36 parts 2,2′-azobisisobutyronitrile 0.05 part

After the air in the polymerization tank was replaced with nitrogen gas, the reaction was started at reflux temperature in a nitrogen atmosphere with stirring. When the polymerization conversion reached about 70%, the dropping of the mixture was started from the dropping device. After completion of the dropwise addition, the mixture was further aged with stirring for 8 hours, and then methyl ethanoate:
167 parts were added, and it cooled to room temperature, and obtained the resin solution for pressure sensitive adhesives containing a copolymer (A). This solution is colorless and transparent, has a non-volatile content of 30.1% by weight and a viscosity of 9,000 mPa · s. The copolymer (A) has an acid value of 77.8 mgKOH / g, a glass transition temperature of −35 ° C., and a weight. The average molecular weight was 1,425,000.

<Production of copolymer (B) (step 2)>
A polymerization reaction apparatus having a stirrer, a thermometer, a reflux condenser, a dropping apparatus, and a nitrogen introducing tube attached to the polymerization tank was prepared, and the copolymer (A) solution obtained in step (1) was added to the polymerization tank and the dropping apparatus, The cyclic amide compound (D), the catalyst, and the organic solvent were charged at the following ratios.

[Polymerization tank]
Copolymer (A) solution 200 parts [Drip device]
ε-caprolactam (D) 60 parts tetrabutylammonium tetrahydroborate (catalyst) 0.5 parts ethyl ethanoate 30 parts

After the air in the polymerization tank was replaced with nitrogen gas, the resin solution was stirred, and the temperature was raised to 120 ° C. over 1 hour while removing the solvent from the system. At this time, the amount of desorbed solvent was 30 parts.
Subsequently, the cyclic amide compound (D) mixture was dripped at this with constant velocity over 1 hour from the dripping apparatus. Furthermore, after reacting and aging for 12 hours with stirring, 140 parts of ethyl ethanoate is added and cooled to room temperature to complete the reaction, and the pressure-sensitive adhesive containing the copolymer (B) having a side chain (I) A resin solution was obtained. This solution is colorless and transparent, has a nonvolatile content of 30.2% by weight, and a viscosity of 8,80.
The pressure-sensitive adhesive resin was a resin having an acid value of 38.9 mgKOH / g, a glass transition temperature of −36 ° C., and a weight average molecular weight of 1350,000.

<Production of copolymer (B-2) (step 3)>
A polymerization reaction apparatus in which a stirrer, a thermometer, a reflux condenser, a dropping apparatus, and a nitrogen introducing pipe are attached to the polymerization tank is prepared, and the copolymer (B-2) obtained in step (2) is prepared in the polymerization tank and the dropping apparatus. A pressure-sensitive adhesive resin solution containing an amino group, an amino group-containing compound (e-4), a catalyst, and an organic solvent were charged at the following ratios.

[Polymerization tank]
200 parts of resin solution for pressure-sensitive adhesive containing copolymer (B) [Drip device]
Triethylamine (e-4) 2 parts tetrabutylammonium tetrahydroborate (catalyst) 0.5 parts ethyl ethanoate 10 parts

After replacing the air in the polymerization tank with nitrogen gas, the temperature was raised to 90 ° C. while stirring the solution. Next, the amino group-containing compound (e-4) mixture was added dropwise to the stirring solution at a constant speed over 1 hour from a dropping device. After completion of the dropwise addition, the mixture was further aged for 6 hours with stirring, and then 36 parts of ethyl ethanoate was added and cooled to room temperature to obtain a pressure-sensitive adhesive resin solution containing a copolymer (B-2). This solution is colorless and transparent, has a non-volatile content of 25.5% by weight and a viscosity of 5,000 mPa · s. This pressure-sensitive adhesive resin has an acid value of 5.4 mgKOH / g and an amine value of 0.2 mgKOH.
/ G, glass transition temperature -36 ° C, weight average molecular weight 1,300,000. In addition, the resin for pressure-sensitive adhesive is amine compound (from C13 nuclear magnetic resonance spectrum (C13-NMR)).
It was confirmed that about 96% of e4) reacted with side chain (I) to form side chain (II).

(Synthesis Example 2)
The composition of the monomer used in the step (1) of Synthesis Example 1 was changed, and charged into the polymerization tank and the dropping device at the following ratios, respectively.
[Polymerization tank]
N-butyl propenoate (a-2) 34.6 parts methyl propenoate (a-2) 15 parts propenoic acid (a-1) 0.3 part 2-hydroxyethyl 2-methylpropenoate (A) 0.1 Part Methyl ethanoate 30 parts 2,2'-Azobisisobutyronitrile 0.05 part [Drip device]
N-butyl propenoate (a-2) 49.8 parts propenoic acid (a-1) 0.2 parts ethyl ethanoate 36 parts 2,2'-azobisisobutyronitrile 0.05 part

After replacing the air in the polymerization tank with nitrogen gas, the mixture was heated to 90 ° C. while stirring and reacted for 8 hours, and the copolymer (A) was contained in the same manner as in Step (1) of Synthesis Example 1. A resin solution for pressure-sensitive adhesive was obtained. This solution is colorless and transparent, has a non-volatile content of 30.3% by weight, and a viscosity of 7,600 mPa.
S, the pressure sensitive adhesive resin has an acid value of 3.9 mg KOH / g, glass transition temperature of -39 ° C.
The weight average molecular weight was 1,100,000.

