JP5834325B2 - Pressure-sensitive adhesive composition and pressure-sensitive adhesive film using the same - Google Patents

Description

  The present invention relates to a pressure-sensitive adhesive composition having novel antistatic performance, and an optical pressure-sensitive adhesive film and laminate using the pressure-sensitive adhesive.

  Due to dramatic advances in electronics in recent years, various flat panel displays (FPD) such as liquid crystal display (LCD), plasma display (PDP), rear projection display (RPJ), EL display, light emitting diode display, etc. It has come to be used as a display device in various fields. For example, these FPDs are not only used indoors, including personal computer displays and liquid crystal televisions, but are also 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. A protective film, an antireflection film, an ITO vapor deposition resin film, or the like is also used for the touch panel.
Such a film is attached to an adherend via a pressure-sensitive adhesive and used in a display device. Since the pressure-sensitive adhesive used in the display device is required to have excellent transparency, a pressure-sensitive adhesive mainly composed of an acrylic resin is generally used.

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

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

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

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

In general, a pressure-sensitive adhesive film has a release film bonded to the adhesive layer for the purpose of protecting the adhesive layer. In use, the release film 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 film 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. Further, it has been pointed out that the same trouble occurs when the polarizing film is charged and adhered to the glass surface for a liquid crystal cell due to static electricity generated when the release film 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 performance decreases with time.

  Internal treatment is a technique of adding an antistatic agent to the polymer during resin molding. Typical antistatic agents in this method 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 further carbon (Patent Documents 1 to 3). To impart antistatic performance using these materials. A considerable amount needs to be added, and more 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, and the cationic system has no problem with antistatic performance, but the thermal stability is low, and the nonionic system There were problems such as low compatibility with polymers.

  As described above, pressure-sensitive adhesives containing these surfactants are easily affected by humidity. Under high humidity, the cohesive force decreases due to the influence of moisture, and an adhesive layer is formed on the adherend during rework. There is a problem that it is easy to remain (so-called “glue residue”). 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 an acrylic resin is used, which is used in electronic tape applications, protective film applications, and polarizing plate fixing applications, respectively. (Patent Documents 5 and 6). However, the use of antistatic pressure-sensitive adhesives containing metal ions in materials used for electrical products and electronic components has the potential for contamination associated with metal ion bleeding, and further, moisture resistance as an adhesive film. Thermal properties are reduced.

  Further, there is known a pressure sensitive adhesive obtained by blending a polyether polyol (Patent Document 7) or a polycaprolactone polyol (Patent Document 8) with an acrylic acid pressure sensitive adhesive containing an acrylic acid resin and a crosslinking agent. 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. Since the polyol being used is easy to absorb moisture due to its high hydroxyl value, 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, pressure-sensitive adhesives (Patent Documents 9 and 10) obtained by copolymerizing an acrylic acid-based monomer to which alkylene oxide is added are known for improving antistatic performance.
In addition, a pressure-sensitive adhesive (Patent Document 11) obtained by copolymerizing a monomer having an acetoacetyl group is known for improving heat resistance.

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 difficult to introduce a very small amount of an acrylic acid monomer to which an alkylene oxide is added.
Therefore, 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 has an auxiliary effect on the antistatic performance. After sticking to the kimono, the polyether polyol (polyether polyol ( As in the case of blending Patent Literature 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 an acrylic acid monomer to which alkylene oxide is added. Therefore, an antistatic agent may be added to the acrylic acid copolymer to which such alkylene oxide is added. In this case, when the antistatic agent moves to the interface on the adherend side and the pressure-sensitive adhesive optical film is peeled off, an improvement in the antistatic performance is recognized. It is known that heat resistance and heat-and-moisture resistance are significantly reduced under high-humidity conditions, such as floating and peeling by the interface transition of the antistatic agent.

  In addition, the pressure-sensitive adhesive disclosed in Patent Document 11 discloses that a monomer component obtained by adding a carbonate group to an acrylic monomer is copolymerized with another monomer component in advance. Yes. However, radical polymerization using an acrylic acid-based monomer having a carbonate group causes a decarboxylation reaction or the like under weakly acidic conditions, resulting in poor polymerization stability and poor copolymerizability. It is difficult to contain in a high concentration, and the antistatic effect as effective as expected cannot be obtained. Further, after being attached to an adherend, when exposed to a high temperature or a high temperature and high humidity condition for a long period of time, the carbonate group contained under the weakly acidic condition is easily decarboxylated as described above, and the optical film The extremely small bubbles accompanying the carbon dioxide generated at the peripheral edge of the slag are generated in a state of being connected in a streak shape.

In view of such a situation, a decrease in the physical properties and optical properties of the pressure sensitive adhesive due to the presence of a permanent antistatic effect is suppressed, and a highly versatile antistatic device that can be used from film label applications to electrical and optical applications. A pressure sensitive adhesive was desired.
Furthermore, pressure-sensitive adhesives that have not only antistatic performance 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 Japanese Patent No. 4667195

  An object of this invention is to provide the pressure-sensitive-type adhesive composition which can obtain the pressure-sensitive-type adhesive film which has antistatic performance, and has further favorable rework property, 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 glass transition temperature obtained by ring-opening addition of a cyclic compound having four or more members having a hydroxyl group and / or a carboxyl group as a functional group and further having two or more oxygen atoms in the side chain. Of -60 to 0 ° C., a crosslinking agent (B) having a functional group capable of reacting with a functional group in the copolymer (A), and the following general formulas (1) and (2) Alternatively, the present invention relates to a pressure-sensitive adhesive composition comprising an ionic compound (C) selected from (3).

General formula (1)

[In General Formula (1), R ^{1 to} R ⁸ may each independently have a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or a substituent. Represents a good alkynyl group, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent, and R ^{5 to} R ⁸ may form a ring with adjacent substituents; Good. ]

General formula (2)

[In General Formula (2), R ^{1 to} R ⁴ may each independently have a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or a substituent. A good alkynyl group, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent, and A ⁺ represents an alkali metal ion. ]

General formula (3)

〔一般式（３）中Ｒ⁵〜Ｒ⁸は、それぞれ独立に、水素原子、置換基を有してもよいアルキル基、置換基を有してもよいアルケニル基、置換基を有してもよいアルキニル基、置換基を有してもよいアリール基、又は、置換基を有してもよい複素環基を表し、隣り合う置換基同士で環を形成してもよい。
Ｒ⁹は、置換基を有してもよいアルキレン結合基、置換基と二重結合を有してもよいアルキレン結合基、置換基と三重結合を有してもよいアルキレン結合基、置換基を有してもよいアリーレン結合基、置換基を有してもよい複素環結合基、又は、エーテル結合基、エステル結合基、チオエーテル結合基、ジチオール結合基、カルボニル結合基、スルフィニル結合基、スルホニル結合基、ホスホニル結合基、アミノ結合基、イミノ結合基、もしくはシリル結合基を表す。
Ｒ¹⁰は、水素原子、置換基を有してもよいアルキル基、置換基を有してもよいアリール基、又は、ハロゲン基を表す。
Ｒ¹¹は、水素原子、置換基を有してもよいアルキル基、置換基を有してもよいアリール基、又は、−Ｒ⁹Ｒ¹⁰を表す。〕

[In General Formula (3), R ^{5 to} R ⁸ may each independently have a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or a substituent. It represents a good alkynyl group, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent, and adjacent substituents may form a ring.
R ⁹ represents an alkylene bonding group that may have a substituent, an alkylene bonding group that may have a substituent and a double bond, an alkylene bonding group that may have a substituent and a triple bond, or a substituent. Arylene bond group which may have, heterocyclic bond group which may have substituent, or ether bond group, ester bond group, thioether bond group, dithiol bond group, carbonyl bond group, sulfinyl bond group, sulfonyl bond Represents a group, a phosphonyl linking group, an amino linking group, an imino linking group, or a silyl linking group.
R ¹⁰ represents a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a halogen group.
R ¹¹ represents a hydrogen atom, an alkyl group that may have a substituent, an aryl group that may have a substituent, or —R ⁹ R ¹⁰ . ]

  In the second invention, the main chain of the copolymer (A) is an ethylenically unsaturated monomer (a1) having a hydroxyl group as a functional group and / or an ethylenically unsaturated monomer having a carboxyl group ( a2) and, if necessary, 100% by weight of the precursor (AP) of the copolymer (A) obtained by copolymerizing an ethylenically unsaturated monomer (a3) other than (a1) and (a2). On the other hand, it relates to the pressure-sensitive adhesive composition of the first invention, characterized in that it contains 1 to 40% by weight of (a1) and / or (a2).

  In the third invention, the bonding group formed by ring-opening addition of a cyclic compound having four or more membered rings having two or more oxygen atoms to the side chain of the copolymer (A) is a hydroxyl group and / or a carboxyl group. Produced by a reaction between a hydroxyl group and / or a carboxyl group in the precursor (AP) of the copolymer (A) having at least a four-membered cyclic compound (f) having two or more oxygen atoms It is related with the pressure sensitive adhesive composition of 1st or 2nd invention characterized by these.

Moreover, 4th invention is that the cyclic compound (f) more than the 4-membered ring which has a 2 or more oxygen atom is cyclic formal (f-1) and / or cyclic carbonate (f-2). The invention relates to a pressure-sensitive adhesive composition according to a third aspect of the invention.
The fifth invention relates to the pressure-sensitive adhesive composition according to the fourth invention, wherein the cyclic formal (f-1) is at least one selected from dioxolanes, dioxanes, and trioxanes. .

Further, the sixth invention is a cyclic compound having four or more membered rings in which the copolymer (A) has two or more oxygen atoms with respect to 100 parts by weight of the precursor (AP) of the copolymer (A). (F) It relates to the pressure-sensitive adhesive composition according to any one of the fourth to fifth inventions characterized by using 1 to 150 parts by weight.
Moreover, 7th invention contains 0.01-10 weight part of ionic compounds (C) with respect to 100 weight part of copolymers (A), Any 1st invention of 6 characterized by the above-mentioned. The present invention relates to a pressure-sensitive adhesive composition.

The eighth invention relates to the pressure-sensitive adhesive composition according to any one of the first to seventh inventions, wherein the crosslinking agent (B) is a polyisocyanate compound (b1).
In the ninth invention, the crosslinking agent (B) is any one of the epoxy compound (b2), the aziridine compound (b3), the carbodiimide compound (b4), the oxazoline compound (b5), or the metal chelate compound (b6). The pressure-sensitive adhesive composition according to any one of the first to seventh inventions.
Moreover, 10th invention is related with the laminated body by which an optical member is laminated | stacked on the pressure sensitive adhesive layer formed from the pressure sensitive adhesive composition in any one of 1st-9th invention.

  The eleventh invention is a liquid crystal in which a glass member for a liquid crystal cell, a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of any of the first to ninth inventions, and an optical member are sequentially laminated. The present invention relates to a cell member.

  According to the present invention, it was possible to provide a pressure-sensitive adhesive composition for use in a pressure-sensitive adhesive film that has antistatic performance and can obtain better reworkability, transparency, and heat-and-moisture resistance.

The matters necessary for carrying out the present invention are specifically described below.
The pressure-sensitive adhesive composition used in the present invention is a ring-opening addition of a cyclic compound having a 4-membered ring or more having a hydroxyl group and / or a carboxyl group as a functional group and further having two or more oxygen atoms in the side chain. A copolymer (A) having a glass transition temperature of −60 to 0 ° C., a crosslinking agent (B) having a functional group capable of reacting with a functional group in the copolymer (A), and an ionic compound (C ) Containing a pressure-sensitive adhesive composition.

  Copolymer (A) formed by ring-opening addition of a cyclic compound having a 4-membered ring or more having a hydroxyl group and / or a carboxyl group as a functional group used in the present invention and further having two or more oxygen atoms in the side chain Is an ethylenically unsaturated monomer (a1) having a hydroxyl group as a functional group and / or an ethylenically unsaturated monomer (a2) having a carboxyl group, and if necessary, other than (a1) and (a2) Four-membered ring having a hydroxyl group and / or a carboxyl group in the precursor (AP) of the copolymer (A) obtained by copolymerizing the ethylenically unsaturated monomer (a3) and two or more oxygen atoms It is a copolymer obtained by reaction with the above cyclic compound (f).

  The ethylenically unsaturated monomer (a1) having a hydroxyl group as a functional group is not particularly limited as long as it has a hydroxyl group in its structure. For example, 2-hydroxyethyl (meth) acrylate [acrylic acid 2-hydroxyethyl and 2-hydroxyethyl methacrylate are collectively referred to as “2-hydroxyethyl (meth) acrylate”. The same applies hereinafter. ], 1-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 1-hydroxybutyl (meth) acrylate, 2-hydroxy (meth) acrylate Butyl, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxy (meth) acrylate Decyl, 12-hydroxylauryl (meth) acrylate, ethyl (meth) acrylate-α- (hydroxymethyl), monofunctional (meth) acrylate glycerol, or (meth) acrylate glycidyl laurate, (meth) acryl Acid glycidyl oleate, (meth) acte Fatty acid ester (meth) acrylic acid esters such as glycidyl stearate ester, polylactone (meth) acrylic acid esters having a hydroxyl group at the terminal by ring-opening addition of a lactone ring, or alkylene oxides such as ethylene oxide and propylene oxide A hydroxyl group-containing aliphatic (meth) acrylic acid ester such as an alkylene oxide addition system (meth) acrylic acid ester having a hydroxyl group at the terminal repeatedly added, or (meth) acrylic acid 2-hydroxyethyl phosphate;

  For example, (meth) acrylic acid 1,2-cyclohexanedimethanol, (meth) acrylic acid 1,3-cyclohexanedimethanol, (meth) acrylic acid 1,4-cyclohexanedimethanol, (meth) acrylic acid cyclohexyl glycidyl ether, (Meth) acrylic acid phenylglycidyl ether, (meth) acrylic acid 2-hydroxy-3-phenoxymethyl, (meth) acrylic acid 2-hydroxy-3-phenoxyethyl, (meth) acrylic acid 2-hydroxy-3-phenoxypropyl , 2-hydroxy-3-phenoxybutyl (meth) acrylate, 2-hydroxy-3-phenoxydecyl (meth) acrylate, 2-hydroxy-3-phenoxyoctadecyl (meth) acrylate, monohydroxy (meth) acrylate Ethyl phthalate, (me ) 2- (4-benzoyl-3-hydroxyphenoxy) ethyl acrylate, 1,4-bis (2-hydroxypropyl) benzene di (meth) acrylate, 1,3-bis (2- Hydroxyl-containing alicyclic or aromatic (meth) acrylic acid esters such as hydroxypropyl) benzene;

For example, 2- (2′-hydroxy-5 ′-(meth) acryloyloxyethylphenyl) -2H-benzotriazole [2- (2′-hydroxy-5′-acryloyloxyethylphenyl) -2H-benzotriazole and 2 Combined with-(2'-hydroxy-5'-methacryloyloxyethylphenyl) -2H-benzotriazole, "2- (2'-hydroxy-5 '-(meth) acryloyloxyethylphenyl) -2H-benzotriazole" Is written. The same applies below. ], 2- (2'-hydroxy-5 '-(meth) acryloyloxyethylphenyl) -5-chloro-2H-benzotriazole, 2- (2'-hydroxy-5'-(meth) acryloyloxypropylphenyl) -2H-benzotriazole,
2- (2′-hydroxy-5 ′-(meth) acryloyloxypropylphenyl) -5-chloro-2H-benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5 ′-(meth) Hydroxyl groups such as acryloyloxyethylphenyl) -2H-benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5 '-(meth) acryloyloxyethylphenyl) -5-chloro-2H-benzotriazole Containing benzotriazole-based (meth) acrylic acid esters;

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

  For example, 2,4-diphenyl-6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis (2-methylphenyl) -6- [2- Hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis (2-methoxyphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy }]-S-triazine, 2,4-bis (2-ethylphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis ( 2-Ethoxyphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis (2,4-dimethylphenyl) -6- [2- Hydroxy 4- {2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis (2,4-diethoxylphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxy Ethoxy}]-S-triazine, 2,4-bis (2,4-diethylphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy})]-hydroxyl group such as S-triazine Containing triazine-based (meth) acrylic acid esters;

  For example, glucose ring system (meth) acrylate esters such as glycosyl methyl (meth) acrylate, glycosyl ethyl (meth) acrylate, glycosyl propyl (meth) acrylate, glycosyl butyl (meth) acrylate;

  For example, repeated addition of hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether, hydroxyhexyl vinyl ether, hydroxyoctyl vinyl ether, hydroxydecyl vinyl ether, hydroxydodecyl vinyl ether, hydroxyoctadecyl vinyl ether, glyceryl vinyl ether, or alkylene oxide such as ethylene oxide or propylene oxide Hydroxyl group-containing aliphatic vinyl ethers such as alkylene oxide addition vinyl ethers having a hydroxyl group at the terminal end;

  For example, 1,2-cyclohexanedimethanol monovinyl ether, 1,3-cyclohexanedimethanol monovinyl ether, 1,4-cyclohexanedimethanol monovinyl ether, 2-hydroxy-3-phenoxymethyl monovinyl ether, 2-hydroxy-3-phenoxy Ethyl monovinyl ether, 2-hydroxy-3-phenoxypropyl monovinyl ether, 2-hydroxy-3-phenoxybutyl monovinyl ether, 2-hydroxy-3-phenoxydecyl monovinyl ether, 2-hydroxy-3-phenoxyoctadecyl monovinyl ether, 2- Vinyl ethers having a hydroxyl group-containing alicyclic or aromatic ring such as (4-benzoyl-3-hydroxyphenoxy) ethyl monovinyl ether;

  For example, 2-hydroxystyrene, 3-hydroxystyrene, 4-hydroxystyrene, 2-hydroxy-α-methylstyrene, 3-hydroxy-α-methylstyrene, 4-hydroxy-α-methylstyrene, 2-methyl-3- Hydroxystyrene, 4-methyl-3-hydroxystyrene, 5-methyl-3-hydroxystyrene, 2-methyl-4-hydroxystyrene, 3-methyl-4-hydroxystyrene, 3,4-dihydroxystyrene, 2,4, Hydroxyl group-containing aromatic vinyl compounds such as 6-trihydroxystyrene and 2-hydroxy-6-vinylnaphthalene;

  For example, (meth) allyl alcohol [allyl alcohol and methallyl alcohol are collectively referred to as “(meth) allyl alcohol”. The same applies hereinafter. ], Isopropenyl alcohol, dimethyl (meth) allyl alcohol, hydroxyethyl (meth) allyl ether, hydroxypropyl (meth) allyl ether, hydroxybutyl (meth) allyl ether, hydroxyhexyl (meth) allyl ether, hydroxyoctyl (meth) Allyl ether, hydroxydecyl (meth) allyl ether, hydroxydodecyl (meth) allyl ether, hydroxyoctadecyl (meth) allyl ether, glyceryl (meth) allyl ether, or an alkylene oxide such as ethylene oxide or propylene oxide repeatedly added to the terminal Hydroxyl group-containing aliphatic (meth) allyl alcohols or (meth) allylate such as alkylene oxide addition system (meth) allyl ether having a hydroxyl group Kind;

  For example, 1,2-cyclohexanedimethanol mono (meth) allyl ether, 1,3-cyclohexanedimethanol mono (meth) allyl ether, 1,4-cyclohexanedimethanol mono (meth) allyl ether, o- (meth) allyl Phenol, m- (meth) allylphenol, p- (meth) allylphenol, 2-hydroxy-3-phenoxymethyl mono (meth) allyl ether, 2-hydroxy-3-phenoxyethyl mono (meth) allyl ether, 2- Hydroxy-3-phenoxypropyl mono (meth) allyl ether, 2-hydroxy-3-phenoxybutyl mono (meth) allyl ether, 2-hydroxy-3-phenoxydecyl mono (meth) allyl ether, 2-hydroxy-3-phenoxy Octadecyl mono (meth) allyl Ether, 2- (4-benzoyl-3-hydroxyphenoxy) Echirumono (meth) having an alicyclic or aromatic ring of the hydroxyl group-containing and allyl ether (meth) allyl ethers;

  For example, ethylenically unsaturated monomers having a plurality of hydroxyl groups such as propenediol, butenediol, heptenediol, octenediol, glycerol di (meth) acrylate, and o-di (meth) allylbisphenol A;

  For example, N-hydroxyethyl (meth) acrylamide [N-hydroxyethyl acrylamide and N-hydroxyethyl methacrylamide are collectively referred to as “N-hydroxyethyl (meth) acrylamide”. The same applies hereinafter. ], Hydroxyl-containing (meth) acrylamides such as N-hydroxypropyl (meth) acrylamide, N-hydroxybutyl (meth) acrylamide, N-hydroxyhexyl (meth) acrylamide, N-hydroxyoctyl (meth) acrylamide;

  Examples thereof include monomers having a hydroxyl group and an alkenyl group such as hydroxystyrene and vinyl alcohol, but are not particularly limited thereto. These may use only 1 type or may use multiple types together.