(Synthesis Example 3)
The cyclic amide compound (D) used in step (2) of Synthesis Example 1 was converted to δ-valerolactam 6
It was prepared in the same manner as in Synthesis Example 1 except that 200 parts of the resulting copolymer (B) solution was used in step (3), and the nonvolatile content was reduced to about 30 with ethyl ethanoate. A copolymer (B-) which is adjusted to wt%, is colorless and transparent, has a non-volatile content of 25.2%, and a viscosity of 4,000 mPa · s.
A resin solution for pressure-sensitive adhesive containing 2) was obtained. The pressure sensitive adhesive resin has an acid value of 5.5 mg KO.
H / g, amine value 0.3 mgKOH / g, glass transition temperature -37 ° C., weight average molecular weight 12
It was 7,000. In the above resin, the side chain (II) -derived copolymer (B-2) had a content of about 95%.

(Synthesis Example 4)
The cyclic amide compound (D) used in the step (2) of Synthesis Example 1 was converted to γ-butyrolactam 6
It was prepared in the same manner as in Synthesis Example 1 except that 200 parts of the resulting copolymer (B) solution was used in step (3), and the nonvolatile content was reduced to about 30 with ethyl ethanoate. A copolymer (B-) which is adjusted to% by weight, is colorless and transparent, has a non-volatile content of 30.3% and a viscosity of 3,800 mPa · s.
A solution of a pressure-sensitive adhesive resin containing 2) was obtained. The pressure sensitive adhesive resin has an acid value of 5.2 mgK.
OH / g, amine value 0.2 mgKOH / g, glass transition temperature -38 ° C., weight average molecular weight 1
130,000. In the resin, the side chain (II) -derived copolymer (B-
2) was about 97% content.

(Synthesis Example 5)
Step (3) of Synthesis Example 1 except that triethylamine, which is the amino group-containing compound (e-4) used in Step (3) of Synthesis Example 1, was changed to 4 parts of phenyl isocyanate of the isocyanate group-containing compound (e-3). ) To prepare a non-volatile content of about 2 with ethyl ethanoate.
The pressure-sensitive adhesive resin solution was adjusted to 5% by weight and was colorless and transparent, and contained a copolymer (B-2) having a non-volatile content of 25.2% and a viscosity of 4,500 mPa · s. The pressure-sensitive adhesive resin has an acid value of 5.
It was 5 mg KOH / g, glass transition temperature -35 ° C., and weight average molecular weight 13,320,000. In the above resin, the side chain (II) -derived copolymer (B-2) had a content of about 95%.

(Synthesis Example 6)
Step of Synthesis Example 1 except that triethylamine, which is the amino group-containing compound (e-4) used in Step (3) of Synthesis Example 1, was changed to 6 parts of phenyl glycidyl ether of glycidyl group-containing compound (e-2) ( Prepared in the same manner as 3), colorless and transparent, non-volatile content 25.1%
A pressure-sensitive adhesive resin solution containing a copolymer (B-2) having a viscosity of 4,700 mPa · s was obtained. The pressure-sensitive adhesive resin had an acid value of 4.6 mgKOH / g, a glass transition temperature of −33 ° C., and a weight average molecular weight of 1,330,000. In the above resin, the side chain (II) -derived copolymer (B-2) had a content of about 95%.

(Synthesis Example 7)
The composition of the monomer used in the step (1) of Synthesis Example 1 was changed, and charged into the polymerization tank and the dropping device at the following ratios, respectively.
[Polymerization tank]
2-ethylhexyl propenoate (a-2) 35 parts n-butyl propenoate (a-2) 5 parts methyl propenoate (a-2) 5 parts propenoic acid tetramethylpiperidine (a-1) 5 parts methyl ethanoate 30 Part 2,2′-Azobisisobutyronitrile 0.05 part [Drip device]
2-ethylhexyl propenoate (a-2) 45 parts tetramethylpiperidine propenoate (a-1) 5 parts ethyl ethanoate 36 parts 2,2'-azobisisobutyronitrile 0.05 part

After replacing the air in the polymerization tank with nitrogen gas, the mixture was heated to 90 ° C. while stirring and reacted for 8 hours, and the copolymer (A) was contained in the same manner as in Step (1) of Synthesis Example 1. A solution of a pressure sensitive adhesive resin was obtained. This solution is light yellow and transparent, has a non-volatile content of 30.2% by weight, and a viscosity of 5,000.
The pressure-sensitive adhesive resin had an amine value of 24.9 mgKOH / g, a glass transition temperature of −40 ° C., and a weight average molecular weight of 610,000.

Resin solution for pressure-sensitive adhesive containing copolymer (A) obtained in the above step (1), cyclic amide (D
), The catalyst and the organic solvent were charged in the following ratios, respectively, and the rest was reacted in the same manner as in Synthesis Example 1, and the nonvolatile content was adjusted to about 30% by weight with ethyl ethanoate, and the copolymer (B) was contained. A transparent solution of a pressure sensitive adhesive resin was obtained.

[Polymerization tank]
200 parts of resin solution for pressure-sensitive adhesive containing copolymer (A) [Drip device]
ε-caprolactam (D) 120 parts tetrabutylammonium tetrahydroborate (catalyst) 0.5 parts ethyl ethanoate 60 parts

This solution is colorless and transparent, has a non-volatile content of 30.1% by weight and a viscosity of 3,800 mPa · s. The pressure-sensitive adhesive resin has an amine value of 8.1 mgKOH / g, a glass transition temperature of −42 ° C., and a weight average. It was a resin with a molecular weight of 650,000.

Next, Synthesis Example except that triethylamine, which is the amino group-containing compound (e-4) used in Step (3) of Synthesis Example 1, was changed to 0.8 part of phenyl isocyanate of the isocyanate group-containing compound (e-3). Preparation is performed in the same manner as in step (3) of 1, and the non-volatile content is adjusted to about 30% by weight with ethyl ethanoate, which is colorless and transparent, non-volatile content of 30.3%, viscosity of 3,200 mPa
-The resin solution for pressure sensitive adhesives containing the copolymer (B-2) of s was obtained. The pressure-sensitive adhesive resin has an amine value of 2.0 mgKOH / g, a glass transition temperature of −41 ° C., and a weight average molecular weight of 580,0.
00. In the resin, the side chain (II) -derived copolymer (B-2) is about 94.
% Content.

(Synthesis Example 8)
The composition of the monomer used in the step (1) of Synthesis Example 7 was changed, and charged into the polymerization tank and the dropping device at the following ratios respectively. (A)
A transparent solution of the pressure sensitive adhesive resin was obtained.
[Polymerization tank]
2-ethylhexyl propenoate (a-2) 39.6 parts n-butyl propenoate (a-2) 5 parts methyl propenoate (a-2) 5 parts propellate tetramethylpiperidine (a-1) 0.3 part Methyl ethanoate 30 parts 2,2'-azobisisobutyronitrile 0.05 part [Drip device]
2-ethylhexyl propenoate (a-2) 49.9 parts tetramethylpiperidine propenoate (a-1) 0.2 parts ethyl ethanoate 36 parts 2,2'-azobisisobutyronitrile 0.05 part

This solution was colorless and transparent, had a non-volatile content of 30.4% and a viscosity of 6,000 mPa · s.
The pressure-sensitive adhesive resin had an amine value of 1.2 mgKOH / g, a glass transition temperature of −43 ° C., and a weight average molecular weight of 710,000.

(Synthesis Example 9)
The cyclic amide compound (D) used in step (2) of Synthesis Example 7 was converted to δ-valerolactam 1
Preparation was carried out in the same manner as in Synthesis Example 7 except that 200 parts of the resulting resin solution for pressure-sensitive adhesive containing the copolymer (B) was used in step (3). The non-volatile content was adjusted to about 30% by weight with ethyl acid, colorless and transparent, non-volatile content 30.3%, viscosity 3,100
A pressure-sensitive adhesive resin solution containing a mPa · s copolymer (B-2) was obtained. The pressure-sensitive adhesive resin has an amine value of 1.9 mgKOH / g, a glass transition temperature of −42 ° C., and a weight average molecular weight of 55.
It was 0.00. In the resin, the content of the side chain (II) -derived copolymer (B-2) was about 98%.

(Synthesis Example 10)
The cyclic amide compound (D) used in the step (2) of Synthesis Example 7 was converted to γ-butyrolactam 1
Preparation was carried out in the same manner as in Synthesis Example 7 except that 200 parts of the resulting resin solution for pressure-sensitive adhesive containing the copolymer (B) was used in step (3). The non-volatile content was adjusted to about 30% by weight with ethyl acid, colorless and transparent, non-volatile content 30.0%, viscosity 3,300
A resin solution for pressure-sensitive adhesive containing a mPa · s copolymer (3) was obtained. The pressure-sensitive adhesive resin has an amine value of 2.0 mgKOH / g, a glass transition temperature of −43 ° C., a weight average molecular weight of 520,
000. In the resin, the side chain (II) -derived copolymer (B-2) is about 9%.
The content ratio was 7%.

(Synthesis Example 11)
Preparation was performed in the same manner as in Synthesis Example 7 except that the number of parts of phenyl isocyanate was changed to 0.6 parts in Step (3) of Synthesis Example 7, and the nonvolatile content was about 30% by weight with ethyl ethanoate.
A copolymer (B) which is colorless and transparent, has a non-volatile content of 30.5% and a viscosity of 3,200 mPa · s.
-2) containing a pressure-sensitive adhesive resin solution. The pressure sensitive adhesive resin has an amine value of 3.5 m.
It was gKOH / g, glass transition temperature -41 degreeC, and the weight average molecular weight 570,000. still,
In the resin, the side chain (II) -derived copolymer (B-2) had a content of about 98%.

(Synthesis Example 12)
Other than changing the amino group-containing compound (e-4) used in the step (3) of Synthesis Example 7 to 1.5 parts of isobenzofuran-1,3-dione as the acid anhydride group-containing compound (e-1). Was prepared in the same manner as in Synthesis Example 7, and the non-volatile content was adjusted to about 30% by weight with ethyl ethanoate, which was a colorless and transparent copolymer having a non-volatile content of 30.2% and a viscosity of 5,000 mPa · s. B-2)
A pressure-sensitive adhesive resin solution was obtained. The resin for pressure sensitive adhesive has an acid value of 8.6 mgKOH / g
, Amine value 0.1 mg KOH / g, glass transition temperature -35 ° C., weight average molecular weight 680,0
00. In the resin, the side chain (II) -derived copolymer (B-2) is about 98.
% Content.

(Synthesis Example 13)
The composition of the monomer used in Synthesis Example 1 was changed, and charged into the polymerization tank and the dropping device at the following ratios respectively. Otherwise, the polymerization was performed in the same manner as in Synthesis Example 1, and the copolymer (A) was contained. A transparent solution of a pressure sensitive adhesive resin was obtained.
[Polymerization tank]
2-methylpropenoate lauryl (a-2) 18 parts ethyl propenoate (a-2) 20 parts ethanylpyrrolidone (a-2) 5 parts 2,4-diamino-6-methacryloyloxyethyl-1,3,5 -Triazine
(A-1) 7 parts ethyl ethanoate 30 parts 2,2'-azobisisobutyronitrile 0.05 part [Drip device]
2 parts lauryl 2-methylpropenoate (a-2) 5 parts ethyl propenoate (a-2) 40 parts 2,4-diamino-6-methacryloyloxyethyl-1,3,5-triazine
(A-1) 5 parts ethyl ethanoate 36 parts 2,2'-azobisisobutyronitrile 0.05 part

After replacing the air in the polymerization tank with nitrogen gas, the mixture was heated to 90 ° C. while stirring and reacted for 8 hours, and the copolymer (A) was contained in the same manner as in Step (1) of Synthesis Example 1. A resin solution for pressure-sensitive adhesive was obtained. This solution is colorless and transparent, has a non-volatile content of 30.1%, and a viscosity of 8,500 mPa · s.
s. The pressure-sensitive adhesive resin had an amine value of 61.0 mgKOH / g, a glass transition temperature of −28 ° C., and a weight average molecular weight of 1,650,000.