  The ethylenically unsaturated monomer (a2) having a carboxyl group as a functional group is not particularly limited as long as it has a carboxyl group in its structure, and more specifically, for example, acrylic acid, methacrylic acid, Acid, 2-carboxyethyl (meth) acrylate, 2-carboxypropyl (meth) acrylate, 3-carboxypropyl (meth) acrylate, 4-carboxybutyl (meth) acrylate, (meth) acrylic acid dimer, malee Acid, fumaric acid, monomethylmaleic acid, monomethylfumaric acid, aconitic acid, sorbic acid, cinnamic acid, α-chlorosorbic acid, glutaconic acid, citraconic acid, mesaconic acid, itaconic acid, tiglic acid, angelic acid, senetic acid, Crotonic acid, isococrotonic acid, mucobromic acid, mucochloric acid, sorbic acid, muco A carboxyl group at the terminal by ring-opening addition of a lactone ring such as acid, aconitic acid, penicillic acid, gellanic acid, citronellic acid, 4-acrylamidobutanoic acid, 6-acrylamidohexanoic acid, or ω-carboxypolycaprolactone mono (meth) acrylate A polylactone-based (meth) acrylic acid ester having a carboxyl group, or an alkylene oxide-added system succinic acid (meth) acrylate having a carboxyl group at the terminal to which an alkylene oxide such as ethylene oxide or propylene oxide is repeatedly added. Of ethylenically unsaturated carboxylic acids;

  For example, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxypropyl phthalate, 2- (meth) acryloyloxybutyl phthalate, 2- (meth) acryloyl Oxyhexyl phthalate, 2- (meth) acryloyloxyoctyl phthalate, 2- (meth) acryloyloxydecyl phthalate, 2-vinylbenzoic acid, 3-vinylbenzoic acid, 4-vinylbenzoic acid, 4-isopropenylbenzenecarboxylic acid, Examples thereof include, but are not limited to, ethylenically unsaturated carboxylic acids having alicyclic or aromatic rings containing carboxyl groups such as cinnamic acid and 7-amino-3-vinyl-3-cephem-4-carboxylic acid. It is not a thing. These may use only 1 type or may use multiple types together.

  The ethylenically unsaturated monomer (a3) other than (a1) to (a2) used as necessary in the present invention is not particularly limited as long as it is an ethylenically unsaturated monomer. For example, (meth) acrylic acid derivatives include methyl (meth) acrylate, ethyl (meth) acrylate, 1-propyl (meth) acrylate, 2-propyl (meth) acrylate, (meth) N-butyl acrylate, sec-butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-amyl (meth) acrylate, iso-amyl (meth) acrylate N-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, iso-octyl (meth) acrylate, ( T) N-nonyl acrylate, (meth) acrylic iso-nonyl, decyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate (Meth) acrylic acid alkyl esters such as;

For example, cyclohexyl (meth) acrylate, 1-methyl-1-cyclopentyl (meth) acrylate, 1-ethyl-1-cyclopentyl (meth) acrylate, 1-isopropyl-1-cyclopentyl (meth) acrylate, (meth ) 1-methyl-1-cyclohexyl acrylate, 1-ethyl-1-cyclohexyl (meth) acrylate, 1-isopropyl-1-cyclohexyl (meth) acrylate, 1-ethyl-1-cyclooctyl (meth) acrylate Benzyl (meth) acrylate, iso-bonyl (meth) acrylate, phenyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, 2-oxo-1,2-phenylethyl (meth) acrylate, (Meth) acrylic acid 2-oxo-1,2-diphenylethyl, (meth) acrylic acid 1- Naphthyl, 2-naphthyl (meth) acrylate, 1-naphthylmethyl (meth) acrylate, 1-anthryl (meth) acrylate, 2-anthryl (meth) acrylate, 9-anthryl (meth) acrylate, (meth ) 9-anthrylmethyl acrylate, 2-methyladamantyl-2-yl (meth) acrylate, 2-ethyladamantyl-2-yl (meth) acrylate, 2-n-propyladamantyl-2 (meth) acrylate -Yl, (meth) acrylic acid 2-isopropyladamantyl-2-yl, (meth) acrylic acid 1- (adamantan-1-yl) -1-methylethyl, (meth) acrylic acid 1- (adamantan-1-yl ) -1-ethylethyl, (meth) acrylic acid 1- (adamantan-1-yl) -1-methylpropyl, (meth) acrylic acid - (adamantan-1-yl) -1-ethylpropyl, (meth) acrylic acid 5-oxo-4-oxa - tricyclo [4.2.1.0 ^{3, 7]} non-2-yl, (meth) Acrylic acid-5-oxo-4-oxa-tricyclo [5.2.1.0 ^3,8 ] dec-2-yl, (meth) acrylic acid-6-oxo-7-oxa-bicyclo [3.2 .1] (meth) acrylic acid cyclic esters such as octa-2-yl, (meth) acrylic acid-7-oxo-8-oxa-bicyclo [3.3.1] oct-2-yl;

  For example, (meth) acrylic acid (meth) allyl, (meth) acrylic acid 1-butenyl, (meth) acrylic acid 2-butenyl, (meth) acrylic acid 3-butenyl, (meth) acrylic acid 1,3-methyl- 3-butenyl, (meth) acrylic acid 2-chloro-2-propenyl, (meth) acrylic acid 3-chloro-2-propenyl, (meth) acrylic acid-o-2-propenylphenyl, (meth) acrylic acid 2- (2 -Propenyloxy) ethyl, 2- (propenyl lactyl (meth) acrylate, 3,7-dimethyloct-6-en-1-yl (meth) acrylate, (meth) acrylic acid (E) -3,7 -Further containing unsaturated groups such as dimethylocta-2,6-dien-1-yl, rosinyl (meth) acrylate, cinnamyl (meth) acrylate, vinyl (meth) acrylate, etc. (Meth) acrylic acid esters;

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

  For example, N-methylaminoethyl (meth) acrylate, N-tributylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, ( (Meth) acrylic acid N, N-diethylaminomethyl, (meth) acrylic acid pentamethylpiperidinyl, (meth) acrylic propenoic acid tetramethylpiperidinyl, 2,4-diamino-6,2-methylpropenoyloxyethyl- amino group-containing (meth) acrylic acid esters such as s-triazine;

  For example, glycidyl (meth) acrylate, (meth) acrylic (3,4-epoxycyclohexyl) methyl, (meth) acrylic acid (3-methyl-3-oxetanyl) methyl, (meth) acrylic acid tetrahydrofurfuryl, (meta ) Acrylic acid-2-oxotetrahydropyran-4-yl, (meth) acrylic acid-4-methyl-2-oxotetrahydropyran-4-yl, (meth) acrylic acid-4-ethyl-2-oxotetrahydropyran- 4-yl, (meth) acrylic acid-4-propyl-2-oxotetrahydropyran-4-yl, (meth) acrylic acid-5-oxotetrahydrofuran-3-yl, (meth) acrylic acid-2,2-dimethyl -5-oxotetrahydrofuran-3-yl, (meth) acrylic acid-4,4-dimethyl-5-oxotetra Drofuran-3-yl, (meth) acrylic acid-2-oxotetrahydrofuran-3-yl, (meth) acrylic acid-4,4-dimethyl-2-oxotetrahydrofuran-3-yl, (meth) acrylic acid-5, 5-dimethyl-2-oxotetrahydrofuran-3-yl, (meth) acrylic acid-2-oxotetrahydrofuran-3-yl, (meth) acrylic acid-5-oxotetrahydrofuran-2-ylmethyl, (meth) acrylic acid-3 Oxygen-containing heterocycle-containing (meth) acrylic acid esters such as 1,3-dimethyl-5-oxotetrahydrofuran-2-ylmethyl and (meth) acrylic acid-4,4-dimethyl-5-oxotetrahydrofuran-2-ylmethyl;

  For example, (meth) acrylic acid (methoxycarbonyl) methyl, (meth) acrylic acid (methoxycarbonyl) ethyl, (meth) acrylic acid (methoxycarbonyl) propyl, (meth) acrylic acid (methoxycarbonyl) butyl, (meth) acrylic Acid (methoxycarbonyl) decyl, (meth) acrylic acid (ethoxycarbonyl) methyl, (meth) acrylic acid (ethoxycarbonyl) ethyl, (meth) acrylic acid (ethoxycarbonyl) propyl, (meth) acrylic acid (ethoxycarbonyl) butyl , (Meth) acrylic acid (ethoxycarbonyl) hexyl, (meth) acrylic acid (ethoxycarbonyl) octyl, (meth) acrylic acid 2- (ethoxycarbonyloxy) ethyl, (meth) acrylic acid 2- (ethoxycarbonyloxy) propyl , (Meth) acrylic acid 2- (ethoxyca (Rubonyloxy) butyl, 2- (ethoxycarbonyloxy) hexyl (meth) acrylate, 2- (ethoxycarbonyloxy) octyl (meth) acrylate, 2- (propoxycarbonyloxy) ethyl (meth) acrylate, (meth) 2- (Butoxycarbonyloxy) ethyl acrylate, 2- (butoxycarbonyloxy) butyl (meth) acrylate, 2- (octyloxycarbonyloxy) ethyl (meth) acrylate, 2- (octyloxy) (meth) acrylate Aliphatic (meth) acrylic acid esters having one carbonyl group such as carbonyloxy) butyl;

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

For example, (meth) acrylic acid-9-methoxycarbonyl-5-oxo-4-oxa-tricyclo [4.2.1.0 ^3,7 ] non-2-yl, (meth) acrylic acid-10-methoxycarbonyl -5-oxo-4-oxa-tricyclo [5.2.1.0 ^3,8 ] non-2-yl, (meth) acrylic acid-4-methoxycarbonyl-6-oxo-7-oxa-bicyclo [3 2.1] having a carbonyl group such as octa-2-yl, (meth) acrylic acid-4-methoxycarbonyl-7-oxo-8-oxa-bicyclo [3.3.1] oct-2-yl ( (Meth) acrylic acid cyclic esters;

  For example, N- (2-oxobutanoylethyl) (meth) acrylamide, N- (2-oxobutanoylpropyl) (meth) acrylamide, N- (2-oxobutanoylbutyl) (meth) acrylamide, N- ( (Meth) acrylamides having a carbonyl group such as 2-oxobutanoylhexyl) (meth) acrylamide, N- (2-oxobutanoyloctyl) (meth) acrylamide, diacetone (meth) acrylamide;

  For example, vinyl acetoacetate, vinyl acetopropionate, vinyl acetoisobutyrate, vinyl acetobutyrate, vinyl acetovalerate, vinyl acetohexanoate, vinyl aceto-2-ethylhexanoate, vinyl aceto-n-octanoate, vinyl acetodecanoate, acetodecane Vinyl acid, vinyl acetooctadecanoate, vinyl acetopivalate, vinyl acetocaprate, vinyl acetocrotonate, vinyl acetosorbate, vinyl propanoyl acetate, vinyl butyryl acetate, vinyl isobutyryl acetate, vinyl palmitoyl acetate, vinyl stearoyl acetate, vinyl pyroyl acetate , Vinyl propanoyl valerate, vinyl butyryl valerate, vinyl isobutyryl valerate, palmitoyl vinyl valerate, stearoyl valerate, pyrvoyl Vinyl Rerin acid, 2-acetoacetoxyethyl vinyl ether, 2-acetoacetoxyethyl butyl vinyl ether, 2-acetoacetoxyethyl hexyl vinyl ether, aliphatic vinyl compounds of having an acyl group such as 2-acetoacetoxyethyl octyl vinyl ether;

  For example, vinyl benzoylformate, vinyl benzoyl acetate, vinyl benzoylpropionate, vinyl benzoylbutyrate, vinyl benzoylvalerate, vinyl benzoylhexanoate, vinyl benzoyldodecanoate, 1-naphthoylvinyl acetate, 1-naphthoylpropionate, 1- Naphthoyl vinyl butyrate, 1-naphthoyl vinyl valerate, 1-naphtho vinyl hexanoate, 2-naphtho vinyl acetate, 2-naphtho vinyl propionate, 2-naphtho vinyl butyrate, 2-naphtho vinyl butyrate, 2- Vinyl naphthoyl hexanoate, vinyl nicotinoyl acetate, vinyl nicotinoyl propionate, vinyl nicotinoyl butyrate, vinyl nicotinoyl valerate, vinyl nicotinoyl hexanoate, vinyl nicotinoyl decanoate, nicotine Vinyl dodecanoate, vinyl isonicotinoyl acetate, vinyl isonicotinoyl propionate, vinyl isonicotinoyl butyrate, vinyl isonicotinoyl valerate, vinyl isonicotinoyl hexanoate, vinyl isonicotinoyl decanoate, vinyl isonicotinoyl dodecanoate, 2-furoyl Vinyl acetate, vinyl 2-furoylpropionate, vinyl 2-furoylbutyrate, vinyl 2-furoylvalerate, vinyl 2-furoylhexanoate, vinyl 2-furoyldecanoate, vinyl 2-furoyldodecanoate, 3-furoyl Vinyl acetate, vinyl 3-furoylpropionate, vinyl 3-furoylbutyrate, vinyl 3-furoylvalerate, vinyl 3-furoylhexanoate, vinyl 3-furoyldecanoate, vinyl 3-furoyldodecanoate, vinyl anthraniloyl acetate , Vinyl anthraniloyl propionate, vinyl anthraniloyl butyrate, vinyl anthraniloyl valerate, vinyl anthraniloyl hexanoate, vinyl anthraniloyl decanoate, vinyl anthraniloyl decanoate, 4- (2-t-ethoxycarbonylethyl) Aromatic vinyl compounds having an acyl group such as oxy) styrene, 4- (2-t-butoxycarbonylethyloxy) styrene, 4- (2-t-butoxycarbonylpropyloxy) styrene;

  For example, acetoacetic acid (meth) allyl, acetopropionic acid (meth) allyl, acetoisobutyric acid (meth) allyl, acetobutyric acid (meth) allyl, acetovaleric acid (meth) allyl, acetohexanoic acid (meth) allyl, aceto-2- Ethylhexanoic acid (meth) allyl, aceto-n-octanoic acid (meth) allyl, acetodecanoic acid (meth) allyl, acetodecanoic acid (meth) allyl, acetooctadecanoic acid (meth) allyl, acetopivalic acid (meth) allyl, acetocaprin Acid (meth) allyl, acetocrotonic acid (meth) allyl, acetosorbic acid (meth) allyl, propanoyl acetate (meth) allyl, butyryl acetate (meth) allyl, isobutyryl acetate (meth) allyl, palmitoyl acetate (meth) allyl, Stearoyl acetate (meth) allyl, (meth) allyl Aliphatic (meth) allyl compounds having an acyl group such as hydrin;

  For example, benzoyl formate (meth) allyl, benzoyl acetate (meth) allyl, benzoylpropionate (meth) allyl, benzoylbutyrate (meth) allyl, benzoylvalerate (meth) allyl, benzoylhexanoic acid (meth) allyl, benzoyldodecanoic acid (Meth) allyl, 1-naphthoylacetic acid (meth) allyl, 1-naphthoylpropionic acid (meth) allyl, 1-naphthoylbutyric acid (meth) allyl, 1-naphthoylvaleric acid (meth) allyl, 1-naphthoylhexane Acid (meth) allyl, 2-naphthoylacetic acid (meth) allyl, 2-naphthoylpropionic acid (meth) allyl, 2-naphthoylbutyric acid (meth) allyl, 2-naphthoylvaleric acid (meth) allyl, 2-naphthoyl Aromatic (meth) allyl having an acyl group such as hexanoic acid (meth) allyl Compounds such ethylenically unsaturated monomers of carbonyl-containing such as and the like, but not particularly limited thereto. These may use only 1 type or may use multiple types together.

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

  For example, sulfomethyl (meth) acrylate, 2-sulfoethyl (meth) acrylate, 2-sulfopropyl (meth) acrylate, 3-sulfopropyl (meth) acrylate, 2-sulfobutyl (meth) acrylate, (meth) 4-sulfobutyl acrylate, 2-sulfobutyl (meth) acrylate, 6-sulfohexyl (meth) acrylate, sulfooctyl (meth) acrylate, sulfodecyl (meth) acrylate, sulfolauryl (meth) acrylate, (meth ) (Meth) acrylic acid alkyl esters containing a sulfonyl group such as sulfostearyl acrylate;

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

  For example, (meth) acryloyloxydimethylethylammonium ethyl sulfate, (meth) acryloylaminopropyltrimethylammonium sulfate, (meth) acryloylaminopropyltriethylammonium sulfate, (meth) acryloyloxyethyldimethylbenzylammonium p-toluenesulfonate, (meth) ) Metal salts and ammonium salts of (meth) acrylic acid esters containing sulfonyl groups such as acryloyloxyethyltrimethylammonium-p-toluenesulfonate and (meth) acryloylaminopropyltrimethylammonium-p-toluenesulfonate;

  For example, (meth) acrylic acid phosphooxyethyl, (meth) acrylic acid phosphooxypropyl, (meth) acrylic acid phosphooxybutyl, (meth) acrylic acid-3-chloro-2-acid phosphooxyethyl, ( (Meth) acrylic acid-3-chloro-2-acid phosphooxypropyl, (meth) acrylic acid-3-chloro-2-acid phosphooxybutyl, phenyl-2- (meth) acryloyloxyethyl phosphate, (meth) acrylic acid Phosphonic acid group-containing (meth) acrylic acid esters such as acid phosphooxyethylene oxide (ethylene oxide addition moles: 4 to 10) and (meth) acrylic acid acid phosphooxypropylene oxide (propylene oxide addition moles: 4 to 10) Kind;

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

  For example, alkylene oxide-containing (meth) acrylic acid derivatives such as an alkylene oxide adduct of (meth) acrylic acid;