The pressure-sensitive adhesive resin solution containing the copolymer (A) obtained in the above step (1), the cyclic amide compound (D), the catalyst and the organic solvent were charged in the following ratios, respectively, and otherwise, Synthesis Example 13 and The reaction was conducted in the same manner, and the non-volatile content was adjusted to about 30% by weight with ethyl ethanoate to obtain a transparent solution of the pressure-sensitive adhesive resin containing the copolymer (B).

[Polymerization tank]
200 parts of resin solution for pressure-sensitive adhesive containing copolymer (A) [Drip device]
γ-nonalactam (D) 160 parts tetrabutylphosphonium hexafluorophosphate (catalyst) 0.5 parts ethyl ethanoate 60 parts

This solution is colorless and transparent, has a non-volatile content of 30.3% by weight, and a viscosity of 7,800 mPa · s. The pressure-sensitive adhesive resin has an amine value of 8.2 mg KOH / g, a glass transition temperature of −32 ° C., and a weight average. It was a resin with a molecular weight of 1,580,000.

Next, except that triethylamine which is the amino group-containing compound (e-4) used in the step (3) of Synthesis Example 1 was changed to 1 part of phenyl isocyanate of the isocyanate group-containing compound (e-3), Synthesis Example 1 Preparation was carried out in the same manner as in step (3), and the non-volatile content was adjusted to about 30% by weight with ethyl ethanoate, which was colorless and transparent, the non-volatile content was 30.4%, and the viscosity was 7,200 mPa · s.
A pressure-sensitive adhesive resin solution containing the copolymer (B-2) was obtained. The pressure-sensitive adhesive resin has an amine value of 0.9 mg KOH / g, a glass transition temperature of −30 ° C., and a weight average molecular weight of 1,500,0.
00. In the resin, the side chain (II) -derived copolymer (B-2) is about 98.
% Content.

(Synthesis Example 14)
The composition of the monomer used in Synthesis Example 13 was changed, and charged into the polymerization tank and the dropping device at the following ratios respectively. Otherwise, the polymerization was performed in the same manner as in Synthesis Example 1, and the copolymer (A) was contained. A transparent solution of a pressure sensitive adhesive resin was obtained.
[Polymerization tank]
2-Methylpropenoate lauryl (a-2) 24.9 parts Ethyl propenoate (a-2) 20 parts Ethanylpyrrolidone (a-2) 5 parts Propenoic acid (a-1) 0.1 part Ethane ethanoate 30 Part 2,2′-Azobisisobutyronitrile 0.05 part [Drip device]
Lauryl 2-methylpropenoate (a-2) 9.9 parts ethyl propenoate (a-2) 40 parts propenoic acid (a-1) 0.1 part ethyl ethanoate 36 parts 2,2′-azobisisobuty Ronitrile 0.05 parts

After the air in the polymerization tank was replaced with nitrogen gas, the mixture was heated to 90 ° C. while stirring and reacted for 8 hours, in the same manner as in the step (1) of Synthesis Example 1, and the feeling of containing the copolymer (A). A resin solution for pressure adhesive was obtained. This solution is colorless and transparent, has a non-volatile content of 30.2%, and a viscosity of 8,500 mPa · s.
Met. The resin for pressure-sensitive adhesives has an acid value of 1.6 mgKOH / g and a glass transition temperature of -30 ° C.
The weight average molecular weight was 1,350,000.

The resin solutions for pressure-sensitive adhesives obtained in Synthesis Examples 1 to 14 are the solution appearance, nonvolatile content (NV), viscosity (Vis), weight average molecular weight (Mw), glass transition temperature (Tg), acid value (AV). The production rate of amine value (AmV) and side chain (II) was evaluated as follows. The results are shown in Table 1.

The symbols in Table 1 are as follows.
PAEH: 2-ethylhexyl propenoate, PAB: n-butyl propenoate, PAM:
Methyl propenoate, PAE: ethyl propenoate, PA: propenoic acid, MPAHE: 2-hydroxyethyl 2-methylpropenoate, MPAL: lauryl 2-methylpropenoate, PA
TMP: tetramethylpiperidine propenoate, PATAZ: 2,4-diamino-6-methacryloyloxyethyl-1,3,5-triazine, EP: etanylpyrrolidone, EAc
: Ethyl ethanoate, MeAc: methyl ethanoate, εCL: ε-caprolactam, γBL:
γ-butyrolactam, δVL: δ-valerolactam, γNL: γ-nonalactam, TEA
: Triethylamine, PhEp: Phenylglycidyl ether, PhAnh: Isobenzofuran-1,3-dione, PhNCO: Phenyl isocyanate, TBAB: Tetrabutylammonium tetrahydroborate, TBPHFP: Tetrabutylphosphonium hexafluorophosphate.

<Appearance of solution>
The appearance of the pressure-sensitive adhesive resin solution was visually evaluated.

<Measurement of nonvolatile content concentration (NV)>
About 1 g of a resin solution for pressure-sensitive adhesive was weighed in a metal container, dried in an oven at 150 ° C. for 20 minutes, and the residue was weighed to calculate the residual ratio, thereby obtaining a non-volatile concentration (%). .

<Measurement of solution viscosity (Vis)>
The temperature of the pressure-sensitive adhesive resin solution was maintained at 25 ° C., and the viscosity (mPa · s) was measured using a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd.) at 12 rpm for 1 minute.

<Measurement of weight average molecular weight (Mw)>
The pressure sensitive adhesive resin is dissolved in tetrahydrofuran and separated and quantified by the difference in molecular size by liquid chromatography using GPC (gel permeation chromatograph) “HPC-8020” manufactured by Tosoh Corporation. Weight average molecular weight of coalescence (Mw)
Was calculated in terms of polyethenylbenzene.

<Measurement of glass transition temperature (Tg)>
Robot DSC (differential scanning calorimeter, “RDC220” manufactured by Seiko Instruments Inc.)
A "SSC5200 disk station" (manufactured by Seiko Instruments Inc.) was connected to and used for measurement.
Apply and dry the resin solution for pressure sensitive adhesive on the peeled polyester film, scrape about 10 mg of the dried copolymer, put it in an aluminum pan as a sample, weigh it and set it in a differential scanning calorimeter, The aluminum pan of the same type without a sample was used as a reference, heated at a temperature of 100 ° C. for 5 minutes, and then rapidly cooled to −120 ° C. using liquid nitrogen. Thereafter, the temperature was raised at 10 ° C./min, and the glass transition temperature (from the DSC chart obtained during the temperature rise (
Tg) (° C) was determined.

<Measurement of acid value (AV)>
About 1.5 g of each sample was accurately weighed in a stoppered Erlenmeyer flask and dissolved by adding 100 ml of a toluene / ethanol (2/1 by volume) mixture. To this was added a phenolphthalein test solution as an indicator, which was held for 30 seconds, and then titrated with a 0.1N alcoholic potassium hydroxide solution until the solution turned light red.
The acid value (mgKOH / g) was determined by the following equation as the value of the resin in the dry state.
Acid value (mgKOH / g) = {(5.611 × a × F) / S} / (Nonvolatile content concentration / 10
0)
Where S: Amount of sample collected (g)
a: Consumption of 0.1N alcoholic potassium hydroxide solution (ml)
F: Potency of 0.1N alcoholic potassium hydroxide solution

<Measurement of amine value (AmV)>
About 1.5 g of each sample is accurately weighed in a stoppered Erlenmeyer flask and dissolved by adding 100 ml of a toluene / ethanol (2/1 by volume) mixture. In addition, carbon disulfide is exactly 2m
l was added and stirred. To this, phenolphthalein reagent is added as an indicator and lasts for 30 seconds. Thereafter, the solution is titrated with a 0.1N alcoholic potassium hydroxide solution until the solution becomes light red.
The amine value was determined as the total amine value of primary and secondary by the following formula. The amine value was a numerical value of the dry state of the resin (unit: mgKOH / g).
Amine value (mgKOH / g) = [{(ba) × F × 5.611} / S] / (Nonvolatile content concentration / 100) −D
Where S: Amount of sample collected (g)
a: Consumption of 0.1N alcoholic potassium hydroxide solution (ml)
b: Consumption of 0.1N alcoholic potassium hydroxide solution in the empty experiment (ml)
F: Potency of 0.1N alcoholic potassium hydroxide solution
D: Acid value (mgKOH / g)

<Production rate of side chain (II)>
The production rate of the side chain (II) was determined using a C13 nuclear magnetic resonance spectrum (C13-NMR).
The pressure-sensitive adhesive resin solution is applied to a release liner and dried. About 10 g of the dried pressure-sensitive adhesive resin is scraped and placed in a 10φ measuring tube (height: about 5 cm).
After adding 2 ml and about 5 ml of chlorobenzene, it was covered and dissolved in an oven at 120 ° C. for 1 hour to obtain a measurement sample. This measurement sample was measured using a nuclear magnetic resonance absorber (manufactured by JEOL Ltd .: JMN-LA400) under the conditions of a measurement temperature of 120 ° C. and a spin intensity of 17 rpm.
Nuclear magnetic resonance absorption shows various patterns due to chemical structure. Same CH bond or C
Since a signal appears at a chemical shift that differs depending on the surrounding structure even in the case of -O bond, pay attention to the characteristic bond in the structure of the copolymer in advance, and use it for the quantification of the copolymer using the intensity of the signal of the chemical shift. be able to. The rate of formation of the copolymer (B-2) having a side chain (II) in the pressure-sensitive adhesive resin is determined by the chemical shift of the carbon atom directly linked to the active hydrogen group expressed by the ring-opening reaction of the cyclic ester compound. The production rate was determined by the identification.

Example 1
Ethyl ethanoate is added to 100 parts of the resin solution for pressure-sensitive adhesives containing the copolymer (B-2) obtained in Synthesis Example 1, and TDI / MHPD (trimethyl ether) is further added as the reactive compound (C). 10 parts of 2-methyl-2- (hydroxymethyl) propane-1,3-diol adduct of diisocyanate) was added to a non-volatile content of about 20%, and stirred well to obtain a pressure-sensitive adhesive. .
This was coated on the release liner so that the thickness after drying was 25 μm, and dried at 100 ° C. for 2 minutes to form an adhesive layer.
After drying, one side of a multilayered polarizing film (also referred to as a polarizing plate) in which both sides of a polyethenol (PEA) polarizer are sandwiched between triacetyl cellulose protective films is bonded to the adhesive layer. Layer / TAC film / PEA / TAC film ”was further aged for one week under conditions of a temperature of 23 ° C. and a relative humidity of 50% to obtain a pressure-sensitive adhesive film.

(Comparative Example 1)
Instead of the pressure-sensitive adhesive resin solution containing the copolymer (B-2) obtained in Synthesis Example 1, a pressure-sensitive type containing the copolymer (A) obtained in Step (1) of Synthesis Example 1 An attempt was made to prepare a pressure-sensitive adhesive film in the same manner as in Example 1 except that the adhesive resin solution was used. However, the viscosity of the pressure-sensitive adhesive suddenly increased and could not be applied.