  For example, di (meth) acrylic acid ethylene oxide, di (meth) acrylic acid triethylene oxide, di (meth) acrylic acid tetraethylene oxide, di (meth) acrylic acid polyethylene oxide, di (meth) acrylic acid propylene oxide, di (Meth) acrylic acid dipropylene oxide, di (meth) acrylic acid tripropylene oxide, di (meth) acrylic acid polypropylene oxide, di (meth) acrylic acid butene oxide, di (meth) acrylic acid pentane oxide, di (meth) 2,2-dimethylpropyl acrylate, hydroxypivalylhydroxypivalate di (meth) acrylate, hydroxypivalylhydroxypivalate hydroxypivalate dicaprolactonate, 1,6-hexane di (meth) acrylate Gio Di (meth) acrylic acid 1,2-hexanediol, di (meth) acrylic acid 1,5-hexanediol di, di (meth) acrylic acid 2,5-hexanediol, di (meth) acrylic acid 1,7 -Heptanediol, di (meth) acrylic acid 1,8-octanediol, di (meth) acrylic acid 1,2-octanediol, di (meth) acrylic acid 1,9-nonanediol di, di (meth) acrylic acid 1,2-decanediol, di (meth) acrylic acid 1,10-decanediol, di (meth) acrylic acid 1,2-decanediol, di (meth) acrylic acid 1,12-dodecanediol, di (meth) 1,2-dodecanediol acrylate, 1,14-tetradecanediol di (meth) acrylate, 1,2-tetradecanediol di (meth) acrylate, di (meth) acrylate 1,16-hexadecanediol acrylate, 1,2-hexadecanediol di (meth) acrylate, 2-methyl-2,4-pentanediol di (meth) acrylate, 3-methyl-1 di (meth) acrylate , 5-pentanediol, 2-methyl-2-propyl-1,3-propanediol di (meth) acrylate, 2,4-dimethyl-2,4-pentanediol di (meth) acrylate, di (meth) 2,2-diethyl-1,3-propanediol acrylate, 2,2,4-trimethyl-1,3-pentanediol di (meth) acrylate, dimethyloloctane di (meth) acrylate, di (meth) 2-ethyl-1,3-hexanediol acrylate, 2,5-dimethyl-2,5-hexanediol di (meth) acrylate, 2-methyl di (meth) acrylate -1,8-octanediol, 2-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, 2,4-diethyl-1,5-pentanediol di (meth) acrylate, di ( (Meth) acrylic acid 1,2-hexanediol, di (meth) acrylic acid 1,5-hexanediol, di (meth) acrylic acid 2,5-hexanediol, di (meth) acrylic acid 1,7-heptanediol, Di (meth) acrylic acid 1,8-octanediol, di (meth) acrylic acid 1,2-octanediol, di (meth) acrylic acid 1,9-nonanediol, di (meth) acrylic acid 1,2-decane Diol, di (meth) acrylic acid 1,10-decanediol, di (meth) acrylic acid 1,2-decanediol, di (meth) acrylic acid 1,12-dodecanediol, di (Meth) acrylic acid 1,2-dodecanediol, di (meth) acrylic acid 1,14-tetradecanediol, di (meth) acrylic acid 1,2-tetradecanediol, di (meth) acrylic acid 1,16-hexadecanediol, 1,2-hexadecanediol di (meth) acrylate, 2-methyl-2,4-pentane di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, di (meth) 2-methyl-2-propyl-1,3-propanediol acrylate, 2,4-dimethyl-2,4-pentanediol di (meth) acrylate, 2,2-diethyl-1, di (meth) acrylate 3-propanediol, 2,2,4-trimethyl-1,3-pentanediol di (meth) acrylate, dimethyloloctane di (meth) acrylate, (Meth) acrylic acid 2-ethyl-1,3-hexanediol, di (meth) acrylic acid 2,5-dimethyl-2,5-hexanediol, di (meth) acrylic acid 2-butyl-2-ethyl-1 , 3-propanediol, 2,4-diethyl-1,5-pentanediol di (meth) acrylate, 1,2-adamantanediol di (meth) acrylate, 1,3-adamantanediol di (meth) acrylate Di (meth) acrylic acid 1,4-adamantanediol, di (meth) acrylic acid tricyclodecanyl dimethylol, di (meth) acrylic acid 1,1,1-trishydroxymethylethane, di (meth) acrylic acid Tricyclodecane dihydroxymethyl, di (meth) acrylic acid tricyclodecane dihydroxymethyl dicaprolactonate, di (meth) a Tetraethylene oxide adduct of lauric acid-2,2-bis (hydroxyphenyl) propane, tetraethylene oxide adduct of 2,2-bis (hydroxyphenyl) methane di (meth) acrylate, di (meth) acrylic acid- Tetraethylene oxide adduct of 4,4'-sulfonyldiphenol, di (meth) acrylic acid-water addition 2,2-bis (hydroxyphenyl) propane tetraethylene oxide adduct, di (meth) acrylic acid-water addition Tetraethylene oxide adduct of 2,2-bis (hydroxyphenyl) methane, di (meth) acrylic acid-water addition 2,2-bis (hydroxyphenyl) propane, di (2-methyl) propenoic acid-water addition2, 2-bis (hydroxyphenyl) methane, di (meth) acrylic acid-2,2-bis (hydroxyphenyl) propa Tetraethylene oxide adducts-dicaprolactonate, di (meth) acrylic acid-2,2-bis (hydroxyphenyl) methane tetraethylene oxide adduct-dicaprolactonate, etc. Kind;

  For example, 1,2,3-propanetriol tri (meth) acrylate, 2-methylpentane-2,4-diol tri (meth) acrylate, 2-methylpentane-2,4-diol tri (meth) acrylate Tricaprolactonate, 2,2-dimethylpropane-1,3-diol tri (meth) acrylate, trimethylolhexane tri (meth) acrylate, trimethyloloctane tri (meth) acrylate, tri (meth) acrylic acid 2,2-bis (hydroxymethyl) 1,3-propanediol, 1,1,1-trishydroxymethylethane tri (meth) acrylate, 1,1,1-trishydroxymethylpropane tri (meth) acrylate, Tri (meth) acrylic acid ethoxylated isocyanuric acid, ε-caprolactone modified tris- (2-acryloyl Oxyethyl) isocyanurate, tri (meth) trifunctional (meth) acrylic acid esters such as acrylic acid and pentaerythritol;

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

  Examples of the alkenyl group-containing compound include ethyl vinyl ether, 1-propyl vinyl ether, 2-propyl vinyl ether, n-butyl vinyl ether, sec-butyl vinyl ether, iso-butyl vinyl ether, tert-butyl vinyl ether, n-amyl vinyl ether, n-hexyl. Aliphatic vinyl ethers such as 2-ethylhexyl vinyl ether, n-octyl vinyl ether, iso-octyl vinyl ether, n-nonyl vinyl ether, iso-nonyl vinyl ether, decyl vinyl ether, dodecyl vinyl ether, octadecyl vinyl ether, lauryl vinyl ether, stearyl vinyl ether;

  For example, cyclohexyl vinyl ether, cyclohexanedimethanol monovinyl ether, 2,3-dihydrofuran, 3,4-dihydrofuran, 2,3-dihydro-2H-pyran, 3,4-dihydro-2H-pyran, 3,4-dihydro 2-methoxy-2H-pyran, 3,4-dihydro-4,4-dimethyl-2H-pyran-2-one, 3,4-dihydro-2-ethoxy-2H-pyran, 3,4-dihydro-2H -Vinyl ethers having a cyclic structure such as sodium pyran-2-carboxylate;

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

  For example, (meth) allylchlorosilane, (meth) allyltrimethoxysilane, (meth) allyltriethoxysilane, (meth) allylaminotrimethylsilane, diethoxyethylvinylsilane, trichlorovinylsilane, trimethoxyvinylsilane, triethoxyvinylsilane, tripropoxy Alkoxysilyl group-containing ethylenically unsaturated monomers such as vinylsilane and vinyltris (2-methoxyethoxy) silane;

  For example, alkenyl group-containing sulfonic acids such as vinyl sulfonic acid, 2-propenyl sulfonic acid, 2-methyl-2-propenyl sulfonic acid, and vinyl sulfuric acid;

For example, metal salts and ammonium salts such as ammonium vinyl sulfonate, sodium vinyl sulfonate, potassium vinyl sulfonate, sodium vinyl alkyl sulfosuccinate;
Metal salts and ammonium salts of 2-methyl-2-propenylsulfonic acid such as ammonium 2-methyl-2-propenylsulfonate, sodium 2-methyl-2-propenylsulfonate, and potassium 2-methyl-2-propenylsulfonate;

  For example, styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2-methoxystyrene, 3-methoxystyrene, 4-methoxystyrene, 4-t-butoxystyrene, 4-t- Butoxy-α-methylstyrene, 4- (2-ethyl-2-propoxy) styrene, 4- (2-ethyl-2-propoxy) -α-methylstyrene, 4- (1-ethoxyethoxy) styrene, 4- ( Aromatic vinyl monomers such as 1-ethoxyethoxy) -α-methylstyrene, 1-butylstyrene, 1-chloro-4-isopropenylbenzene;

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

  Hexyl 4-vinylbenzoate, octyl 4-vinylbenzoate, nonyl 4-vinylbenzoate, decyl 4-vinylbenzoate, dodecyl 4-vinylbenzoate, tetradecyl 4-vinylbenzoate, hexadecyl 4-vinylbenzoate, 4 -Octadecyl vinylbenzoate, eicosyl 4-vinylbenzoate, docosyl 4-vinylbenzoate, hexyl 4-isopropenylbenzoate, octyl 4-isopropenylbenzoate, nonyl 4-isopropenylbenzoate, 4-isopropenylbenzoic acid Decyl, 4-isopropenyl benzoate dodecyl, 4-isopropenyl benzoate tetradecyl, 4-isopropenyl benzoate hexadecyl, 4-isopropenyl benzoate octadecyl, 4-isopropenyl benzoate eicosyl, 4-isopropenyl benzoate docosyl, etc. Head of Vinyl benzoate ester or isopropenyl benzoic acid ester monomer having an alkyl group;

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

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

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

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

  For example, alkenyl group-containing sulfonic acids such as styrene sulfonic acid, 2-propenyloxybenzene sulfonic acid, 2-methyl-2-propenyl sulfonic acid, 2-methyl-2-propenyloxybenzene sulfonic acid;

For example, ammonium styrene sulfonate, monomethyl ammonium styrene sulfonate, dimethyl ammonium styrene sulfonate, trimethyl ammonium styrene sulfonate, tetramethyl ammonium styrene sulfonate, ethyl ammonium styrene sulfonate, diethyl ammonium styrene sulfonate, styrene sulfonic acid Styrene sulfones such as triethylammonium, tetraethylammonium styrenesulfonate, propylammonium styrenesulfonate, dipropylammonium styrenesulfonate, tripropylammonium styrenesulfonate, butylammonium styrenesulfonate, pentylammonium styrenesulfonate or hexylammonium styrenesulfonate Ammonium salts of acids;
Metal salts of styrene sulfonic acid such as sodium styrene sulfonate, potassium styrene sulfonate, lithium styrene sulfonate, magnesium styrene sulfonate, zinc styrene sulfonate, iron styrene sulfonate;
Metal salts and ammonium salts of alkenyl group-containing vinyloxybenzenesulfonic acid such as ammonium vinyloxybenzenesulfonate, sodium vinyloxybenzenesulfonate, potassium vinyloxybenzenesulfonate, etc .;
2-methyl-2-propenyloxybenzenesulfonate ammonium, 2-methyl-2-propenyloxybenzenesulfonate sodium, 2-methyl-2-propenyloxybenzenesulfonate potassium and the like 2-methyl-2-propenyloxybenzenesulfonate Metal salts and ammonium salts of acids;

  For example, (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, N-propyl (Meth) acrylamide, N-tert-butyl (meth) acrylamide, N-hexyl (meth) acrylamide, N-octyl (meth) acrylamide, N-nonyl (meth) acrylamide, N-tricosyl (meth) acrylamide, N-nonadecyl (Meth) acrylamide, N-docosyl (meth) acrylamide, N-methylene (meth) acrylamide, N-tridecyl (meth) acrylamide, N- (4-carbamoylphenyl) (meth) acrylamide, β- (2-furyl) ( Meta) Rilamide, 2,3-bis (2-furyl) acrylamide, N- (9H-fluoren-2-yl) (meth) acrylamide, 2,3,3-trichloro (meth) acrylamide, N-[(R) -1 -Phenylethyl] (meth) acrylamide, N-[(S) -1-phenylethyl] (meth) acrylamide, N- (5,5-dimethylhexyl) (meth) acrylamide, (Z) -N-methyl-3 -(Phenyl) (meth) acrylamide, (Z) -3- (phenyl) (meth) acrylamide, N, N-diethyl-3-phenyl (meth) acrylamide, N- [2- (1H-imidazol-5-yl) ) Ethyl] (meth) acrylamide, (Z) -N, N-dimethyl-3- (phenyl) (meth) acrylamide, crotonamide, maleamide, fumarua Mido, Mesaconamide, Citraconamide, Itaconamide, 3-Phenyl-2-propenamide, 2-Methylprop-2-enoylamine, N, N-dimethyl (meth) acrylamide, N, N-diethyl- (meth) acrylamide, N- [3- (N ′, N′-dimethylamino) propyl]-(meth) acrylamide, N- (dibutylaminomethyl) (meth) acrylamide, N-methyl-N-phenyl (meth) acrylamide, N-vinylmethanamide Aliphatic or aromatic (meth) acrylamides such as N-vinylacetamide;

  For example, N-methoxymethyl (meth) acrylamide, N-methoxyethyl (meth) acrylamide, N-methoxypropyl (meth) acrylamide, N-methoxybutyl (meth) acrylamide, N-methoxyhexyl (meth) acrylamide, N-methoxy Octyl (meth) acrylamide, N-methoxydecyl (meth) acrylamide, N-methoxydodecyl (meth) acrylamide, N-methoxyoctadecyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-ethoxyethyl (meth) acrylamide N-ethoxypropyl (meth) acrylamide, N-ethoxybutyl (meth) acrylamide, N-ethoxyhexyl (meth) acrylamide, N-ethoxyoctyl (meth) acrylamide, N-iso Roxymethyl (meth) acrylamide, N-isopropoxyethyl (meth) acrylamide, N-isopropoxypropyl (meth) acrylamide, N-isopropoxybutyl (meth) acrylamide, N-isopropoxyhexyl (meth) acrylamide, N-isopropoxy Octyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-butoxyethyl (meth) acrylamide, N-butoxypropyl (meth) acrylamide, N-butoxybutyl (meth) acrylamide, N-butoxyhexyl (meth) acrylamide N-butoxyoctyl (meth) acrylamide, N-isobutoxymethyl (meth) acrylamide, N-isobutoxyethyl (meth) acrylamide, N-isobutoxypropyl (meth) Acrylamide, N-isobutoxybutyl (meth) acrylamide, N-isobutoxyhexyl (meth) acrylamide, N-isobutoxyoctyl (meth) acrylamide, N- (pentoxymethyl) (meth) acrylamide, N-1-methyl- 2-methoxyethyl (meth) acrylamide, N- (oxetane-2-ylmethoxymethyl) (meth) acrylamide, N- (oxetane-3-ylmethoxymethyl) (meth) acrylamide, N, N-di (methoxymethyl) (Meth) acrylamides containing N-alkoxy groups such as (meth) acrylamide and N, N-di (ethoxymethyl) (meth) acrylamide;

For example, (meth) acrylamides containing sulfonic acids such as (meth) acrylamide sulfonic acid, tert-butyl- (meth) acrylamide sulfonic acid, (meth) acrylamide-2-methyl-1-propanesulfonic acid;
For example, cyclic amide group-containing (meth) acrylamides such as 4-acryloylmorpholine, N-vinyl-2-pyrrolidone, N-vinyl-ε-caprolactam;

For example, nitrile group-containing ethylenic compounds such as (meth) acrylonitrile, α-chloroacrylonitrile, crotonnitrile, maleinonitrile, fumaronitrile, mesacononitrile, citraconnitrile, itacononitrile, 2-propenenitrile, 2-cyanoethyl (meth) acrylate, etc. Unsaturated monomers;
For example, a nitrogen atom-containing heterocyclic vinyl-based monomer such as 2-vinylpyridine, 4-vinylpyridine, 2-vinylpiperazine, N-vinylimidazole, 4-vinylpiperazine, 2,4-diamino-6-vinyl-s-triazine, etc. Mer;

For example, maleimide derivatives such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide;
For example, vinyl esters of carboxylic acids such as vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caprate, vinyl laurate, vinyl versatate, vinyl pivalate, vinyl palmitate, vinyl stearate;

For example, saturated carboxylic acids such as (meth) allyl acetate, (meth) allyl propionate, (meth) allyl butyrate (meth) allyl caprate, (meth) allyl laurate, allyl octylate, coconut oil fatty acid, vinyl pivalate, etc. (Meth) allyl esters of acids;
For example, glycidyl group-containing vinyl esters such as glycidyl cinnamate, allyl glycidyl ether, vinylcyclohexene monooxirane, 1,3-butadiene monooxirane;

For example, vinyl esters such as vinyl chloride, vinylidene chloride and allyl chloride;
For example, dienes such as allene, 1,2-butadiene, 1,3-butadiene, 2-methyl-1,3-butadiene, 2-chloro-1,3-butadiene;
For example, cis-diallyl succinate, diallyl 2-methylidene succinate, vinyl (E) -but-2-enoate, (Z) -octadeca-9-enoate, (9Z, 12Z, 15Z) -octadeca-9, Ethylenically unsaturated monomers containing polyfunctional unsaturated bonds such as vinyl 12,15-trienoate;

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

  Further, for example, a copolymerizable ethylenically unsaturated monomer obtained by reacting the above-mentioned glycidyl group-containing ethenyl ester with a fatty acid, the above-mentioned halogenated alkylstyrene and a long-chain alcohol, poly (ethylene oxide) ), And a copolymerizable ethylenically unsaturated monomer obtained by reacting at least one alcoholic hydroxyl group-containing compound selected from poly (ethylene oxide) monoalkyl ethers, is also the ethylene of (a3) described above. Included in the unsaturated monomer. Furthermore, a high molecular weight ethylenically unsaturated monomer having a weight average molecular weight (Mw) of 200 to 2,000,000 and an ethylenically unsaturated double bond, a so-called macromonomer may be used. In particular, it is not limited to these. These may use only 1 type or may use multiple types together.

  In the present invention, the ethylenically unsaturated monomer (a1) having a hydroxyl group as a functional group and / or the ethylenically unsaturated monomer (a2) having a carboxyl group is a precursor (AP) of a copolymer (A). It is preferable to copolymerize by containing 1 to 40% by weight in 100% by weight of the total ethylenically unsaturated monomer. More preferably, it is 1 to 30% by weight. When (a1) and / or (a2) is less than 1% by weight, it is only difficult to perform a ring-opening addition reaction of a cyclic compound (f) having four or more membered rings having two or more oxygen atoms described later. In addition, the reaction with the cross-linking agent (B) becomes difficult, and not only the antistatic effect is not obtained, but also the cohesive force is liable to decrease, so that foaming, floating and peeling are likely to occur during heat and wet heat. There is a case. On the other hand, if it exceeds 40% by weight, the glass transition temperature is improved, so that the adhesive force may be reduced or the antistatic effect may be reduced.

In the present invention, an ethylenically unsaturated monomer having a hydroxyl group (a1) and / or an ethylenically unsaturated monomer having a carboxyl group (a2) and, if necessary, ethylene other than (a1) and (a2) Copolymer (A) obtained by copolymerizing the unsaturated unsaturated monomer (a3)
The precursor (AP) is synthesized by a method such as bulk polymerization, solution polymerization, emulsion polymerization or suspension polymerization using a polymerization initiator according to a conventional method. 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-methylpropionate) 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2-hydroxymethylpropionitrile), 2,2′-azobis [2- (2-imidazolin-2-yl) An azo compound such as propane].

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

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

  The cyclic compound (f) having four or more membered rings having two or more oxygen atoms according to the present invention is not particularly limited as long as it is a cyclic compound having two or more oxygen atoms. A compound in which the cyclic compound (f) undergoes ring-opening addition to the functional group of the monomer (a1) and / or the ethylenically unsaturated monomer (a2) having a carboxyl group to form a side chain; and The ring-opening addition of the cyclic compound (f) may be a single addition of only one molecule, or the ring compound (f) is further subjected to ring-opening addition to the hydroxyl group and / or carboxyl group generated at the end of the side chain. Multiple ring-opening additions may be performed. Thus, when ring-opening addition is multiplexed, the side chain can be made longer. As a result, the side chain can move more flexibly, so that the hydroxyl group and / or carboxyl group at the end of the side chain can react with the crosslinking agent (B) described later more efficiently. In addition, since there are a plurality of oxygen atoms in the side chain, there is an advantage that the affinity with the adherend becomes higher and the movement of the antistatic agent becomes easier, so that the antistatic effect is improved.

  Examples of the cyclic compound (f) having four or more members having two or more oxygen atoms include cyclic formal (f-1) and / or cyclic carbonate (f-2). Those having two or more are preferable, and even if they have alicyclic, aromatic or heterocyclic rings, they can be used without any problem.

  Examples of cyclic formal (f-1) include dioxolanes (f-1-1) and (poly) ethylene glycol obtained by acetalizing carbonyl of ethylene glycol or reacting formaldehyde with oxirane. Dioxanes that can be synthesized by a method of reacting in the presence of a mineral acid such as a mineral acid or an aromatic sulfonic acid catalyst, or a method of cyclodimerizing ethylene oxide using an acid catalyst such as sulfuric acid or boron trifluoride ( f-1-2) or trioxanes (f-1-3) mainly composed of trimer of formaldehyde.