(Comparative Example 2)
Instead of the pressure-sensitive adhesive resin solution containing the copolymer (B-2) obtained in Synthesis Example 1, the pressure-sensitive adhesive resin solution containing the copolymer (A) obtained in Synthesis Example 2 A pressure-sensitive adhesive film was produced in the same manner as in Example 1 except that was used.

(Examples 2 to 5)
Instead of the pressure-sensitive adhesive resin solution containing the copolymer (B-2) obtained in Synthesis Example 1, pressure-sensitive adhesion containing the copolymer (B-2) obtained in Synthesis Example 3-6. A pressure-sensitive adhesive film was produced in the same manner as in Example 1 except that the agent resin solution was used.

(Examples 6 to 9)
In Example 6, instead of 10 parts of TDI / MHPD as the reactive compound (C) in the resin solution for pressure-sensitive adhesive containing the copolymer (B-2) used in Synthesis Example 1, HBAP (2, 2 ′ -Bishydroxymethylbutanol tris [3- (1-aziridinyl) propionate]) 0
. 1 part, in Example 7, 1 part of TGMXDA (N, N, N ′, N′-tetraglycidyl-m-xylylenediamine), in Example 8, V-05 (“carbodilite V-05” which is a carbodiimide compound): A pressure-sensitive adhesive film was prepared in the same manner as in Example 1 except that 1 part of Nisshinbo Co., Ltd. and 1 part of Al chelate (aluminum tris (acetylacetonate)) were added in Example 9. . In Example 7, the solvent was ethyl ethanoate (
A pressure-sensitive adhesive film was produced in the same manner as in Example 1 except that EAc) was changed to isopropyl alcohol (IPA).

(Comparative Example 3)
Instead of the pressure-sensitive adhesive resin solution containing the copolymer (B-2) obtained in Synthesis Example 1, a pressure-sensitive type containing the copolymer (A) obtained in Step (1) of Synthesis Example 13 An attempt was made to prepare a pressure-sensitive adhesive film in the same manner as in Example 1 except that the adhesive resin solution was used. However, the increase in the viscosity of the pressure-sensitive adhesive suddenly progressed and could not be applied.

(Comparative Example 4)
Instead of the pressure-sensitive adhesive resin solution containing the copolymer (B-2) obtained in Synthesis Example 1, a pressure-sensitive type containing the copolymer (A) obtained in Step (1) of Synthesis Example 14 A pressure-sensitive adhesive film was produced in the same manner as in Example 1 except that the adhesive resin solution was used.

(Example 10)
Instead of the pressure-sensitive adhesive resin solution containing the copolymer (B-2) obtained in Synthesis Example 1, a pressure-sensitive type containing the copolymer (B) obtained in Step (2) of Synthesis Example 13 Except for changing the number of parts of TDI / MHPD used as the reactive compound (C) to 1 part using the resin solution for adhesives,
In the same manner as in Example 1, a pressure-sensitive adhesive film was produced.

(Example 11)
For the pressure-sensitive adhesive containing the copolymer (B-2) obtained in Synthesis Example 13 instead of the resin solution for the pressure-sensitive adhesive containing the copolymer (B-2) obtained in Synthesis Example 1. Example 1 except that the resin solution was used and the number of parts of TDI / MHPD used as the reactive compound (C) was changed to 1 part.
In the same manner, a pressure-sensitive adhesive film was produced.

(Examples 12 and 13)
Instead of TDI / MHPD as the reactive compound (C), the resin solution for pressure-sensitive adhesive containing the copolymer (B-2) obtained in Synthesis Example 13 was replaced with XDI / EHPD (Xylylene) in Example 12. 2-isocyanate 2-methyl-2- (hydroxymethyl) propane-1,3-diol adduct), and in Example 13, 1 part each of HMDI / burette (hexamethylene diisocyanate burette adduct) was added. Except for this, a pressure-sensitive adhesive film was produced in the same manner as in Example 1.

(Example 14)
Pressure Sensitive Adhesive Resin Solution 100 Comprising Copolymer (B) Obtained in Step (2) of Synthesis Example 7
Ethyl ethanoate is added to the part, and TDI / MHPD is further added as the reactive compound (C).
(Tolylene diisocyanate 2-methyl-2- (hydroxymethyl) propane-1,3-diol adduct) Add 1 part, adjust the non-volatile content to about 20%, stir well, pressure sensitive An adhesive was obtained.
This was coated on a release liner so that the thickness after drying was 20 μm, and dried at 100 ° C. for 2 minutes to form an adhesive layer.
After drying, a 38 μm thick PET film is bonded to the adhesive layer to form a laminate structure of “release liner / adhesive layer / PET film”, and further aged for one week at a temperature of 23 ° C. and a relative humidity of 50%. A pressure adhesive film was obtained.

(Example 15)
A pressure-sensitive type containing the copolymer (B-2) obtained in Synthesis Example 7 instead of the pressure-sensitive adhesive resin solution containing the copolymer (B) obtained in the step (2) of Synthesis Example 7. A pressure-sensitive adhesive film was produced in the same manner as in Example 14 except that the adhesive resin solution was used.

(Examples 16 and 17)
Instead of TDI / MHPD as the reactive compound (C), the resin solution for pressure-sensitive adhesive containing the copolymer (B-2) obtained in Synthesis Example 7 was replaced with XDI / MHPD (Xylidine) in Example 16. 1 part of 2-methyl-2- (hydroxymethyl) propane-1,3-diol adduct of diisocyanate) and 1 part of HMDI / burette (hexamethylene diisocyanate burette adduct) in Example 17 were added. Except for this, a pressure-sensitive adhesive film was produced in the same manner as in Example 14.