  More specific examples of dioxolanes (f-1-1) include 1,2-dioxolane, 1,3-dioxolane, 2-methyl-1,3-dioxolane, 2,2-dimethyl-1, 3-dioxolane, 4-phenyl-1,3-dioxolane, glycerol formal, dimethylane, glycetal, dioxadrol, dexoxadorol, leboxadrol, chloralide, 2,2-dimethyl-4-ethyl-4-[(2, 6-dichlorophenyl) methoxymethyl] -1,3-dioxolane, hondalen, spiroxepin, trixolane, ciheptrane, etaconazole, pipoxolane, propiconazole, planferrin, oxabetrinyl, doxophilin, itraconazole, 1,4-dioxaspiro [4.5] decane 2,2-dimethyl 1,3-dioxolane-4-carbaldehyde, methyl (2-methyl-1,3-dioxolan-2-yl) acetate, (2-phenyl-1,3-dioxolan-2-yl) acetate 2-hydroxyethyl, 2,2-dimethyl-1,3-dioxolan-4-ylmethyl dodecanoate, 2-phenyl-1,3-dioxolane-2-ethyl acetate, 2,4-dimethyl-1,3-dioxolane-2-ethyl acetate, 2- [Bis (2-propenyloxy) methyl] -4,5-bis (2-propenyloxy) -1,3-dioxolane, domiodol, 4-methyl-1,3-dioxolane-4-ethanol, 2-ethyl -2-Methyl-1,3-dioxolane-4-methanol, 2-isobutyl-2-methyl-1,3-dioxolane-4-methanol, 1,4-dioxas B [4.5] decane-2-methanol, 2,2-dimethyl-1,3-dioxolane-4-methanol, 4,4-dimethyl-1,3-dioxolane-5-methanol, 1,3-dioxolane- 5,5-dimethanol, 2- (1,2-dihydroxyethyl) -1,3-dioxolane, (R)-(−)-2,2-dimethyl-1,3-dioxolane-4-methanol, 2- Benzyl-1,3-dioxolane-4-methanol, (+)-4,5-bis [hydroxy (diphenyl) methyl] -2,2-dimethyl-1,3-dioxolane, (2-phenyl-1,3- Dioxolan-4-yl) methanol, (4S) -α, α, α ′, α-tetraphenyl-2,2-dimethyl-1,3-dioxolane-4α, 5β-dimethanol, 4α, 5β-bis (hydroxy) Diphenyl Methyl) -2,2-dimethyl-1,3-dioxolane, 2-ethoxy-4- (4-methyl-1,3-dioxolan-2-yl) phenol, (4S, 5S) -2,2-dimethyl- α, α, α ′, α′-tetraphenyl-1,3-dioxolane-4,5-dimethanol, 2,2-dimethyl-1,3-dioxolane-4α, 5β-diylbis (diphenylmethanol), (4S ) -2,2-dimethyl-4α, 5β-bis (α-hydroxybenzhydryl) -1,3-dioxolane, α, α, α ′, α′-tetraphenyl-2,2-dimethyl-1,3 -Dioxolane-4α, 5β-dimethanol, 2,2-dimethyl-α, α, α ', α'-tetraphenyl-1,3-dioxolane-4α, 5β-dimethanol, (4S, 5S) -2, 2-Dimethyl 1,3-dioxolane-4,5 Bis (diphenylmethanol) α, α ′-(2,2-dimethyl-1,3-dioxolane-4,5-diyl) bis (α-phenylbenzyl alcohol), (4S, 5S) -2,2-dimethyl- α, α, α ′, α′-tetraphenyl-1,3-dioxolane-4,5-bis (methanol), 2,2-dimethyl-1,3-dioxolane-4α, 5β-bis (diphenylmethanol), (4S) -2,2-dimethyl-4α, 5β-bis (α-hydroxy-α-phenylbenzyl) -1,3-dioxolane, (4S, 5S) -α, α, α ′, α′-tetraphenyl -2,2-dimethyl-1,3-dioxolane-4α, 5β-dimethanol, [(4S, 5S) -2,2-dimethyl-4,5-dihydro-1,3-dioxole] -4,5- Diylbis (diphenylmethanol), α, α '-[(4S, 5S) 2,2-dimethyl-1,3-dioxolane-4,5-diyl] bis (α-phenylbenzyl alcohol), α, α, α ′, α′-tetraphenyl-2,2-dimethyl-1,3- Dioxolane-4,5-dimethanol, α, α, α ′, α′-tetraphenyl-2,2-dimethyl-1,3-dioxolane-4α, 5β-bismethanol, α, α ′-(2,2 -Dimethyl-1,3-dioxolane-4,5-diyl) bis (diphenylmethanol), (4S, 5S) -α, α, α ′, α′-tetraphenyl-2,2-dimethyl-1,3- Dioxolane-4,5-dimethanol, (+)-trans-α ′, α ′-(2,2-dimethyl-1,3-dioxolane-4,5-diyl) bis (diphenylmethanol), 1,1, 4,4-Tetraphenyl-2-O, 3-O-isopropylidene-D-tre Thor, [(4S, 5S) -2,2-dimethyl-1,3-dioxolane-4,5-diyl] bis (diphenylmethanol), (4S) -2,2-dimethyl-4α, 5β-bis (hydroxy Diphenylmethyl) -1,3-dioxolane, 2,2-dimethyl-1,3-dioxolane-4,5-bis (α ′, α′-diphenylmethanol), (4S) -2,2-dimethyl-α, α, α ′, α′-tetraphenyl-1,3-dioxolane-4α, 5β-dimethanol, (4S, 5S) -2,2-dimethyl-4α, 5β-bis (α-hydroxy-α-phenylbenzyl) ) -1,3-dioxolane, 2,2-dimethyl-1,3-dioxolane-4α, 5β-bis (α, α′-diphenylmethanol), α, α ′-(2,2-dimethyl-1,3) -Dioxolane-4α, 5β-diyl) bis (diphenylmethyl) Nord) dioxane, 2- [2- (1,3-dioxolan-2-yl) ethyl] -2,3-dihydro-1H-isoindole-1,3-dione, (2-methyl-2-ethyl-1 , 3-Dioxolan-4-yl) methyl acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl methacrylate, [cyclohexanespiro-2- (1,3-dioxolan-4-yl )] Methyl acrylate, [cyclohexanespiro-2- (1,3-dioxolan-4-yl)] methyl methacrylate, (2-methyl-2-oxo-1,3-dioxolan-4-yl) methyl acrylate, (2 -Methyl-2-oxo-1,3-dioxolan-4-yl) methyl methacrylate, 5- (4-methyl-1,3-dioxolan-2-yl) -1,3-benzodioxy Dioxolane derivatives such as sole;

For example, 1,2-oxathiolane 2-oxide, 1,2-oxathiolane 1-oxide, 1,2-oxaselenolane 2-oxide, 1-oxa-2-tellacyclopentane 2-oxide, 2-chloro-4- Methyl-1,3,2-dioxalsolane trimethylenesulfoxylate, 1,3,5-dioxathiane, 2-chloro-4-methyl-1,3,2-dioxaphospholane, 2-sulfide, -Chloro-1,3,2-dioxalsenane, 2-bromo-1,3,2-dioxalsenane, 2-chloro-1,3,2-dioxaphosphorinane 2-sulfide, 2-thiolato-1,3,2 In addition to two oxygen atoms such as -dioxaphosphorinane 2-selenide, dioxane derivatives having other atoms can be mentioned.

  More specifically, examples of the dioxanes (f-1-2) include 1,2-dioxane, mucbilin, placortin, 3-methyl-4-acetyl-6-hexyl-1,2-dioxane-3- All, 3-methyl-4-acetyl-6,6-bis (4-fluorophenyl) -1,2-dioxane-3-ol, 3-methyl-4-acetyl-6-phenyl-1,2-dioxane- 3-ol, 4-acetyl-3,4-dimethyl-6,6-diphenyl-1,2-dioxane-3-ol, 6,6-diphenyl-3-methyl-1,2-dioxane-3-ol, 6,6-Bis (4-methylphenyl) -3-methyl-1,2-dioxane-3-ol, 3-hydroxy-3-methyl-6,6-diphenyl-1,2-dioxane-4-carboxylic acid Ethyl, 4 Acetyl-4-methyl-6,6-bis (4-methylphenyl) -1,2-dioxane-3-ol, 3,3,6,6-tetrakis (4-methoxyphenyl) -1,2-dioxane, 3,6-bis (4-methoxyphenyl) -3,6-bis (4-methylphenyl) -1,2-dioxane, 3,3,6,6-tetrakis (2-methoxyphenyl) -1,2- Dioxane, 3,6-bis (4-methoxyphenyl) -3,6-bis (4-chlorophenyl) -1,2-dioxane, 3,3,6,6-tetrakis (4-phenoxyphenyl) -1,2 -Dioxane, 3,3,6,6-tetrakis (4-methylphenyl) -1,2-dioxane, 3,6-bis (4-methylphenyl) -3,6-diphenyl-1,2-dioxane, 3, , 6-bis (2,4- Methylphenyl) -3,6-diphenyl-1,2-dioxane, 3,3,6,6-tetraphenyl-1,2-dioxane, 4-acetyl-6-hexyl-3-methyl-1,2-dioxane -3-ol, 4-acetyl-3,4-dimethyl-6,6-diphenyl-1,2-dioxane-3-ol, 4-acetyl-6-phenyl-3-methyl-1,2-dioxane-3 -Ol, 6,6-diphenyl-4- (phenylaminocarbonyl) -3-methyl-1,2-dioxane-3-ol, 6,6-diphenyl-4-benzoyl-3-methyl-1,2-dioxane -3-ol, (3S) -3β, 6αdimethyl-4α, 5β-bis (4-acetoxy-3-methoxyphenyl) -1,2-dioxane, 6,6-diphenyl-4-acetyl-3-methyl- 4-D Tyl-1,2-dioxane-3-ol, (3S) -4α-acetyl-6,6-diphenyl-3-methyl-1,2-dioxane-3α-ol, (3S) -3β, 6α-dimethyl -4α, 5β-bis (4-hydroxy-3-methoxyphenyl) -1,2-dioxane, 4-acetyl-6,6-bis (4-methylphenyl) -3-methyl-1,2-dioxane-3 -Ol, 4-acetyl-6,6-bis (4-chlorophenyl) -3-methyl-1,2-dioxane-3-ol, 4-acetyl-6,6-bis (4-methoxyphenyl) -3- Methyl-1,2-dioxane-3-ol, 4-acetyl-6,6-bis (4-fluorophenyl) -3-methyl-1,2-dioxane-3-ol, α, 6-dimethyl-6 [4-Methyl-6- (2,6,6-trimethyl-1 Cyclohexen-1-yl) -3-hexenyl] -1,2-dioxane-3-acetic acid, 4-ethyl-6- (2-ethyl-3-hexenyl) -6-methyl-1,2-dioxane-3- Methyl acetate, (3R, αR, 6R) -6- [2-[[(4aR, 8aS) -1,4,4αβ, 7,8,8αβ-hexahydro-1,1,3,6-tetramethylnaphthalene] -2-yl] ethyl] -α, 6-dimethyl-1,2-dioxane-3-acetic acid, (R) -2-[(3R, 6R) -6β-methyl-6-[[(2S) -2 , 3,3α, 4,5,9β-hexahydro-3aα, 4α, 7,9bα-tetramethylnaphtho [1,2-b] furan] -2α-yl] -1,2-dioxane-3β-yl] propion Methyl acid, (2S) -2-[(3S, 6S) -6- [2-[(1S, 2R, 4aα, 8αβ) -decahydro-1,2α, 4a- Trimethyl-5-methylenenaphthalene-1β-yl] ethyl] -6-methyl-1,2-dioxan-3-yl] propanoic acid, (R) -2-[(3R, 6S) -6β-methyl-6- [2-[[(2R, 4aβ, 8aβ) -decahydro-1,1-dimethyl-3,6-dimethylenenaphthalene] -2α-yl] ethyl] -1,2-dioxane-3β-yl] propionic acid, etc. 1,2-dioxane derivatives of

  For example, 1,3-dioxane, parardol, doxypicomine, 2,4-diphenyl-1,3-dioxane, 5-hydroxy-1,3-dioxane, 2-cyclohexyl-1,3-dioxane, 1,3-dioxane- 2-one, 2α, 4α-dimethyl-1,3-dioxane, 5,6-dimethyl-1,3-dioxane, 5,5-diethyl-1,3-dioxane, 4,6-dibutyl-1,3- Dioxane, 2-ethyl-1,3-dioxane, 2-methylene-1,3-dioxane, 4,6-dimethyl-1,3-dioxane, 2,2-diphenoxy-1,3-dioxane, 2,2, 4-trimethyl-1,3-dioxane, 5,5-difluoro-1,3-dioxane, 2α-tert-butyl-4α-methyl-1,3-dioxane, 2-phenyl-4-methyl- , 3-dioxane, 4-methyl-4-phenyl-1,3-dioxane, 4,6-dimethyl-2-methylene-1,3-dioxane, 4,5,5-trimethyl-1,3-dioxane, 4, , 6-Dineopentyl-1,3-dioxane, 2-ethyl-5-methyl-1,3-dioxane, 2,5-dimethyl-5-phenyl-1,3-dioxane, 2-pentadecyl-1,3-dioxane 2-hexyl-1,3-dioxane, 2-butyl 2,5,5-trimethyl-1,3-dioxane, 5- (1-methylethyl) -1,3-dioxane, 2-phenyl-2-benzoyl -1,3-dioxane, 2,4,4,6-tetramethyl-1,3-dioxane, 2α, 4α, 5α-trimethyl-1,3-dioxane, 2α-hexyl-1,3-dioxane-5β- Oar 5,5-dimethyl-2-vinyl-1,3-dioxane, 4- (1-methylethenyl) -1,3-dioxane, 2-methyl-1,3-dioxane-2- (1-propanol), 4, 5-dimethyl-1,3-dioxane-5-methanol, 4,5-dimethyl-1,3-dioxane-4-methanol, 4,4,5-trimethyl-1,3-dioxane-5-ol, 5- Ethyl-2- (2-furyl) -4-propyl-1,3-dioxane, 5,5'-spirobi [1,3-dioxane], 4-methyl-1,3-dioxane, 2,2-dimethyl- 5-phenyl-1,3-dioxane-4,6-dione, 3,3-dimethyl-1,5-dioxaspiro [5,5] undecan-9-one, 2- (1,3-dioxane-2-yl ) Ethyltriphenylphosphonium bromide, 2 , 2-Dimethyl-5-methyl-1,3-dioxane-4,6-dione, 4-phenyl-1,3-dioxane, 5,5-dimethyl-1,3-dioxane-2-one, 5-bromo -2,2,5-trimethyl-1,3-dioxane-4,6-dione, 5-propyl-2- [2- (4-trifluoromethylphenyl) ethyl] -1,3-dioxane, 5-propyl -2- [4- (3,4,5-trifluorophenyl) cyclohexyl] -1,3-dioxane, 5-propyl-2- [4- (3,5-difluorophenyl) ethyl] -1,3- Dioxane, 5-propyl-2- [4- (3-fluoro-4-trifluoromethoxyphenyl) cyclohexyl] -1,3-dioxane, 5-propyl-2- [4- (4-trifluoromethylphenyl) butyl ] -1,3-Geo Xanthine, 5-propyl-2- [4- (3,5-difluorophenyl) cyclohexyl] -1,3-dioxane, 5-propyl-2- [4- {4- (3-fluoro-4-chlorophenyl)- 3,5-difluorophenyl} cyclohexyl] -1,3-dioxane, 4- (5-pentyl-1,3-dioxan-2-ylcyclohexane) carboxylic acid, 4- [5-pentyl- (1,3-dioxane) ) -2-yl] -cyclohexanecarboxylic acid 3,4,5-trifluorophenyl ester, 1- [2- (1,3-dioxan-2-yl) ethyl] cyclohexyl-3,4,5-trifluorobenzene 1- [2- (5-propyl-1,3-dioxan-2-yl) ethyl] cyclohexyl-3,4,5-trifluorobenzene, (Z) -6- (2- (2-chlorophene) Nyl) -4- (2-hydroxyphenyl) -1,3-dioxan-5-yl) hex-4-enoic acid, (Z) -6-(-2- [4-methoxyphenoxy-o-phenyl]- 4-o-hydroxyphenyl-1,3-dioxane-cis-5-yl) hex-4-enoic acid], (Z) -6- (2-3- [6-chloro-4H-chromen-4-one) 6-chloro-4-oxo-4H-chromen-3-yl] -4- (2-hydroxyphenyl-1,3-dioxane-cis-5-yl) hex-4-enoic acid, (Z) -6 ((2R, 4R, 5S) -2- (2-chlorophenyl) -4- (2-hydroxyphenyl) -1,3-dioxan-5-yl) hex-4-enoic acid, (Z) -6- ( (2S, 4S, 5R) -2- (2-Chlorophenyl) -4- (2-methoxyphenyl) Nyl) -1,3-dioxan-5-yl) hex-4-enoic acid, (Z) -6-((2S, 4S, 5R) -2- (2-chlorophenyl) -4- (2-acetoxyphenyl) ) -1,3-dioxan-5-yl) hex-4-enoic acid, methyl- (Z) -6-((2S, 4S, 5R) -2- (2-chlorophenyl) -4- (2-hydroxy) Phenyl) -1,3-dioxane-5-yl) hex-4-enoate, (Z) -6-((2S, 4S, 5R) -2- (2-chlorophenyl) -4- (2-hydroxyphenyl) -1,3-dioxan-5-yl) hex-4-enoate methyl, (Z) -6-((2S, 4S, 5R) -4- (2-acetoxyphenyl) -2- (2-chlorophenyl) -1,3-dioxane-5-yl) hex-4-enoic acid, etc. 1,3-dioxane derivatives;

  For example, 1,4-dioxane, 1,4-dioxane-2,3-dithione, 2,5-dimethyl-1,4-dioxane, piperoxane, safroxane, glycolide, DL-lactide, 5α, 6α-dimethyl-1, 4-dioxane-2-one, 2,5-divinyl-1,4-dioxane, 2,2′-bi (1,4-dioxane), 2,2,3,3,5,6,6-heptachloro- 1,4-dioxane, methylene-1,4-dioxane, (2R, 3S) -2,3-dichloro-1,4-dioxane, 2-methyl-3-methylene-1,4-dioxane, 2,5- Dimethyl-3-methylene-1,4-dioxane, 2-ethyl-5-methyl-1,4-dioxane, 3,6-diethyl-1,4-dioxane-2,5-dione, 2,6-dimethyl- 1,4-dioxane, 2-methyl-1,4 -Dioxane-2,3-diol, 2- (2-furanyl) -1,4-dioxane, 3,6-diisobutyl-1,4-dioxane-2,5-dione, 2,2,3,3,5 , 6-hexafluoro-5,6-dichloro-1,4-dioxane, 2,3-bis (oxiranylmethyl) -1,4-dioxane, 1,4-dioxane-2-yl hydroperoxide, 3, 6-dipropyl-1,4-dioxane-2,5-dione, 2,5,6-trimethyl-1,4-dioxane-2,3-diol, 2,3,3-trifluoro-2- (trifluoro Methyl) -1,4-dioxane, 5,6-dimethyl-1,4-dioxane-2,3-diol, 2-[(tetrahydro-2H-pyran) -2-ylmethyl]-1,4-dioxane, (1,4-dioxane-2-yl) methyl acetate, , 2,3,3-tetrafluoro-5,5,6,6-tetrachloro-1,4-dioxane, 1,4-dioxane-2,6-dimethanol, 2- (1,4-dioxane-2 -Yl) -1,4-naphthoquinone, 1,4-dioxane-2,5-bismethanol, N, N'-bis (benzyloxy) -1,4-dioxane-2,5-diimine, 3,6- Bis [(trimethylsilyl) oxy] -1,4-dioxane-2,5-dione, -2,3,3-trifluoro 5,5,6,6-tetrachloro-2- (trifluoromethyl) -1, 4-dioxane, 2,3-epoxy-2,3,5,5,6-pentafluoro-6- (trifluoromethyl) -1,4-dioxane, 2,2 ′-(3,6-dimethoxy-1 , 4-Dioxane-2,5-diylidene) diacetate, bis [morpholine-4 (Dithioformic acid)], 1,4-dioxane-2α, 3β-diyl, 2,5-bis (chloromethyl) -1,4-dioxane, 3,3-dichloro-5- (1-methylpropoxy) −1 , 4-Dioxane-2-one, 2,5-dimethyl-1,4-dioxane, 2- (2-fluoro-2-phenylsulfonylethyl) -1,4-dioxane, 2,3,3,5,6 Pentafluoro-2- (trifluoromethyl) -5,6-dichloro-1,4-dioxane, (2H8) -1,4-dioxane, trans-2,3-dichloro-1,4-dioxane, 2- [3- (3,3-Dimethyl-2-isopropyloxiranyl) -1-methylene-2-propynyl] -1,4-dioxane, 2,5-dihydroxy-3,6-dimethyl-3,6-diphosphono -2,5-diphospha (V) -1,4-dioxane-2 , 5-dione, N, N ′-[(1,4-dioxane-2,5-diyl) bis (methylene)] bis [N- (carboxymethyl) glycine], (3S, 5R) -3α-isopropyl- 5α-[(2S) -1- [butoxycarbonyl] pyrrolidin-2-yl] -6-[(E) -bromomethylene] -1,4-dioxan-2-one, 3,5,5,6-tetra Fluoro-3,6-bis (trifluoromethyl) -1,4-dioxane-2-one, 2,2,3,5,6-pentafluoro-5- (pentafluoroethoxy) -3,6-bis ( Trifluoromethyl) -1,4-dioxane, (3S, 5S) -3α-isopropyl-5β-[(2S) -1- [butoxycarbonyl] pyrrolidin-2-yl] -6-[(E) -bromomethylene ] -1,4-dioxan-2-one, (3S, 5S) -3α-isopropyl-5β-[(2S) -1- [butoxy Carbonyl] pyrrolidin-2-yl] -6-methylene-1,4-dioxane-2-one, 3,3,6,6-tetramethyl-1,4-dioxane-2,5-dione, [(2S , 3R) -1,4-dioxane-2,3-diyl] bis (thio) bis (thiophosphonic acid O, O-diethyl), α-[(3,3-dimethyl-2-isopropyloxiranyl) ethynyl] Α-methyl-1,4-dioxane-2-methanol, 2,3-dichloro-p-dioxane, 3,6-bis (methylmercuric acetate) -1,4-dioxane, 1,4-dioxane-2- ON, (3S, 5S) -3α-isopropyl-5α-[(2S) -1- [N- (4-methoxy-1,4-dioxobutyl) -L-Ala-L-Ala-] pyrrolidine-2- Yl] -6-methylene-1,4-dioxane-2-one, 5-methoxy-1,4-di Oxacyclohexane, 2,2,3,5,6-pentafluoro-5-[(trifluoroethenyl) oxy] -3,6-bis (trifluoromethyl) -1,4-dioxane, 2,3,5 6-tetramethyl-1,4-dioxane-2,5-diol, (3S, 5S) -3α-isopropyl-5β-[(2S) -1- [N- (4-methoxy-1,4-dioxobutyl) -L-Ala-L-Ala-] pyrrolidin-2-yl] -6-methylene-1,4-dioxane-2-one, 1,1,1,2,4,5,5,5-octafluoro- 2,4-bis [[2,3,5,5,6-pentafluoro-3,6-bis (trifluoromethyl) -1,4-dioxane-2-yl] oxy] -3-pentanone, 1, 3-dihydroxyacetone (dimer), 1,4-dioxane-2α, 5β-diol, 1, 4-dioxane-2,3-diol, 1,4-dioxane-2,5-dione, [(1,4-dioxane-2,3-diyl) bisthio] bis (thiophosphonic acid O, O-diethyl) and the like Examples include 1,4-dioxane derivatives.

  More specific examples of the trioxanes (f-1-3) include 1,3,5-trioxane, 2,4,6-triethyl-1,3,5-trioxane, 2,4,6- Tripropyl-1,3,5-trioxane, 2,4,6-triisopropyl-1,3-5-trioxane, 2,4,6-tributyl-1,3,5-trioxane, 2,4,6- Triisobutyl-1,3,5-trioxane, 2,4,6-trihexyl-1,3,5-trioxane, 2,4,6-trioctyl-1,3,5-trioxane, 2,2,4,4 , 6,6-hexamethyl-1,3,5-trioxane, 2,4,6-tris (1-methylethyl) -1,3,5-trioxane, 2- (1,1-dimethylethyl) -1, 3,5-trioxane, 2,4,6-triacetyl 1,3,5-trioxane, 2,4-diethyl-6-methyl-1,3,5-trioxane, 2-ethyl-4,6-dimethyl-1,3,5-trioxane, 2,4,6- Tricyclopentyl-1,3,5-trioxane, 2-cyclohexyl-4,6-dimethyl-1,3,5-trioxane, 2,4,6-tricyclohexyl-1,3,5-trioxane, 2-cyclohexyl- 4,6-dibenzyl-1,3,5-trioxane, 2,4,6-tribenzyl-1,3,5-trioxane, 2,4,6-triphenethyl-1,3,5-trioxane, 2,4 , 6-Tris (4-pentenyl) -1,3,5-trioxane, 1,3,5-trioxane-2-one, 1,3,5-trioxane-2,4-dione, 1,3,5- Trioxane-2,4 6-trione, 2,4,6-tris (chloromethyl) -1,3,5-trioxane, 2,4,6-tris (dichloromethyl) -1,3,5-trioxane, 2,4,6-tris (2-chloroethyl) -1,3,5-trioxane, 2,2-dichloro-1,3,5-trioxane, 2,2,4,4-tetrachloro-1,3,5-trioxane, 2,2 ′, 2 ″-(1,3,5-trioxane-2,4,6-triyl) trisethanol, 2,2 ′, 2 ″-[(1,3,5-trioxane-2,4,6 -Triyl) trismethylene] tris (1,3-propanediol), 1,3,5-trioxane-2,4,6-tris (methyl propanoate), 4,4 ', 4 "-(1,3 , 5-Trioxane-2,4,6-triyl) tributyric acid, 1,3,5 -Trioxane-2,4,6-tricarboxylic acid triethyl, 2- (triethylsilyl) -1,3,5-trioxane, 2- (trimethylsilyl) -1,3,5-trioxane, 2,4,6-triimine- 1,3,5 such as 1,3-5-trioxane, 2,4,6-trivinyl-1,3,5-trioxane, 1,3,5-trioxane-2,4,6-tripropionitrile, thiamelide -Trioxane derivatives etc. are mentioned.

  For example, 1,2,4-trioxane, 3- (2-furanyl) -5,5,6,6-tetramethyl-1,2,4-trioxane, 3- (4-quinolinyl) -5,5,6 , 6-Tetramethyl-1,2,4-trioxane, 4- (5,5,6,6-tetramethyl-1,2,4-trioxane-3-yl) benzaldehyde, 3,3 '-(p- Phenylene) bis (5,5,6,6-tetramethyl-1,2,4-trioxane), 3- (2,6-dimethyl-5-heptenyl) -5,5,6,6-tetramethyl-1 , 2,4-Trioxane, 4- (5,5,6,6-tetramethyl-1,2,4-trioxane-3-yl) benzyl alcohol, phenylcarbamic acid 4- (5,5,6,6- Tetramethyl-1,2,4-trioxane-3-yl) benzyl, -[4- (5,5,6,6-tetramethyl-1,2,4-trioxane-3-yl) benzylidene] -2-carbamoylhydrazine, 3- (2-methyl-6-p-tolyl-5 -Hexenyl) -5,5,6,6-tetramethyl-1,2,4-trioxane, 3- (2-methyl-5-decenyl) -5,5,6,6-tetramethyl-1,2, 4-trioxane, (6S) -6α-[(R) -α-methylbenzyl] spiro [1,2,4-trioxane-3,1′-cyclopentane], 6- (1-phenylethenyl) spiro [ 1,2,4-trioxane-3,1'-cyclohexane], dispiro [cyclohexane-1,3 '-[1,2,4] trioxane-6', 1 "-cyclohexane], 6- (1-phenyl Vinyl) spiro [1,2,4-trioxy -3,1'-cyclopentane], 3,3-dimethyl-6- [1- (biphenyl-4-yl) vinyl] -1,2,4-trioxane, 6-bromomethyl-6-methyl-3- Phenyl-1,2,4-trioxane, 6-bromomethyl-6-methyl-3-heptyl-1,2,4-trioxane, 6-iodomethyl-6-methyl-3-phenyl-1,2,4-trioxane, 3,3,6,6-tetrafluoro-1,2,4-trioxane, 3,6-difluoro-1,2,4-trioxane, 3-phenyl-1,2,4-trioxane-6-ol, 5, -Methyl-3-phenyl-1,2,4-trioxane-6-ol, 5,5-dimethyl-3-phenyl-1,2,4-trioxane-6-ol, 3-phenyl-6-methyl-1 , 2,4-trio Sun-6-ol, 3-phenyl-6-methyl-1,2,4-trioxane-6-yl hydroperoxide, 3,3,6-trimethyl-1,2,4-trioxane-6-ol, α, α-Dimethyl-3-phenyl-1,2,4-trioxane-6-methanol, 3-phenyl-6-methyl-1,2,4-trioxane-6-methanol, 2-methyl-6- (3,3 -Dimethyl-1,2,4-trioxane-6-yl) -1,6-heptadien-3-ol, 4- (3,3-dimethyl-1,2,4-trioxane-6-yl) -4- Penten-1-ol, 1-phenyl-4- (spiro [1,2,4-trioxane-3,1'-cyclopentane] -6-yl) -4-penten-1-ol, 1-phenyl-4 -(Spiro [1,2,4-trioxy 1,3-dioxolane, 1,3-dioxane such as 1,3-dioxolane, 1,3-dicyclolane] -6-yl) -4-penten-1-ol 1,3,5-trioxane is preferably used in terms of reactivity.

As the cyclic carbonate (f-2) in the present invention, a method of depolymerizing a polymer obtained by the reaction of glycol and dialkyl carbonate (see JP-A-2-56356), or the reaction of the corresponding alkylene oxide and carbon dioxide. Can be synthesized. The cyclic carbonate has a 5-membered ring, 6-membered ring or 7-membered ring structure. Specific examples thereof include ethylene carbonate, propylene carbonate, butylene carbonate, 4-pentyl-1,3-dioxolan-2-one. 4-butyl-1,3-dioxolane-2-one, 4-propyl-1,3-dioxolane-2-one, 4- (isopropoxymethyl) -1,3-dioxolane-2-one, 4-hexyl -1,3-dioxolan-2-one, 4-hexyl-5-methylene-1,3-dioxolan-2-one, 4,5-dimethyl-1,3-dioxolan-2-one, 4,4,5 , 5-Tetramethyl-1,3-dioxolane-2-one, 4-octyl-1,3-dioxolane-2-one, 4-nonyl-5-vinyl-1,3-dioxolane-2- 4-decyl-1,3-dioxolan-2-one, 4,5-bismethylene-1,3-dioxolan-2-one, 4,4-dimethyl-1,3-dioxolan-2-one, 4, 4,5,5-tetraethyl-1,3-dioxolane-2-one, hexahydro-1,3-benzodioxol-2-one, 4-isopropyl-4-methyl-5-methylene-1,3-dioxolane -2-one, vinylene carbonate, allylethylene carbonate, allyl succinic anhydride, 4-vinyl-1,3-dioxolane-2-one, 4-phenethyl-5-vinyl-1,3-dioxolan-2-one, 4 -Methylene-1,3-dioxolan-2-one, 4- (3-butenyl) -1,3-dioxolan-2-one, 4- (5-hydroxy-6,6-dimethyltetrahydro (Ro-2H-pyran-2-yl) -1,3-dioxolan-2-one, 4-[(E) -iodomethylene] -5-cyclopropyl-1,3-dioxolan-2-one, 4-cyclohexyl -5-vinyl-1,3-dioxolane-2-one, 4- (allyloxy) -4,5,5-trimethyl-1,3-dioxolan-2-one, 4-[(1E) -1,3- Butadienyl] -1,3-dioxolane-2-one, 4-ethyl-4-methyl-5-methylene-1,3-dioxolan-2-one, 4- (2-methyl-2-propenylidene) -5,5 -Dimethyl-1,3-dioxolane-2-one, 4- [4- (methoxycarbonyloxy) butyl] -1,3-dioxolan-2-one, 4-vinyl-5,5-diethyl-1,3- Dioxolan-2-one, 4- Phenyl-5-vinyl-1,3-dioxolan-2-one, 4,5,5-trimethyl-4- (1-propynyl) -1,3-dioxolan-2-one, 4-vinyl-5,5- Bis (2-cyclohexylethyl) -1,3-dioxolane-2-one, 4,5,5-trimethyl-4- (3-methyl-3-buten-1-ynyl) -1,3-dioxolane-2- ON, 4- (vinyloxymethyl) -1,3-dioxolane-2-one, 4,4-dimethyl-5-[(E) -3-buten-1-ylidene] -1,3-dioxolane-2- ON, 4-[(E) -3-buten-1-ylidene] -1,3-dioxolan-2-one, 4,4-dimethyl-5-[(Z) -1-phenyl-3-butene-1 -Ilidene] -1,3-dioxolan-2-one, methacrylic acid ( -Oxo-1,3-dioxolan-4-yl) methyl, 4-methyl-5-[(E) -3-buten-1-ylidene] -1,3-dioxolan-2-one, 4-methyl-5 -[(Z) -3-buten-1-ylidene] -1,3-dioxolan-2-one, 4,4-dimethyl-5-[(Z) -2-butyn-1-ylidene] -1,3 -Dioxolan-2-one, 4,4-dimethyl-5-[(E) -ethylidene] -1,3-dioxolan-2-one, 4,4-dimethyl-5-[(Z) -3-butene- 1-ylidene] -1,3-dioxolan-2-one, 4- (1-hexynyl) -4-methyl-1,3-dioxolan-2-one, 4- (1-propenyloxymethyl) -1,3 -Dioxolan-2-one, 4-[(1E) -1-methyl-3-butenylidene -1,3-dioxolan-2-one, 4-[(1Z) -1-phenyl-3-butenylidene] -1,3-dioxolan-2-one, 4,4-dipentyl-5-[(1E)- 1,3-butadienyl] -1,3-dioxolane-2-one, 4-phenyl-5-methylene-1,3-dioxolane-2-one, 4-methyl-5-methylene-1,3-dioxolane-2 -One, 4-methyl-4-vinyl-5-methylene-1,3-dioxolane-2-one, 4-propargyl-5-methylene-1,3-dioxolan-2-one, 4-[(E)- Bromomethylene] -1,3-dioxolan-2-one, [(E) -2-oxo-5,5-dimethyl-1,3-dioxolane-4-ylidene] ethyl acetate, 4-[(E) -2 -(Tert-Butoxycarbonyloxy ) Ethylidene] -1,3-dioxolan-2-one, 4-ethyl-5-methylene-1,3-dioxolan-2-one, 4- (hydroxymethyl) -1,3-dioxolan-2-one, 4-[(E) -2- (tert-butoxycarbonyloxy) ethylidene] -5-methyl-1,3-dioxolan-2-one, 4,5-divinyl-1,3-dioxolan-2-one, 4 -(1-Naphtyl) -5-vinyl-1,3-dioxolan-2-one, 4,4-bis (2-cyclohexylethyl) -5-[(1E) -1,3-butadienyl] -1,3 -Dioxolan-2-one, (4S) -4-phenyl-4-methyl-5- (1,3-butadienyl) -1,3-dioxolan-2-one, 4- (2-propyne-1-ylidene) -5,5-dimethyl-1, -Dioxolan-2-one, 4,4-dimethyl-5-methylene-1,3-dioxolan-2-one, 5-butyl-5-methyl-4-methylene-1,3-dioxolan-2-one, glycerin Carbonate, 4- (butoxymethyl) -1,3-dioxolane-2-one, 4- (allyloxymethyl) -1,3-dioxolane-2-one, 4- (hydroxymethyl) -1,3-dioxolane- 2-one, 4- (methoxymethyl) -1,3-dioxolane-2-one, 4- (4-ethenylbenzyloxymethyl) -1,3-dioxolane-2-one, 4-ethyl-4-methyl -5- (3-phenylpropylidene) -1,3-dioxolane-2-one, 4-ethyl-4-methyl-5-benzylidene-1,3-dioxolan-2-one, 4- (hex Thiomethyl) -1,3-dioxolan-2-one, 4,4-dimethyl-5-[(E) -2-phenylethylidene] -1,3-dioxolan-2-one, 4- (p-tolyl)- 1,3-dioxolan-2-one, 4-methyl-5-phenyl-1,3-dioxolan-2-one, 4-benzyl-1,3-dioxolan-2-one, 4- (benzyloxymethyl)- 1,3-dioxolane-2-one, 4-phenyl-1,3-dioxolane-2-one, 4-phenyl-4-methyl-5-methylene-1,3-dioxolan-2-one, 4-phenyl- 1,3-dioxolan-2-one, 4-methyl-4-phenyl-1,3-dioxolan-2-one, 4-phenoxy-1,3-dioxolan-2-one, 4-butoxy-4,5- Dimethyl-5-pheny Ru-1,3-dioxolan-2-one, (4S) -4β- (phenylethynyl) -4-phenethyl-5-[(Z) -benzylidene] -1,3-dioxolan-2-one, 4- [ 4- (Phenoxycarbonyloxy) butyl] -1,3-dioxolan-2-one, 4- [4- (glycidylcarbamoyloxy) butyl] -1,3-dioxolan-2-one, 4-oxiranyl-1,3 -Dioxolan-2-one, 4- [4- (2-oxo-1,3-dioxolan-4-ylmethylcarbamoyloxy) butyl] -1,3-dioxolan-2-one, 4- (2-oxo- 1,3-dioxolan-4-ylmethylcarbamoyloxymethyl) -1,3-dioxolan-2-one, 4,4'-bi [1,3-dioxolan-2-one], 4,4'-teto Methylene bis (1,3-dioxolan-2-one), 4,4 '-(ethylenebisthiobistetramethylene) bis (1,3-dioxolan-2-one), 4,4'-[1,6-hexane Diylbis (oxymethylene)] bis (1,3-dioxolan-2-one), 4,4 '-[hexamethylenebis (thioethylene)] bis (1,3-dioxolan-2-one), 4,4' -[Isobutylidenebis (4,1-phenylene) bisoxybismethylene] bis (1,3-dioxolan-2-one), 4,4 '-[isopropylidenebis [(4,1-phenylene) oxymethylene ]] Bis (1,3-dioxolan-2-one), 4,4-dimethyl-5-[(Z) -benzylidene] -1,3-dioxolan-2-one, 4- [2- (benzyloxy) ethyl ] -1,3-dioxolane-2-one, 4- [2- (trityloxy) ethyl] -1,3-dioxolan-2-one, 4,5-diphenyl-1,3-dioxolan-2-one, 4,4-dimethyl-5- [1- (1-naphthyl) ethenyl] -1,3-dioxolan-2-one, 4,4-dimethyl-5- [1- (2-naphthyl) ethenyl] -1, 3-dioxolan-2-one, 4,4-dimethyl-5- [1- (4-methylphenyl) ethenyl] -1,3-dioxolan-2-one, 4,4-dimethyl-5- [1- ( 4-methoxyphenyl) ethenyl] -1,3-dioxolan-2-one, 4,4-dimethyl-5- [1- (4-hydroxyphenyl) ethenyl] -1,3-dioxolan-2-one, 4, 4-Dimethyl-5- (1-methylene-2-fur Nyl-2-propenyl) -1,3-dioxolane-2-one, 4,4-dimethyl-5-[(E) -1-methylene-3-phenyl-2-propenyl] -1,3-dioxolane-2 -One, 4,4-dimethyl-5- (1-phenylethenyl) -1,3-dioxolane-2-one, 4-methyl-5- (1-phenylethenyl) -1,3-dioxolane-2 -One, 4,4-dimethyl-5-[(E) -3-phenyl-1-propenyl] -1,3-dioxolane-2-one, 4- (1-phenylethenyl) -1,3-dioxolane -2-one, 4,4-dimethyl-5- (1-phenyl-1-propenyl) -1,3-dioxolan-2-one, 4,4-dimethyl-5- (1,2-diphenylethenyl) -1,3-dioxolan-2-one, 4,4-dimethyl Ru-5- (2-Methyl-1-phenyl-1-propenyl) -1,3-dioxolan-2-one, 4,4,5-trimethyl-5- (1-phenylethenyl) -1,3- Dioxolane-2-one, 4- (benzyloxymethyl) -1,3-dioxolane-2-one, 4,4-diphenyl-1,3-dioxolan-2-one, 4,4 '-[(1,3 -Phenylene) bis (oxymethylene)] bis (1,3-dioxolan-2-one, 4,4-dimethyl-5-[(Z) -1-naphthylmethylene] -1,3-dioxolan-2-one, 4,4-Dimethyl-5-[(Z) -4-methoxybenzylidene] -1,3-dioxolan-2-one, 4,4-dimethyl-5-[(Z) -4-hydroxybenzylidene] -1, 3-Dioxolan-2-one, 4- (Fe Nylethynyl) -4-methyl-1,3-dioxolane-2-one, 4- (phenylethynyl) -4,5-dimethyl-1,3-dioxolan-2-one, 4- [1- (4-methoxyphenoxy) ) Vinyl] -5,5-diethyl-1,3-dioxolan-2-one, 4- [1- (4-methoxyphenoxy) ethenyl] -5,5-dimethyl-1,3-dioxolan-2-one, 4- [3- (Benzyloxy) propyl] -5-methyl-1,3-dioxolan-2-one, 7- [2- (2-oxo-1,3-dioxolan-4-yl) ethoxy] -2H -1-benzopyran-2-one, 7- [2- (2-oxo-4-methyl-1,3-dioxolan-4-yl) ethoxy] -2H-1-benzopyran-2-one, 4- (tri Fluoromethyl)-