(Comparative Example 5)
Instead of the pressure-sensitive adhesive resin solution containing the copolymer (B) obtained in Step (2) of Synthesis Example 7, the copolymer (A) obtained in Step (1) of Synthesis Example 7 was used. A pressure-sensitive adhesive film was produced in the same manner as in Example 14 except that the pressure-sensitive adhesive resin solution was used.

(Comparative Example 6)
A pressure-sensitive adhesive containing the copolymer (B) obtained in Synthesis Example 8 instead of the pressure-sensitive adhesive resin solution containing the copolymer (B) obtained in Step (2) of Synthesis Example 7 A pressure-sensitive adhesive film was produced in the same manner as in Example 14 except that the resin solution was used.

(Comparative Example 7)
Instead of the pressure-sensitive adhesive resin solution containing the copolymer (B-2) obtained in Synthesis Example 1, a pressure-sensitive type containing the copolymer (A) obtained in Step (1) of Synthesis Example 14 Using the adhesive resin solution,
A pressure-sensitive adhesive film was produced in the same manner as in Example 1 except that 0.5 part of 1-butyl-3-methylpyridinium trifluoromethanesulfonate was added as an antistatic agent.

The pot life and coating processability of the obtained pressure-sensitive adhesive were evaluated by the following methods. The results are shown in Table 2. Moreover, the following items were evaluated about the obtained pressure sensitive adhesive film. The evaluation results are shown in Table 3.

<Evaluation method of pot life>
About the obtained pressure sensitive adhesive, the viscosity at 25 ° C. is changed every 10 hours until 10 hours later,
Using a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd.), measurement was performed under conditions of 12 rpm and 1 minute rotation, and the pot life was evaluated in three stages.
○: “There is no change in viscosity. The rate of increase in viscosity up to 8 hours is less than 2 times. Very good.”
Δ: “A slight increase in viscosity is observed, and the rate of increase in viscosity up to 5 hours is less than twice. Good.”
X: “A sudden increase in viscosity was observed and gelled in less than 5 hours.

<Evaluation method of coatability>
The obtained pressure-sensitive adhesive was applied to a release liner with a comma coater at a speed of 2 m / min, dried in a 100 ° C. oven to form an adhesive layer with a thickness of 25 μm, and a thickness on the surface of the adhesive layer. A 50 μm polyester film was laminated to prepare a pressure-sensitive adhesive film. The state of the adhesive layer surface (coating surface) after peeling off the release liner was visually observed, and 3
Rated by stage.
○: “Smooth coated surface was obtained. Very good.”
Δ: “Slight repellency and foaming are observed at the end of the coated surface, but good”
×: “Repelling, foaming and streaking are recognized on the coated surface, and there are practical problems.”

<Antistatic evaluation method (surface resistance value)>
The release liner of the pressure-sensitive adhesive film is peeled off, and the surface resistance value of the exposed adhesive layer surface is 2
Under each condition of 3 ° C.-35, 45, 55% RH, measurement was made using a surface resistance measuring device (Mitsubishi Chemical Corporation: MCT-HT450) (unit: Ω / □), and antistatic performance evaluation and did.

<Evaluation method of optical characteristics>
The pressure-sensitive adhesives obtained in the examples and comparative examples were coated and dried on the release liner in the same manner as described above to form an adhesive layer with a thickness of 25 μm, and the release liner was bonded to the surface of the pressure-sensitive adhesive. A film was obtained. After this was aged for 1 week at a temperature of 23 ° C. and a relative humidity of 50%, both release liners were removed, and the appearance of the adhesive layer was visually judged.
NDH-300A ”(manufactured by Nippon Denshoku Industries Co., Ltd.).
○: “Good appearance. HAZE: less than 1. No problem at all.”
Δ: “No cloudiness or the like is observed, and HAZE: 1 or more and less than 3. Can be used practically.”
X: “Slightly cloudy or HAZE: 3 or more. There is a practical problem. Unusable.”

<Evaluation method of removability (reworkability)>
The obtained pressure-sensitive adhesive film 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, 50 ° C.
Was held in an autoclave at 5 atm for 20 minutes to obtain a laminate of a pressure-sensitive adhesive film and a glass plate. After leaving this laminate at 23 ° C. and 50% relative humidity for 1 week, 180 °
The glass surface was peeled off at a speed of 300 mm / min in the degree direction, and the fogging of the glass surface after peeling was visually observed and evaluated in three stages.
○: “No cloudiness and good appearance. No problem”
Δ: “Slight cloudiness is observed, but there is no practical problem”
X: “Transfer of the adhesive layer is recognized over the entire surface, which is not practical”.

<Method for evaluating heat resistance and heat and humidity resistance>
The obtained pressure-sensitive adhesive film is cut into a size of 150 mm × 80 mm, the release liner is peeled off, and a laminator is placed on both surfaces of a 1.1 mm thick float glass plate so that the absorption axes of the respective polarizing plates are orthogonal to each other. Used to stick. Subsequently, the glass plate with the polarizing plate attached thereto was held in an autoclave at 50 ° C. and 5 atm for 20 minutes to obtain a laminate of the pressure-sensitive adhesive sheet and the glass plate.
The laminate was left to stand at 80 ° C. for 1000 hours and at 100 ° C. for 1000 hours, and the floating peeling, deviation, and light leakage (white spots) when light was transmitted through the laminate were visually observed, The heat resistance was evaluated.
In addition, when the laminate was left to stand at 60 ° C. and a relative humidity of 90% for 1000 hours and at 80 ° C. and a relative humidity of 90% for 1000 hours, Light leakage (white spots) was visually observed to evaluate wet heat resistance.
Here, “displacement” is the displacement of the sticking position observed around the polarizing plate attached to the glass due to contraction of the polarizing plate.
The heat resistance and moist heat resistance were evaluated based on the following four criteria. In Examples 14 to 17 and Comparative Examples 5 and 6, since the base material was a PET film, only “floating peeling” was evaluated.
A: “Floating peeling, whitening, and displacement were not recognized at all, and it was good.”
○: “No floating peeling or whitening is observed, the displacement is less than 0.2 mm, and there is no problem in practical use.”
Δ: “Slightly floating peeling or whitening is observed, but the deviation is less than 0.2 to 0.5 mm, and there is no practical problem.”
×: “There are floating floats and white spots that are not practical.”