5- (Phenylthio) -1,3-dioxolane-2-one, 5- (Benzyloxy) -1,3-dioxolane-2-one, 4- (Isobutoxymethyl) -1,3-dioxolane-2-one 4- (4-Nonylbenzyloxymethyl) -1,3-dioxolan-2-one, 4- (4-chlorophenylthiomethyl) -1,3-dioxolan-2-one, 4- [3- (chloromethyl ) Phenyl] -1,3-dioxolane-2-one, 4- [4- (chloromethyl) phenyl] -1,3-dioxolan-2-one, 4,4-dipropyl-5- [1- (4- Methoxyphenoxy) ethenyl] -1,3-dioxolan-2-one, 4,4-dipentyl-5- [1- (4-methoxyphenoxy) ethenyl] -1,3-dioxolan-2-one, 4,4- Diiso Lopyl-5- [1- (4-methoxyphenoxy) ethenyl] -1,3-dioxolan-2-one, 4,4-diphenethyl-5- [1- (4-methoxyphenoxy) ethenyl] -1,3- Dioxolan-2-one, 4,4-bis (2-cyclohexylethyl) -5- [1- (4-methoxyphenoxy) ethenyl] -1,3-dioxolan-2-one, 4- [1- (phenylthio) Cyclohexyl] -1,3-dioxolane-2-one, 4- (3-methoxy-4-ethoxyphenyl) -5- (hydroxymethyl) -1,3-dioxolan-2-one, 4- (phenoxycarbonyloxymethyl) ) -1,3-dioxolan-2-one, 4-benzylidene-5,5-dimethyl-1,3-dioxolan-2-one, 4-[(2-naphthyl) methylene] 5,5-Dimethyl-1,3-dioxolane-2-one, 4- (4-chlorobenzylidene) -5,5-dimethyl-1,3-dioxolan-2-one, 4- [4- (trifluoromethyl ) Benzylidene] -5,5-dimethyl-1,3-dioxolane-2-one, 5-methyl-5-phenyl-4- (3-phenylpropylidene) -1,3-dioxolan-2-one, 5,5 -Dimethyl-4- (3-phenylpropylidene) -1,3-dioxolane-2-one, 4- [4- (chlorocarbonyloxy) butyl] -1,3-dioxolan-2-one, 4-chloro-1 , 3-Dioxolan-2-one, 4-chloro-4,5-dimethyl-1,3-dioxolan-2-one, 4- (chlorocarbonyloxymethyl) -1,3-dioxolan-2-one, 4- ( p-chlorophenoxymethyl) -1,3-dioxolan-2-one, 4- (chloromethyl) -1,3-dioxolan-2-one, fluoroethylene carbonate, 4-fluoro-5-methyl-1,3- Dioxolane-2-one, 4- (fluoromethyl) -1,3-dioxolane-2-one, 4- (2,2,3,3,4,4,5,5,5-nonafluoropentyl) -1 , 3-dioxolan-2-one, 4,5-difluoro-1,3-dioxolan-2-one, 4-fluoro-4-methyl-1,3-dioxolan-2-one, 4,4-difluoro-1 , 3-Dioxolan-2-one, 4,5-Dichloro-1,3-dioxolan-2-one, 4- (α, α-Difluorobenzyl) -1,3-dioxolan-2-one, 4-[( Tetrahydrofuran-3 -Yl) difluoromethyl] -1,3-dioxolane-2-one, (4S, 5R) -4,5-diphenyl-1,3-dioxolan-2-one, 4α, 5α-dimethyl-1,3-dioxolane -2-one, (4R, 5R) -4,5-dimethyl-1,3-dioxolane-2-one, (4S, 5S) -4,5-dimethyl-1,3-dioxolane-2-one, ( 4S) -4β-methyl-1,3-dioxolane-2-one, (R) -4-methyl-1,3-dioxolane-2-one, (S) -5-ethyl-1,3-dioxolane-2 -One, 4-[(triphenylsilyl) methyl] -5,5-dimethyl-1,3-dioxolan-2-one, 4- [9- (3-thienyl) nonyl] -1,3-dioxolane-2 -One, 4- (methylaminomethyl) -1,3-di Xoxolan-2-one, 4- (4-chlorophenylthio) -1,3-dioxolane-2-one, 4- (phenylthio) -1,3-dioxolan-2-one, 4- (4-methoxyphenylthio) -1,3-dioxolane-2-one, 4- (4-bromophenylthio) -1,3-dioxolane-2-one, 4-fluoro-4-[(4-methoxyphenyl) thio] -1,3 -Dioxolane-2-one, 4-fluoro-4- (4-bromophenylthio) -1,3-dioxolane-2-one, 4- (phenylthiofluoromethyl) -1,3-dioxolan-2-one, 4- (phenylthiodifluoromethyl) -1,3-dioxolane-2-one, 4- (phenylthiomethyl) -1,3-dioxolane-2-one, 4- [difluoro (phenylsulfonyl) Methyl] -1,3-dioxolan-2-one, 4- [difluoro (phenylsulfinyl) methyl] -1,3-dioxolan-2-one, 4,4 '-[sulfonylbis (p-phenyleneoxymethylene)] Bis (1,3-dioxolan-2-one), 4- (4-methylphenylthio) -1,3-dioxolan-2-one, 4-fluoro-4- (4-methylphenylthio) -1,3 -Dioxolan-2-one, 4-[[4- (fluoromethyl) phenyl] thio] -1,3-dioxolan-2-one, 4,4,5,5-tetramethyl-2- (phenylsulfonyloxyimino ) -1,3-dioxolane, 2- (4-nitrophenoxy) -4-methyl-2-phospha (V) -1,3-dioxolan-2-one, 4-fluoro-4- (phenylthio) -1,3-dioxolane-2-one, 4-fluoro-4- (4-chlorophenylthio) -1,3-dioxolane-2-one, 4- (glycidyloxymethyl) -1,3-dioxolane-2- ON, glycidylcarbamic acid (2-oxo-1,3-dioxolan-4-yl) methyl, 4- (norborna-5-en-2-yl) -1,3-dioxolan-2-one, 4- [2 -(2-naphthyl) ethyl] -5-methoxy-1,3-dioxolane-2-one, 4- [2- (1-naphthyl) ethyl] -5-methoxy-1,3-dioxolan-2-one, 4,4-Dimethyl-5- (3-thienylmethylene) -1,3-dioxolane-2-one, 4- [2- [dimethyl (trimethylsilyloxy) silyl] ethyl] -1,3-dioxolan-2-one 4 [2-[(Methyl) bis (trimethylsilyloxy) silyl] ethyl] -1,3-dioxolane-2-one, 4- [2- (trimethylsilyl) ethyl] -1,3-dioxolan-2-one, 4- [4- (Glycidylcarbamoyloxy) butyl] -1,3-dioxolan-2-one, 4- [4- (2-oxo-1,3-dioxolan-4-ylmethylcarbamoyloxy) butyl] -1,3 -Dioxolan-2-one, 4- [4- (glycidylcarbamoyloxy) butyl] -1,3-dioxolan-2-one, 4- (2-oxo-1,3-dioxolan-4-ylmethylcarbamoyloxymethyl) ) -1,3-dioxolan-2-one and other 5-membered ring carbonates;

  For example, trimethylene carbonate, 4-methyl-1,3-dioxane-2-one, 2,2-dimethoxypropane-1,3-diyl carbonate, 5-methyl-1,3-dioxane-2-one, 5,5 -Dimethyl-1,3-dioxan-2-one (also called neopentyl glycol carbonate), 5-methyl-5-propyl-1,3-dioxane-2-one, 5-hydroxymethyl-5-methyl-1, 3-Dioxane-2-one, 4-phenyl-1,3-dioxane-2-one, 5- (hydroxymethyl) -5-ethyl-1,3-dioxane-2-one, 4-methylene-1,3 -Dioxane-2-one, 5,5-dimethyl-4-ethenyl-1,3-dioxane-2-one, 5-cyano-5-methyl-1,3-dioxane-2-one, 4,4-dimethyl -1, -Dioxane-2-one, 5-butyl-1,3-dioxane-2-one, 5,5-diethyl-1,3-dioxane-2-one, 5-ethyl-5-phenyl-1,3-dioxane -2-one, 2-oxo-5-ethyl-1,3-dioxane-5-ylmethyl methacrylate, 5-methyl-5-phenyl-1,3-dioxane-2-one, 4-styryl-5,5 -Dimethyl-1,3-dioxane-2-one, 4-styryl-1,3-dioxane-2-one, 4- (1-heptenyl) -1,3-dioxane-2-one, 4-ethenyl-6 -Phenyl-1,3-dioxane-2-one, 4-isopropenyl-6-phenyl-1,3-dioxane-2-one, 4-allyl-6-phenyl-1,3-dioxane-2-one, 4-ethenyl-6-tert- Tyl-1,3-dioxane-2-one, 4-styryl-5,5-dimethyl-6-isopropyl-1,3-dioxane-2-one, 5- [2- (2-amino-9H-purine- 9-yl) ethyl] -1,3-dioxane-2-one, 4- (1-phenylethenyl) -1,3-dioxane-2-one, 5,5-diphenyl-1,3-dioxane-2 -One, 5-methyl-4- (1-phenylethenyl) -1,3-dioxane-2-one, 4,4-dimethyl-6- (1-phenylethenyl) -1,3-dioxane-2 -One, 5-methylene-1,3-dioxane-2-one, 4-[(E) -styryl] -1,3-dioxane-2-one, 5-octyl-1,3-dioxane-2-one 5-dodecyl-1,3-dioxane-2-one, 2-oxo-5 -Methyl-1,3-dioxane-5-carboxylic acid benzyl, 4,6-dimethyl-1,3-dioxane-2-one, 4-methoxybenzoic acid 2-oxo-5-methyl-1,3-dioxane- 5-ylmethyl, 2-oxo-5-methyl-1,3-dioxane-5-ylmethyl benzoate, 4-oxo-5-methyl-1,3-dioxane-5-ylmethyl 4-nitrobenzoate, 4,4 , 6-Trimethyl-1,3-dioxane-2-one, 5-ethyl-5- (methoxycarbonyloxymethyl) -1,3-dioxane-2-one, 5-ethyl-5- (ethoxycarbonyloxymethyl) -1,3-dioxane-2-one, 5- (4-butoxyphenyl) -1,3-dioxane-2-one, 5- [4- (pentyloxy) phenyl] -1,3-dioxane- -One, 5- (4-propoxyphenyl) -1,3-dioxane-2-one, 5- [4- (hexyloxy) phenyl] -1,3-dioxane-2-one, 5-allyl-1, 3-Dioxane-2-one, 5- (benzyloxycarbonyl) -1,3-dioxane-2-one, 5-methyl-4- (benzoyloxymethyl) -1,3-dioxane-2-one, 5- Methyl-4- (4-nitrobenzoyloxymethyl) -1,3-dioxane-2-one, 5-methyl-4- (4-methoxybenzoyloxymethyl) -1,3-dioxan-2-one, 5- (4-Methylene-5-hexene-1-ylidene) -1,3-dioxane-2-one, 4-fluoro-1,3-dioxane-2-one, 4-fluoro-4-methyl-1,3- Dioxane-2- 5-ethyl-5- (4-vinylbenzyloxymethyl) -1,3-dioxane-2-one, 4-fluoro-4-methyl-1,3-dioxane-2-one, 5-ethyl-5 -(4-Vinylbenzyloxymethyl) -1,3-dioxane-2-one, 5- (Benzyloxy) -1,3-dioxane-2-one, 5-hydroxy-1,3-dioxane-2-one 4-methylene-5,5-dimethyl-1,3-dioxane-2-one, 5-ethyl-5- (2-hydroxyethyl) -1,3-dioxane-2-one, 4- [1- ( Phenylthio) cyclohexyl] -1,3-dioxan-2-one, 4- [4- (octyloxy) phenylazo] -6-hexyl-1,3-dioxane-2-one, 4- (4-methoxyphenylazo) -6-hexyl -1,3-dioxane-2-one, 4- [4- (octyloxy) phenylazo] -6-decyl-1,3-dioxane-2-one, 2-oxo-5-methyl-1,3-dioxane Allyl-5-carboxylate, 4- [1- (phenylthio) cyclohexyl] -5,5-dimethyl-1,3-dioxane-2-one, 4-allyl-6-methyl-1,3-dioxane-2- ON, 5-ethyl-5- (benzyloxymethyl) -1,3-dioxane-2-one, 5- [2- (benzyloxy) ethoxy] -1,3-dioxane-2-one, 5- (allyloxy) ) -1,3-Dioxane-2-one, 5- [3- (2-hydroxyethylthio) propoxy] -1,3-dioxan-2-one, 5- (benzyloxycarbonylamino) -1,3- Dioxane -One, 5- [6- [4- (4-pentylcyclohexyl) phenoxy] hexyloxy] -1,3-dioxan-2-one, 4- (iodomethyl) -6- [2- (4-methoxybenzyloxy) ) Ethyl] -1,3-dioxane-2-one, (5S) -4-vinyl-5β- (2,2-dimethoxyethyl) -1,3-dioxane-2-one, 5-allyl-5-propargyl -1,3-dioxane-2-one, 4-vinyl-5- (1-methyl-5-imidazolylmethyl) -1,3-dioxane-2-one, 5-benzylidene-1,3-dioxane-2- ON, 5- (glycidyloxymethyl) -5-ethyl-1,3-dioxane-2-one, 5- (allyloxymethyl) -5-ethyl-1,3-dioxane-2-one, 5,5- Bis (Azidomethi L) -1,3-dioxane-2-one, 5-methyl-5-[[2- (vinylsulfonyl) ethyl] thiomethyl] -1,3-dioxane-2-one, 5- (allyloxymethyl)- 5-ethyl-1,3-dioxane-2-one, 5,5 '-(oxybismethylene) bis (5-ethyl-1,3-dioxane-2-one), 5,5'-(4,7 -Dithiadecane-1,10-diyl) bis (1,3-dioxane-2-one), 5,5 '-(ethylenebisthiobistetramethylene) bis (1,3-dioxane-2-one), 5- Methyl-5- (2-oxo-1,3-dioxolan-4-ylmethyl) -1,3-dioxan-2-one, 5-ethyl-5- (2-oxo-1,3-dioxolan-4-ylmethyl) ) -1,3-Dioxane-2-one, 5- [ 2-Oxo-1,3-dioxolan-4-yl) methyl] -5-propyl-1,3-dioxan-2-one, 5- (2-oxo-1,3-dioxolan-4-ylmethoxy) -5 6-membered ring carbonates such as 2-ethyl-1,3-dioxan-2-one;

  For example, 1,3-dioxepan-2-one, 5-methyl-1,3-dioxepan-2-one, 4-methyl-1,3-dioxepan-2-one, 5,5-dimethyl-1,3- Dioxepan-2-one, 5-phenyl-1,3-dioxepan-2-one, 4-phenyl-1,3-dioxepan-2-one, 4-fluoro-1,3-dioxepan-2-one, 4- Fluoro-4-methyl-1,3-dioxepan-2-one, 4- [1- (phenylthio) cyclohexyl] -1,3-dioxepan-2-one, 5,5 '-(ethylenebisthiobistrimethylene) bis 7-membered ring carbonates such as (1,3-dioxepan-2-one) are mentioned, but 5-membered ring carbonates such as ethylene carbonate, propylene carbonate, and glycerin carbonate are Preferably used from the viewpoint of refractoriness.

  In the present invention, the precursor of the copolymer (A) obtained by copolymerizing the ethylenically unsaturated monomer represented by (a1) and / or (a2) and, if necessary, (a3) (AP) is subjected to a ring-opening addition reaction with the above-mentioned cyclic formal (f-1) or cyclic carbonate (f-2) to a hydroxyl group and / or a carboxyl group, whereby a side chain has an aerobic bonding group. A polymer (A) can be obtained.

  The ring-opening addition of the cyclic compound (f) may be a single addition of one molecule as described above, or the cyclic compound (f) is further opened to the hydroxyl group and / or carboxyl group generated at the end of the side chain. Multiple ring-opening additions such as ring addition may be performed. Thus, when ring-opening addition is multiplexed, the side chain can be made longer. As a result, as described above, the side chain can increase the affinity with the adherend and can be an effective conductive path.

  The cyclic compound (f) of the present invention is preferably used in an amount of 1 to 150 parts by weight based on 100 parts by weight of the precursor (AP) of the copolymer (A). When the amount of the cyclic compound (f) is less than 1 part by weight, the antistatic agent such as the ionic compound (C) is difficult to move, so that effective antistatic performance may not be obtained. On the other hand, when the amount exceeds 150 parts by weight, the cohesive force is reduced, and thus foaming and cracking may easily occur during heat or wet heat.

In the present invention, to perform ring-opening addition of a cyclic compound to the side chain,
[Production method 1]
Alternatively, the precursor (AP) of the copolymer (A) can be obtained by copolymerizing the ethylenically unsaturated monomer represented by (a1) and / or (a2) and (a3) if necessary. After the obtained (Step 1), the copolymer (A) is obtained by subjecting the hydroxyl ester and / or carboxyl group contained in the precursor (AP) to a ring-opening addition reaction with the cyclic ester (f) (Step 2). ) Method and
[Production method 2]
Alternatively, the cyclic ester (f) is allowed to coexist in advance with the ethylenically unsaturated monomer represented by (a1) and / or (a2) and, if necessary, (a3), to give an ethylenically unsaturated monomer. A method of obtaining a copolymer (A) by copolymerizing and simultaneously performing a ring-opening addition reaction of the cyclic ester (f) (step 3);
The aerobic bonding group can be introduced into the copolymer (A) by any one of the methods.

  In the present invention, as described above, there are two methods for introducing an aerobic bonding group into the side chain of the copolymer (A). The method of introducing an aerobic bonding group in 2] is preferred.

In addition, the ring-opening addition reaction of the cyclic compound (f) is carried out by a catalyst described later, whereby the carbon-oxygen bond is cleaved by nucleophilic attack on the carbon atom adjacent to the ether oxygen, and the hydroxyl group in the copolymer (A) A ring opening addition is performed as a starting point, and a new hydroxyl group is generated at the terminal. Thereafter, the cyclic compound (f) is generally subjected to ring-opening addition and anionic polymerization in the same manner. Accordingly, the reactivity of the ring-opening addition to the hydroxyl group or carboxyl group of the copolymer (A) is significantly faster than the reactivity to the hydroxyl group. Therefore, when the hydroxyl group and the carboxyl group coexist, the cyclic compound Since most of (f) reacts preferentially with a hydroxyl group and hardly undergoes ring-opening addition to a carboxyl group, caution is required.
The ring-opening addition reaction in the case where the functional group in the copolymer (A) is only a carboxyl group is an electrophilic addition to the oxygen atom of the cyclic compound by a catalyst described later to produce a carbocation, and the copolymer The carboxyl group in (A) serves as a starting point for ring-opening addition, and a new carboxyl group is generated at the terminal. Similarly, the cyclic compound (f) undergoes ring-opening addition and is cationically polymerized. However, since the reactivity to the hydroxyl group is remarkably fast, the water content is generally the starting point and cationic polymerization is generally performed. It is.

  The cyclic compound (f) is preferably contained in an amount of 1 to 150 parts by weight with respect to 100 parts by weight of the precursor (AP) of the copolymer (A), and more specifically, an ethylenically unsaturated group having a hydroxyl group. It is preferable to make it react so that it may become in the range of 1.2-100 mol with respect to 1 mol of monomers (a1) and / or the ethylenically unsaturated monomer (a2) which has a carboxyl group, It is more preferable to react so that it may become in the range of -80 mol, It is still more preferable to react so that it may exist in the range of 1.8-60 mol, It exists in the range of 1.8-40 mol The reaction is particularly preferred. If it deviates from the above range, both tack and cohesion may not be satisfied when used in a pressure sensitive adhesive.

  In the present invention, a catalyst may be appropriately used in the reaction for introducing an ester group into the side chain. Anionic polymerization catalysts include ammonia, amines, quaternary ammonium salts, quaternary phosphonium salts, alkali metal hydroxides, alkaline earth metal hydroxides, tosylic acids, Lewis postponements, tin, lead, titanium , Iron, zinc, zirconium, cobalt, and other organometallic compounds, metal halides, and the like. Examples of the cationic polymerization catalyst include proton acids such as sulfuric acid, phosphoric acid, perchloric acid and sulfonic acid, or Lewis acids such as boron fluoride and aluminum chloride.

  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, tetra Propylammonium iodide, tetrapropylammonium hydroxide, tetrapropylammonium perchlorate, tetra-n-propylammonium hydrogensulfate, tetra-n-propylammonium pearlate (VII), tetrabutylammonium bromide, tetrabutylammonium trichloride bromide, Trabutylammonium chloride, tetrabutylammonium iodide, tetrabutylammonium hydroxide, tetrabutylammonium hexafluorophosphate, tetrabutylammonium hydrogensulfate, tetrabutylammonium nitrate, tetrabutylammonium tetrahydroborate, tetrabutylammonium tetrafluoroborate, Tetrabutylammonium cyanotrihydroborate, tetrabutylammonium difluorotriphenylstannate, tetrabutylammonium fluoride trihydrate, tetrabutylammonium tetrathiophenate (IV), tetrabutylammonium fluoride hydrate, tetra-n-butyl Ammonium dihydrogen trifluoride, Tetra-n-butylammonium trifluoromethanesulfonate, tributylammonium bis (2,3-dimercapto-2-butenedininitrate-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 perchlorate , Tetraoctyl ammonium bromide, tetraoctadecyl ammonium bromide and the like.

Examples of the 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), Tetrabutylphospho Umubisu (4,5-mercapto-1,3-dithiol-2 thionating ^-S 4, ^{S 5)} Nikoreto (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;
Alkaline earth metal hydroxides such as magnesium hydroxide, calcium hydroxide, strontium hydroxide and barium hydroxide;
Can be mentioned.

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

Examples of organic zirconium compounds include zirconium acetate, zirconium benzoate, 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 acetate, lead (Z) -octadeca-9-enoate, lead 2-ethylhexanoate, lead benzoate, lead naphthenate and the like.
Examples of organic iron compounds include iron 2-ethylhexanoate and iron acetylacetonate.
Examples of the organic cobalt compounds include cobalt acetate, cobalt benzoate, and cobalt 2-ethylhexanoate.

Examples of the organic zinc compounds include zinc acetate, zinc oxalate, zinc naphthenate, and zinc 2-ethylhexanoate.
Examples of metal halides include stannous chloride, stannous bromide, stannous iodide, and the like.
Examples of tosyl acids include p-toluenesulfonic acid, benzenesulfonic acid, xylenesulfonic acid, ethylbenzenesulfonic acid, chlorobenzenesulfonic acid and the like, and alkali metal salts, ammonium salts, amine salts, and hydrates thereof. included.

  Furthermore, Lewis acids such as boron trifluoride, manganese acetate, 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. As a usage-amount of a catalyst, it is preferable to use 0.0001-20 weight part with respect to 100 weight part of cyclic ester compounds (f), and the range of 0.0001-10 weight part is more preferable. If the amount exceeds 20 parts by weight, the product may be colored, or the catalyst that has not been deactivated may adversely affect the adhesive properties.

  As described above, the hydroxyl group and / or carboxyl group in the copolymer (A) in the present invention is a tyrenically unsaturated monomer (a1) having a hydroxyl group as a functional group, or an ethylenically unsaturated monomer having a carboxyl group. It is derived from the monomer (a2), or is a hydroxyl group or carboxyl group at the end of the side chain produced by ring-opening addition reaction of the cyclic compound (f).

In the present invention, when the functional group of the copolymer (A) is a hydroxyl group, the hydroxyl value is preferably from 0.01 to 50 mgKOH / g, more preferably from 0.1 to 30 mgKOH / g. When the copolymer (A) has a carboxyl group and a hydroxyl group, and the crosslinking agent (B) capable of reacting with the carboxyl group is used, 0.1 to 10 mgKOH / g is preferable, and 0.1 to 8 mgKOH. / G is more preferable.
On the other hand, when the functional group of the copolymer (A) is a carboxyl group, the acid value is preferably from 0.01 to 50 mgKOH / g, more preferably from 0.1 to 30 mgKOH / g. And when the crosslinking agent (B) which can react with a hydroxyl group is used, 0.1-10 mgKOH / g is preferable. When it is outside the above numerical ranges, there is a risk that the heat-and-moisture resistance when used as a pressure-sensitive adhesive decreases.

  When the hydroxyl value or the acid value is lower than 0.01 mgKOH / g, the reactivity of the crosslinking agent (B) with respect to the hydroxyl group or the carboxyl group is inferior, and the cohesive force of the cured resin may be insufficient. Moreover, when a hydroxyl value or an acid value becomes higher than 50 mgKOH / g, there exists a possibility that the pot life of the pressure sensitive adhesive composition which mix | blended the crosslinking agent (B) may become short. However, the end of the side chain may have a functional group other than a hydroxyl group and a carboxyl group depending on the desired physical properties.

  In the present invention, in order to adjust the hydroxyl value or acid value of the copolymer (A), a sealing compound (D) is newly sealed with a hydroxyl group and / or a carboxyl group in the copolymer (A). Thus, the hydroxyl value or the acid value can be adjusted. The sealing compound (D) needs to have a functional group capable of reacting with a hydroxyl group and / or a carboxyl group in the copolymer (A). Specific examples include a silane compound (d1), an acid anhydride group-containing compound (d2), a monoisocyanate compound (d3), and an amine compound (d4). Moreover, sealing compound (D) may be used individually or may be used in combination of 2 or more type.

Examples of the silane compound (d1) used in the present invention include hydrosilanes, alkoxysilanes, chlorosilanes, silanols, silylamines, and cyclic compounds thereof.
Examples of hydrosilanes include trimethylsilane, triethylsilane, tripropylsilane, tributylsilane, trihexylsilane, diethylmethylsilane, butyldimethylsilane, dimethylphenylsilane, triphenylsilane, methylphenylethenylsilane, and pentamethyldisiloxane. , Allyldimethylsilane, tris (trimethylsiloxy) silane, 1,1,1,3,5,5,5-heptamethyltrisiloxane, 1,1,1,3,5,7,7,7-octamethyltetra Examples thereof include hydrosilanes having a monofunctional Si—H group such as siloxane and 1,3,5,7,9-octaphenylcyclotetrasiloxane.

  Examples of alkoxysilanes include methoxytrimethylsilane, methoxytriethylsilane, methoxydimethylethynylsilane, dimethylethoxyethynylsilane, ethoxytrimethylsilane, ethoxytriethylsilane, allyloxytrimethylsilane, ethoxydimethylethenylsilane, trimethylpropoxysilane, and trimethyl. Isopropoxysilane, 1-methylpropoxytrimethylsilane, butoxytrimethylsilane, isobutoxytrimethylsilane, t-butoxytrimethylsilane, hexyloxytrimethylsilane, 3-aminopropyldimethylethoxysilane, tetrahydrofurfuryloxytrimethylsilane, phenoxytrimethylsilane, cyclohexyl Oxytrimethylsilane, 1-cyclohexenyloxytrime Alkoxysilanes having a monofunctional alkoxy group such as silane, dimethylethoxyphenylsilane, benzyloxytrimethylsilane, methoxytripropylsilane, benzyldimethylethoxysilane, 2-ethylhexyloxytrimethylsilane, octyloxytrimethylsilane, dodecyloxytrimethylsilane Is mentioned.

  Examples of chlorosilanes include trimethylchlorosilane, dimethylethenylchlorosilane, allyldimethylchlorosilane, dimethylpropylchlorosilane, dimethylisopropylchlorosilane, triethylchlorosilane, t-butyldimethylchlorosilane, dimethylphenylchlorosilane, methylphenylethenylchlorosilane, benzyldimethylchlorosilane, Examples thereof include chlorosilanes having a monofunctional chlorosilyl group, such as tripropylchlorosilane, dimethyloctylchlorosilane, tributylchlorosilane, diphenylmethylchlorosilane, diphenylethenylchlorosilane, triphenylchlorosilane, trihexylchlorosilane, dimethyloctadecylchlorosilane, and tribenzylchlorosilane.

  Examples of silanols include silanol compounds having a monofunctional silanol group such as trimethylsilanol, triethylsilanol, and triphenylsilanol.

  Examples of silylamines include trimethylsilyldimethylamine, trimethylsilyldiethylamine, dimethylaminotrimethylsilane, allylaminotrimethylsilane, N-methyl-N-trimethylsilylacetamide, anilinotrimethylsilane, 1-trimethylsilylpyrrole, 1-trimethylsilylpyrrolidone, 1- Silylamines having a monofunctional silylamino group such as trimethylsilylimidazole and 1-trimethylsilyl-1,2,4-triazole; 1,1,3,3-tetramethyldisilazane, hexamethyldisilazane, 1,3-divinyl Silylamines having a bifunctional silylamino group such as -1,1,3,3-tetramethyldisilazane, N, N′-bis (trimethylsilyl) -N-phenylurea; 5,5 hexamethylcyclotrisilazane, silylamines and the like can be mentioned bearing trifunctional or more cyclic silylamino group such as 1,1,3,3,5,5,7,7-octamethylcyclotetrasilazane.

  The acid anhydride group-containing compound (d2) includes, for example, known dicarboxylic acid compound anhydrides and derivatives having a molecular weight of about 90 to 500, and those having an acid anhydride ring of a tri- or higher functional polycarboxylic acid, Any of an aliphatic compound, an aromatic compound, and an alicyclic compound may be sufficient.

Examples of the aliphatic dicarboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, chloro (Z) -but-2-ene diene. Acid, (E) -but-2-enedioic acid, dodecanedioic acid, heptanedioic acid, 2-methyl- (Z) -but-2-enedioic acid, pentanedioic 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. or,
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, phenyltetrahydrofuran-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.), derivatives of 2,5-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 Anhydride derivatives such as 2,5-dione, phenyl 2,5-dihydrofuran-2,5-dione, 2,3-diphenyl 2,5-dihydrofuran-2,5-dione and the like.

  Examples of the aromatic dicarboxylic acid include o-phthalic acid, isophthalic acid, terephthalic 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-1H-indenedicarboxylic acid, etc. These aromatic dicarboxylic acid anhydrides can be used. Further, 1,3-dihydroisobenzofuran-1,3-dione, 4-methyl-1,3-dihydroisobenzofuran-1,3-dione and the like can be mentioned, and hexahydro-1,3-dihydroisobenzofuran- 1,3-dione derivatives ((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-dihydroiso 1,3-dihydroisobenzofuran-1,3-dione such as Nzofuran-1,3-dione, methylbutenyl-1,2,3,6-tetrahydro-1,3-dihydroisobenzofuran-1,3-dione) Derivatives 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, cis-4-cyclohexene-1,2-dicarboxylic acid, and the like. The anhydrides of these alicyclic dicarboxylic acids and the like 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 acid anhydride, biphenyldicarboxylic acid anhydride, 5-norbornene-2,3-dicarboxylic acid 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 acid anhydride, 1-cyclopentene-1,2-dicarboxylic acid anhydride, methylcyclohexene dicarboxylic acid anhydride, 1,8-naphthalenedicarboxylic acid anhydride, o Tahidoro dioxo-4,5-isobenzofurandione carboxylic 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 higher polycarboxylic acids having two or more anhydride rings include 1,2,3,4-butanetetracarboxylic dianhydride and 1,2,3,4-cyclobutanetetracarboxylic acid. Dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tri Carboxycyclopentyl ethane dianhydride, 2,3,5,6-tetracarboxycyclohexane dianhydride, 2,3,5,6-tetracarboxynorbornane dianhydride, 3,5,6-tricarboxynorbornane-2- Ethanoic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohex 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-isobenzofuran carboxylic acid ester, butene oxide di-1,3-dihydro-1,3-dioxo-5-isobenzofuran carboxylic acid ester, 3,3 ', 4,4'-benzophenone tetracarboxylic acid Anhydride, 2,2 ′, 3,3′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenylsulfone tetracarboxylic dianhydride, 2 2 ′, 3,3′-biphenylsulfonetetracarboxylic 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-furan Tetracarboxylic dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfur 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 (triphenyl) Phthalic 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, ethylene oxide bis (anhydrotrimellitate), 3 , 4-Dicarboxy-1,2,3,4-tetrahydro-1-naphthalenebutanedioic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-6-methyl-1-naphthalene Butanedioic dianhydride, 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 acid Anhydride, allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic anhydride, methallylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic An acid anhydride etc. are mentioned.

  These acid anhydrides can be used alone or in combination of two or more as the acid anhydride group-containing compound (d2). Use of a cyclic anhydride group-containing compound having one anhydride ring is preferable because a pressure-sensitive adhesive composition excellent in adhesiveness, heat resistance, moist heat resistance and transparency can be obtained.

  Examples of the monoisocyanate compound (d3) used in the present invention include methyl isocyanate, ethyl isocyanate, propyl isocyanate, butyl isocyanate, octyl isocyanate, decyl isocyanate, hexadecyl 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-methylben Diisocyanate, (R)-(−)-1- (1-naphthyl) ethyl isocyanate, (R)-(+)-1-phenylethyl isocyanate, (S)-(−)-1-phenylethyl isocyanate, p -Toluenesulfonyl isocyanate and the like.

  The monoisocyanate compound (d3) used in the present invention can be used alone or in combination of two or more.

  As the amine compound (d4) 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-aminoca Aliphatic amines such as pronitrile and rosinamine;

  For example, cyclohexylamine, aniline, benzylamine, phenethylamine, p-methoxyphenethylamine, 1-phenylethylamine, 1- (4-methylphenyl) ethylamine, 1- (3-methoxyphenyl) ethylamine, 2- (phenylmethoxy) cyclopentane Amine, 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-pipecoli N-aminoethylpiperidine, N-aminoethyl-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-methyl Pyrazinamide, 2- Mino-3,5-dibromopyrazine, picolinamide, isonicotinamide, 2-aminonicotinic acid, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-amino-3-methylpyridine, 2-aminomethyl Pyridine, 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-3,5- Examples thereof include amines possessing an alicyclic, aromatic or heterocyclic ring structure such as dichloro-4,6-dimethylpyridine and 3-aminoethyl-6-chloropyridine.

In the present invention, the hydroxyl value or acid value is adjusted by using a silane compound (d1) or a monoisocyanate compound (d3) as the sealing compound (D) when the functional group of the copolymer (A) is a hydroxyl group. It is preferable to use a monofunctional one. Further, when the acid anhydride group-containing compound (d2) is used, it is not only possible to change from a hydroxyl group to a carboxyl group, but also an ester bond is newly formed, which is preferable for improving antistatic performance.
When the functional group of the copolymer (A) is a carboxyl group, the amine compound (d4) is preferably used as the sealing compound (D).

  In the present invention, by changing the structure of the side chain terminal of the copolymer (A) depending on the type of the sealing compound (D) used, various functions can be imparted when used in a pressure-sensitive adhesive composition. it can. For example, when a silane compound is used, the adhesion can be improved, for example, the adhesion to glass is improved. Moreover, when a monoisocyanate compound is used, heat resistance and heat-and-moisture resistance improve by the urethane bond to form. Furthermore, when an amine compound is used, the antistatic performance can be improved by the amide bond or acid-base bond that is formed.

  In the present invention, a catalyst may be appropriately used in the sealing reaction for adjusting the hydroxyl value or the acid value. Examples of the catalyst include ammonia, amines, quaternary ammonium salts, quaternary phosphonium salts, alkali metal hydroxides, alkaline earth metal hydroxides, Lewis acids, tin, lead, titanium, iron, zinc, Examples thereof include organometallic compounds containing metal such as zirconium and cobalt, and metal halides.

  In the copolymer (A) in the present invention, the glass transition temperature (Tg) needs to be −60 to 0 ° C. in order to exhibit good adhesive properties (tack, adhesive strength, cohesive strength). When Tg is lower than −60 ° C., the cohesive force is lowered and the durability may be lowered. On the other hand, when Tg exceeds 0 ° C., tack is not expressed and adhesion is lowered, which is not preferable.

In the copolymer (A) of the present invention, if the Tg of a homopolymer that can be formed from each ethylenically unsaturated monomer or cyclic compound (f) that is a constituent component of each resin is known, each individual Based on the Tg of the polymer and the composition ratio of the ethylenically unsaturated monomer or the cyclic compound (f), the Tg of the copolymer (A) can be theoretically determined, and as a result, the pressure-sensitive adhesive is crosslinked. It is possible to determine the Tg of the agent composition.
By the way, in the case of a pressure sensitive adhesive, it is common to mix | blend a small amount of below-mentioned crosslinking agent (B) with respect to the copolymer (A) which is a main component. Since the adhesive layer formed from such a pressure-sensitive adhesive is loosely crosslinked (in other words, sparse), unlike the cured coating film that is densely crosslinked, the Tg of the adhesive layer is the same as before the crosslinking. It is approximately equal to the Tg of the polymer (A). Therefore, various ethylenically unsaturated monomers or cyclic compounds (f) are used so that the Tg of the pressure sensitive adhesive layer formed from the pressure sensitive adhesive is 0 ° C. or lower, preferably −5 ° C. or lower. Select the type and quantity.
On the other hand, the adhesive layer formed with a so-called crosslinkable IPN structure obtained by blending a large amount of the below-mentioned crosslinking agent (B) with the copolymer (A) has a Tg after crosslinking significantly different from that before crosslinking. Therefore, it is preferable to obtain by DSC measurement (differential scanning calorimetry) or dynamic viscoelasticity measurement.

In the copolymer (A) of the present invention, the weight average molecular weight (Mw) is in the range of 500,000 to 2,000,000 in order to maintain good durability (heat resistance, heat and moisture resistance) and reworkability. It is necessary to be. When the Mw of the copolymer (A) exceeds 2,000,000, not only the fluidity is lowered, but also the compatibility with the ionic compound (C) described later is lowered. In some cases, the coatability is lowered, the durability such as floating or peeling is lowered, and the coating film is whitened.
When Mw of the copolymer (A) is less than 500,000, cohesive failure of the pressure-sensitive adhesive layer is likely to occur after the optical pressure-sensitive adhesive film is attached to a cell member for liquid crystal such as glass. There is.

Next, a crosslinking agent (B) is demonstrated.
In this invention, a pressure sensitive adhesive is obtained by making a copolymer (A) contain a crosslinking agent (B).
As described above, the crosslinking agent (B) of the present invention is used to form a crosslinked structure of the pressure-sensitive adhesive composition, and further to form a crosslinkable IPN structure in addition to the crosslinked structure. Specifically, it is a compound that can react with the hydroxyl group and / or carboxyl group of the copolymer (A).
When the functional group in the copolymer (A) is a carboxyl group, examples of the functional group of the crosslinking agent (B) include an isocyanate group, an oxirane group, an amino group, an aziridyl group, an oxazoline group, and a metal chelate group. When the functional group in the union (A) is a hydroxyl group, the functional group of the crosslinking agent (B) includes an isocyanate group and an N-hydroxymethyl group.
In particular, the polyisocyanate compound (b1) having an isocyanate group is preferably used because it is excellent in the adhesion of the pressure-sensitive adhesive after the crosslinking reaction and the adhesion to the coating layer.

  Examples of the polyisocyanate compound (b1) having an isocyanate group include aromatic polyisocyanates, aliphatic polyisocyanates, araliphatic polyisocyanates, and alicyclic polyisocyanates.

  Aromatic polyisocyanates include 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-triisocyanate. Range isocyanate, 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.

  Aliphatic polyisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (also known as HDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodeca Examples include methylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate.

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

  As alicyclic polyisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (also known as IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, Examples thereof include methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), 1,4-bis (isocyanatomethyl) cyclohexane and the like.

  Moreover, 2-methylpentane-2,4-diol adduct of the above polyisocyanate, trimer having an isocyanurate ring, etc. can be used together. Polyphenylmethane polyisocyanate (also known as PAPI), naphthylene diisocyanate, modified polyisocyanate thereof, and the like can be used. As the polyisocyanate-modified product, a carbodiimide group, a uretdione group, a uretoimine group, a burette group reacted with water, a group of isocyanurate groups, or a modified product having two or more of these groups can be used. A reaction product of a polyol and a diisocyanate can also be used as a polyisocyanate.

  These polyisocyanate compounds include 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), xylylene diisocyanate, 4,4′-methylenebis. From the viewpoint of weather resistance, it is particularly preferable to use a non-yellowing or hardly yellowing polyisocyanate compound such as (cyclohexyl isocyanate) (also known as hydrogenated MDI).

  When the polyisocyanate compound (b1) is used as the crosslinking agent (B), a known catalyst can be used as necessary for promoting 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, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, diazabicycloundecene (also known as DBU), etc. You can also.

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 (also known as DBTDL), dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, tributyl Examples thereof include tin acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate, and tin 2-ethylhexanoate.
Examples of non-tin compounds include titanium compounds such as dibutyltitanium dichloride, tetrabutyltitanate and butoxytitanium trichloride, lead compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate and lead naphthenate, 2- Iron-based such as iron ethylhexanoate and iron 2,4-pentadionate, cobalt-based such as cobalt benzoate and cobalt 2-ethylhexanoate, zinc-based such as zinc naphthenate and zinc 2-ethylhexanoate, naphthene Examples thereof include zirconium acid.
Among the above catalysts, dibutyltin dilaurate (also known as DBTDL), tin 2-ethylhexanoate and the like are preferable in terms of reactivity and hygiene.

  Examples of the epoxy compound (b2) include 2,2-bis (hydroxyphenyl) propane / 2-chloromethyloxirane type oxirane resins, 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 type, 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 oxiranes thereof Resin, phenol novolak type, orthocresol novolak type, para tertiary butylphenol novolak type, paraoctylphenol novolak type, nonylphenol novolak type and co-condensation type oxirane resins, ethylene oxide diglycidyl ether, polyethylene oxide diglycidyl ether, glycerin Diglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, diglycidyl aniline, N N, N ', N'-tetraglycidyl -m- xylylenediamine, 1,3-bis (N, N'-diglycidyl aminomethyl) cyclohexane.