From the results of Table 3, since Comparative Examples 1 and 3 had an acid value or an amine value of 50 mgKOH / g or more, they could not be applied. Moreover, since Comparative Examples 2, 4-6 do not have a cyclic amide compound (D), it turns out that sufficient antistatic performance cannot be obtained. Further, in Comparative Example 7, the releasability cannot be maintained due to bleeding of the antistatic agent, and further, when left at a severe temperature or a high temperature and high humidity for a long period of time, foaming or peeling off occurs. It turns out that it is inferior to durability.
On the other hand, the pressure-sensitive adhesive and pressure-sensitive adhesive film using the pressure-sensitive adhesive resin obtained by the method for producing the pressure-sensitive adhesive resin of the present invention have coating processability, heat resistance, and heat and humidity resistance. It can be seen that the optical properties, antistatic properties and reworkability of the optical film are excellent.

The pressure-sensitive adhesive of the present invention is suitable for use as an optical member, and in addition to general labels and seals, paints, elastic wall materials, coating waterproofing materials, flooring materials, tackifiers, adhesives, laminated structures Adhesives, sealing agents, molding materials, surface modification coating agents, binders (magnetic recording media, ink binders, casting binders, fired brick binders, graft materials, microcapsules, glass fiber sizing, etc.), urethane foam (hard , Semi-rigid, soft), urethane RIM, UV / EB cured resin, high solid paint, thermosetting elastomer, microcellular, textile processing agent, plasticizer, sound absorbing material, vibration damping material, surfactant, gel coat agent, artificial Marble resin, impact resistance imparting agent for artificial marble, resin for ink, film (laminate adhesive, protective film, etc.) , Glass resin combined, reactive diluent, various molding materials,
It can be used very effectively as a raw material for elastic fibers, artificial leather, synthetic leather, and various resin additives and raw materials.

Claims (14)

A pressure-sensitive adhesive comprising a copolymer (B) having a side chain (I) having an active hydrogen group at its terminal, and a reactive compound (C),
The side chain (I) is formed by a ring-opening reaction between the active hydrogen group of the copolymer (A) and the cyclic amide compound (D),
The copolymer (A) is a monomer copolymer containing an active hydrogen group-containing α, β-unsaturated monomer (a-1),
A pressure-sensitive adhesive, wherein the active hydrogen group of the active hydrogen group-containing α, β-unsaturated monomer (a-1) is at least a carboxyl group or an amino group . Cyclic amide compound (D) is a pressure sensitive adhesive according to claim 1, characterized in that a compound having a heterocycle of 3 to 18 carbon atoms. The pressure-sensitive adhesive according to claim 1 or 2, wherein the cyclic amide compound (D) is a lactam (d). The pressure-sensitive adhesive according to any one of claims 1 to 3 , wherein the copolymer (B) has an amine value of 0.1 to 50 mgKOH / g. The pressure-sensitive adhesive according to any one of claims 1 to 3 , wherein the copolymer (B) has an acid value of 0.1 to 50 mgKOH / g. The pressure-sensitive adhesive according to claim 4, wherein the copolymer (B) has a side chain (II) obtained by reacting an active hydrogen group at the terminal of the side chain (I) with a sealing compound (E). Agent. 6. The pressure-sensitive adhesive according to claim 5, wherein the copolymer (B) has a side chain (II) obtained by reacting an active hydrogen group at the terminal of the side chain (I) with a sealing compound (E). Agent. The sealing compound (E) is an acid anhydride group-containing compound (e-1), a glycidyl group-containing compound (e-2), an isocyanate group-containing compound (e-3), and an amino group-containing compound (e-4). The pressure-sensitive adhesive according to claim 6 , wherein the pressure-sensitive adhesive is one or more compounds selected from the group consisting of: The sealing compound (E) is an acid anhydride group-containing compound (e-1), a glycidyl group-containing compound (e-2), an isocyanate group-containing compound (e-3), and an amino group-containing compound (e-4). The pressure-sensitive adhesive according to claim 7 . A step of obtaining a copolymer (A) by copolymerizing an active hydrogen group-containing α, β-unsaturated monomer (a-1) and an α, β-unsaturated monomer (a-2). ,and,
A step of generating a side chain (I) by ring-opening addition of an active hydrogen group in the copolymer (A) and the cyclic amide compound (D) ;
Next, the process comprising reacting the end of the side chain (I) with the sealing compound (E) to form a side chain (II ) to obtain a copolymer (B), Manufacturing method of resin for pressure type adhesives. A pressure-sensitive adhesive comprising the resin for pressure-sensitive adhesive obtained by the production method according to claim 10 and a reactive compound (C). A pressure-sensitive adhesive film formed by forming an adhesive layer comprising the pressure-sensitive adhesive according to any one of claims 1 to 9 and 11 on a substrate (F). The laminated body formed by forming the contact bonding layer which consists of a pressure sensitive adhesive in any one of Claims 1-9 and 11 on an optical member. The laminated body formed by laminating | stacking an optical member, the contact bonding layer which consists of a pressure sensitive adhesive in any one of Claims 1-9, and glass sequentially.