  Examples of the aziridine compound (b3) include N, N′-diphenylmethane-4,4′-bis (1-aziridinecarboxite), N, N′-toluene-2,4-bis (1-aziridinecarboxite). Bisisophthaloyl-1- (2-methylaziridine), tri-1-aziridinylphosphine oxide, N, N′-hexamethylene-1,6-bis (1-aziridinecarboxite), 2-methylpentane -2,4-diol-tri-β-aziridinylpropionate, 2,2-bis (hydroxymethyl) 1,3-propanediol-tri-β-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-dioltris [3- (1-aziridinyl) -2-methylpropionate], 2,2-bis (hydroxymethyl) 1,3-propanedioltetra [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.

As the carbodiimide compound (b4), a compound having two or more carbodiimide groups (—N═C═N—) in the molecule is preferably used, and known polycarbodiimides can be used. Moreover, as a carbodiimide compound (b4), 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′- One of dicyclohexylmethane diisocyanate, tetramethylxylylene diisocyanate, or a mixture thereof can be used.

  As the carbodiimidization catalyst, 1-phenyl-2-phospholene-1-oxide, 3-methyl-2-phospholene-1-oxide, 1-ethyl-3-methyl-2-phospholene-1-oxide, 1-ethyl- Phosphorene oxides such as 2-phospholene-1-oxide or their 3-phospholene isomers can be used.

  An example of such a high molecular weight polycarbodiimide is a carbodilite series manufactured by Nisshinbo Industries, Ltd. Of these, Carbodilite V-01, 03, 05, 07, 09 is preferable because of its excellent compatibility with organic solvents.

  As the oxazoline compound (b5), a compound having two or more oxazoline groups in the molecule is preferably used. Specifically, 2′-methylenebis (2-oxazoline), 2,2′-ethenebis (2-oxazoline) is used. 2,2′-ethenebis (4-methyl-2-oxazoline), 2,2′-propenebis (2-oxazoline), 2,2′-tetramethylenebis (2-oxazoline), 2,2′-hexamethylene Bis (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, vinyl monomers such as 2-isopropenyl-2-oxazoline and 2-isopropenyl-4,4-dimethyl-2-oxazoline and other monomers that can be copolymerized with these vinyl monomers It may be a copolymer with the body.

  Examples of the metal chelate compound (b6) include aluminum, iron, copper, zinc, tin, titanium, titanium, nickel, antimony, magnesium, vanadium, chromium, zirconium and other polyvalent metals such as 2,4-pentanedione and aceto Examples thereof include compounds coordinated with ethyl acetate.

Next, the ionic compound (C) will be described.
The ammonium salt compound (C1) represented by the following general formula (1), the alkali metal salt compound (C2) represented by the following general formula (2), and the following general formula (3) used in the present invention. The ammonium salt compound (C3) represented by

General formula (1)

[In General Formula (1), R ^{1 to} R ⁸ may each independently have a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or a substituent. Represents a good alkynyl group, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent, and R ^{5 to} R ⁸ may form a ring with adjacent substituents; Good. ]

General formula (2)

[In General Formula (2), R ^{1 to} R ⁴ may each independently have a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or a substituent. A good alkynyl group, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent, and A ⁺ represents an alkali metal ion. ]

General formula (3)

[In General Formula (3), R ^{5 to} R ⁸ may each independently have a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or a substituent. It represents a good alkynyl group, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent, and adjacent substituents may form a ring.
R ⁹ represents an alkylene bonding group that may have a substituent, an alkylene bonding group that may have a substituent and a double bond, an alkylene bonding group that may have a substituent and a triple bond, or a substituent. Arylene bond group which may have, heterocyclic bond group which may have substituent, or ether bond group, ester bond group, thioether bond group, dithiol bond group, carbonyl bond group, sulfinyl bond group, sulfonyl bond Represents a group, a phosphonyl linking group, an amino linking group, an imino linking group, or a silyl linking group.
R ¹⁰ represents a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a halogen group.
R ¹¹ represents a hydrogen atom, an alkyl group that may have a substituent, an aryl group that may have a substituent, or —R ⁹ R ¹⁰ . ]

In the ammonium salt compound (C1) or (C3), the cation part is N ⁺ R ⁵ R ⁶ R ⁷ R ⁸ , and all the constituent parts including the anion part are organic matter. It is characterized by high compatibility with agents and solvents. In addition, when the ammonium salt compound (C1) or (C3) is used, the antistatic performance is hardly affected by environmental humidity.

  Further, the alkali metal salt compound (C2) has a feature that the cation part is an alkali metal ion, and therefore the production process can be shortened and can be produced at low cost. However, when an alkali metal salt compound (C2) is used, there is a possibility of contaminating electronic components such as internal circuits, transistors, ICs, and CPUs. The Further, when the alkali metal salt compound (C2) is used, if the adherend is aluminum or the like, the floating is likely to occur in a high temperature and high humidity environment. Furthermore, when the alkali metal salt compound (C2) is used, the antistatic performance is easily affected by environmental humidity.

  Therefore, in the present invention, it is more preferable to use the ammonium salt compound (C1) or (C3) represented by the general formula (1) or (3).

  As the alkyl group which may have a substituent, an alkyl group having 1 to 30 carbon atoms is preferable, for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group. , Octadecyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, 1-ethylpentyl group, cyclopentyl group, cyclohexyl group, trifluoromethyl group, 2-ethylhexyl group, phenacyl group, 1-naphthoylmethyl Group, 2-naphthoylmethyl group, 4-methylsulfanylphenacyl group, 4-phenylsulfanylphenacyl group, 4-dimethylaminophenacyl group, 4-cyanophenacyl group 4-methylphenacyl group, 2-methylphenacyl group 3-fluorophenacyl group, 3-trifluoromethylphenacyl group, 3- Torofenashiru group, and the like.

As an alkenyl group which may have a substituent, a C2-C10 alkenyl group is preferable, for example, a vinyl group, an allyl group, a styryl group etc. are mentioned.
The alkynyl group which may have a substituent is preferably an alkynyl group having 2 to 10 carbon atoms, and examples thereof include an ethynyl group, a propynyl group, and a propargyl group.

  As the aryl group which may have a substituent, an aryl group having 6 to 30 carbon atoms is preferable, and a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-anthryl group, a 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 9-fluorenyl group, terphenyl group, quarterphenyl group, o-, m-, and p-tolyl group, xylyl group, o- , M-, and p-cumenyl group, mesityl group, pentarenyl group, binaphthalenyl group, turnaphthalenyl group, quarternaphthalenyl group, heptaenyl group, biphenylenyl group, indacenyl group, fluoranthenyl group, acenaphthylenyl group, aceanthrylenyl group, Phenalenyl, fluorenyl, anthryl, bianthracenyl, teranthraceni Group, quarter anthracenyl group, anthraquinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, preadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, hexa Examples thereof include a phenyl group, a hexacenyl group, a rubicenyl group, a coronenyl group, a trinaphthylenyl group, a heptaphenyl group, a heptacenyl group, a pyranthrenyl group, and an oberenyl group.

  The heterocyclic group that may have a substituent is preferably an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom. For example, thienyl group, benzo [b] thienyl group, naphtho [2,3-b] thienyl group, thiantenyl group, furyl group, pyranyl group, isobenzofuranyl group, chromenyl group, xanthenyl group, phenoxathinyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H-indolyl group, indolyl group, 1H-indazolyl group, purinyl group, 4H- Quinolidinyl group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxanilyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH-carbazolyl group, carbazolyl group, β-carbolinyl group, phenanthridinyl group, acridinyl group, perimidinyl group Nyl group, phenanthrolinyl group, phenazinyl group, phenalsadinyl group, isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, phenoxazinyl group, isochromanyl group, chromanyl group, pyrrolidinyl group, pyrrolinyl group, imidazolidinyl group, imidazolinyl group, pyrazolidinyl group Group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, morpholinyl group, thioxanthryl group and the like.

  As a halogen group, halogen groups, such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, are mentioned, for example.

  The alkylene linking group which may have a substituent is preferably an alkylene group having 1 to 30 carbon atoms, such as a methylene linking group, an ethylene linking group, a propylene linking group, a butylene linking group, a hexylene linking group, or an octylene linking group. Group, decylene bond group, dodecylene bond group, okdadecylene bond group, isopropylene bond group, isobutylene bond group, sec-butylene bond group, tert-butylene bond group, 1-ethylpentylene bond group, cyclopentylene bond group, cyclohexene Silene bond group, trifluoromethylene bond group, 2-ethylhexylylene bond group, phenacylene bond group, 1-naphthoylmethylene bond group, 2-naphthoylmethylene bond group, 4-methylsulfanylphenacylene bond group, 4-phenylsulfanyl Phenacylene linking group, 4-dimethylaminophen Nacylene bond group, 4-cyanophenacylene bond group 4-methylphenacylene bond group, 2-methylphenacylene bond group, 3-fluorophenacylene bond group, 3-trifluoromethylphenacylene bond group, 3-nitrophenacylene Examples include a linking group.

Examples of the alkylene linking group which may have a substituent and a double bond include C2-C10 alkylene linking groups having one or more double bonds.
Examples of the alkylene linking group that may have a substituent and a triple bond include C 2-10 alkylene linking groups having one or more triple bonds.

  The arylene linking group which may have a substituent is preferably an arylene linking group having 6 to 30 carbon atoms, such as a phenylene linking group, a biphenylene linking group, a naphthylene linking group, a 9-anthrylene linking group, a phenanthrylene linking group, or a pyrenyllene linking group. Group, naphthacenylene bond group, indenylene bond group, azulylene bond group, fluorenylene bond group, terphenylene bond group, quarterphenylene bond group, tolylene bond group, xylylene bond group, cumenylene bond group, mesitylene bond group, pentalenylene bond group, binaphthalylene bond group Group, Turnaphthalenylene bond group, Quarter Naphthalenylene bond group, Heptalenylene bond group, Biphenylenylene bond group, Indasenylene bond group, Fluoranthenylene bond group, Acenaphthyleneylene bond group, Aseantrirenylene bond group Phenalylene bond group, fluorenylene bond group, anthrylene bond group, bianthracenylene bond group, teranthracenylene bond group, quarter anthracenylene bond group, anthraquinolylene bond group, phenanthrylene bond group, triphenylenylene bond group, pyrenylene Bonding group, chrysenylene bonding group, naphthacenylene bonding group, preadenylene bonding group, picenylene bonding group, peryleneylene bonding group, pentaphenylene bonding group, pentacenylene bonding group, tetraphenylenyl group, hexaphenylene bonding group, hexasenylene bonding group, rubisenylene bonding A group, a coronenylene linking group, a trinaphthyleneylene linking group, a heptaphenylene linking group, a heptasenylene linking group, a pyrantrenylene linking group, an oberenylene linking group and the like.

  The heterocyclic linking group which may have a substituent is preferably an aromatic or aliphatic heterocyclic linking group containing a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom. For example, thienylene bond group, benzo [b] thienylene bond group, naphtho [2,3-b] thienylene bond group, thiantrenylylene bond group, furylylene bond group, pyranylene bond group, isobenzofuranylene bond group, chromenylene bond group , Xanthenylene bond group, phenoxathiinylylene bond group, 2H-pyrrolylylene bond group, pyrrolylylene bond group, imidazolylene bond group, pyrazolylene bond group, pyridylylene bond group, pyrazinylylene bond group, pyrimidinylylene bond group, pyridazinylylene bond group, indolinylylene bond group Group, isoindoleylene linking group, 3H-indoleylene linking group, indoleylene linking group, 1H-indazolylene linking group, purinylylene linking group, 4H-quinolidinylylene linking group, isoquinolylene linking group, quinolylene linking group, lid Dinylylene linking group, naphthyridinylylene linking group, quinoxanylylene linking group, quinazolinylylene linking group, cinnolinylylene linking group, pteridinylylene linking group, 4aH-carbazolylene linking group, carbazolylline linking group, β-carbolinylylene linking group, phenanthridinylylene linking group Linking group, perimidinylylene linking group, phenanthrolinylylene linking group, phenazinylylene linking group, phenalsadinylylene linking group, isothiazolylylene linking group, phenothiazinylylene linking group, isoxazolylylene linking group, flazanyrrylene linking group, phenoxa Dilinylene bond group, isochromanirylene bond group, chromanylylene bond group, pyrrolidinylylene bond group, pyrrolinylylene bond group, imidazolidinylylene bond group, imidazolinylylene bond group, pyrazolid Examples include a nylylene linking group, a pyrazolinylylene linking group, a piperidylylene linking group, a piperazinylylene linking group, an indolinylylene linking group, an isoindolinylylene linking group, a quinuclidinylylene linking group, a morpholinylylene linking group, and a thioxanthryllylene linking group.

  Other bonding groups include ether bonding groups, ester bonding groups, thioether bonding groups, dithiol bonding groups, carbonyl bonding groups, sulfinyl bonding groups, sulfonyl bonding groups, phosphonyl bonding groups, amino bonding groups, imino bonding groups, or silyls. A linking group or the like represents a linking group containing an oxygen atom, a nitrogen atom, a phosphorus atom, or a sulfur atom.

  Furthermore, the alkyl group which may have a substituent mentioned above, or an alkylene bond group, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, a substituent and a double bond. An alkylene bond group which may have a substituent and a triple bond, an aryl group which may have a substituent, or an arylene bond group and a heterocyclic group which may have a substituent Alternatively, the hydrogen atom of the heterocyclic bond group may be further substituted with another substituent.

  Examples of such substituents include halogen groups such as fluorine atom, chlorine atom, bromine atom and iodine atom, trifluoromethyl group, perfluoroethyl group, perfluoroalkyl group, trichloromethyl group, perchloroalkyl group, and tribromomethyl. Halogenated alkyl groups such as methoxy groups, alkoxy groups such as methoxy groups, ethoxy groups, tert-butoxy groups, aryloxy groups such as phenoxy groups, p-tolyloxy groups, methoxycarbonyl groups, butoxycarbonyl groups, phenoxycarbonyl groups, vinyloxy Alkoxycarbonyl groups such as carbonyl groups, aryloxycarbonyl groups, acyloxy groups such as acetoxy groups, propionyloxy groups, benzoyloxy groups, acetyl groups, benzoyl groups, isobutyryl groups, acryloyl groups, methacryloyl groups, methoxa groups An acyl group such as a methyl group, an alkylsulfanyl group such as a methylsulfanyl group and a tert-butylsulfanyl group, an arylsulfanyl group such as a phenylsulfanyl group and a p-tolylsulfanyl group, an alkylamino group such as a methylamino group and a cyclohexylamino group, Dialkylamino groups such as dimethylamino group, diethylamino group, morpholino group and piperidino group, arylamino groups such as phenylamino group and p-tolylamino group, alkyl groups such as methyl group, ethyl group, tert-butyl group and dodecyl group, Aryl group such as phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group, etc., hydroxyl group, carboxyl group, sulfonamide group, formyl group, mercapto group, sulfo group, mesyl group Group, p-tolue Sulfonyl, amino, nitro, nitroso, cyano, trifluoromethyl, trichloromethyl, trimethylsilyl, phosphinico, phosphono, alkylsulfonyl, arylsulfonyl, trialkylammonium, dimethylsulfonyl Group, triphenylphenacylphosphoniumyl group and the like.

  Among such substituents, a preferred substituent is an electron-withdrawing substituent. When the electron-withdrawing substituent is substituted, the ionic compound is generally easily dissociated and the antistatic performance is improved.

  Such electron-attracting substituents are generic names for substituents that attract electrons from the other party by resonance effects and induced effects, and many of them have a positive value for the substituent constant σ in Hammett's rule. It is. These substituents are not particularly limited, and specific examples thereof include Chemical Review Vol. 91, Nos. 165 to 195, published in 1991, with a σp greater than 0. More specifically, halogen groups, cyano groups, carboxyl groups, nitro groups, nitroso groups, acyl groups, alkyloxycarbonyls Group, aryloxycarbonyl group, alkylsulfonyl group, arylsulfonyl group, trialkylammonium group, amide group, perfluoroalkyl group, perfluoroalkylthio group, perfluoroalkylcarbonyl group, sulfonamide group, 4-cyanophenyl group and the like.

  Further, like the above-described substituents, examples of a preferable linking group include an electron-withdrawing linking group. The presence of an electron-withdrawing linking group is preferable because the ionic compound is easily dissociated and the antistatic performance is improved. As such a linking group, a carbonyl linking group, a sulfonyl linking group or the like is preferably used.

R ^{1 to} R ⁴ are preferably an alkyl group which may have a substituent or an aryl group which may have a substituent, more preferably a substituent, in view of the stability of the compound. It is an aryl group that may have.
R ^{5 to} R ⁸ are preferably an alkyl group which may have a substituent in consideration of the stability of the compound.

In view of the stability of the compound, R ⁹ is preferably a sulfonyl bond group, and R ¹⁰ is preferably a halogen group. R ¹¹ is preferably a combination of a sulfonyl bond group and a halogen group or a halogenated alkyl group, as in R ⁹ and R ¹⁰ .

  In the present invention, representative examples of the ammonium salt compound (C1) represented by the general formula (1) are shown in the following Tables 1 to 6 as exemplified compounds (C1-1) to (C1-92), and the general formula Representative examples of the alkali metal salt compound (C2) represented by (2) are shown in the following Table 7 as exemplified compounds (C2-1) to (C2-10), and also represented by the general formula (3). Specific examples of the ammonium salt compound (C3) are specifically exemplified in the following Tables 8 to 14 as exemplary compounds (C3-1) to (C3-106), but are not limited thereto. . In the exemplified compounds, Me is a methyl group, Et is an ethyl group, Bu is a normal butyl group, Pr is a normal propyl group, i-Pr is an isopropyl group, Hex is a hexyl group, Oct is an octyl group, and c-Hex is cyclohexyl. Group, Dec represents a decyl group, Cet represents a cetyl (also referred to as hexadecyl) group, and Ph represents a phenyl group.

  Further, the pressure-sensitive adhesive composition of the present invention is used in combination with the ammonium salt compound (C1), alkali metal salt compound (C2), or ammonium salt compound (C3) in combination with other antistatic agents. An agent may be used. Although it does not specifically limit as a compound to use together, A well-known surfactant and organic salt of alkali metal are mentioned, These can be used individually or in combination.

  The pressure-sensitive adhesive composition of the present invention comprises 100 parts by weight of the copolymer (A) containing the ionic compound (C) which is the alkali metal salt compound (C2) or the ammonium salt compound (C3). The content is preferably 0.01 to 10 parts by weight, more preferably 0.3 to 3.0 parts by weight. If the amount is less than 0.01 parts by weight, sufficient antistatic performance may not be obtained, and even if 10 parts by weight or more is added, it may be difficult to obtain further antistatic performance, and further heat resistance May result in defects.

The pressure-sensitive adhesive composition of the present invention preferably contains an organic solvent, and as long as the effects of the present invention are not impaired, a silane coupling agent, a softener, a dye, a pigment, an antioxidant, a tackifier You may mix | blend a fire, a plasticizer, a filler, an anti-aging agent, etc.
For example, the viscosity of the pressure-sensitive adhesive composition can be adjusted by further adding an organic solvent such as acetone, ethyl acetate, cyclohexane, toluene, methyl ethyl ketone, isopropyl alcohol, other hydrocarbon solvents, or water. The viscosity can also be reduced by heating the pressure sensitive adhesive composition.

Since the pressure-sensitive adhesive composition of the present invention has a large number of aerobic bonding groups in the side chain of the copolymer (A), there is a balance between durability such as heat resistance and moist heat resistance and effective antistatic performance. good. That is, in the adhesive layer of the pressure-sensitive adhesive film obtained from the pressure-sensitive adhesive composition of the present invention, the aerobic bonding group and the ionic compound (C) are immobilized by pseudo-coordination bonding. The antistatic agent such as the ionic compound (C) hardly migrates to the adherend interface even after being attached to the adherend and exposed to a high temperature or high temperature and high humidity for a long period of time. No foaming, floating, or peeling caused by bleeding.
In addition, since there are a large number of aerobic bonding groups, it has a pendant state in which a large number of unpaired electrons of this aerobic bond exist, and it is oriented near the adherend interface such as glass for liquid crystal cells. The distance between unpaired electrons is shortened, a network is formed through the unpaired electrons, and a conductive path is formed. Here, when peeling the release film laminated on the pressure-sensitive adhesive film and sticking the adherend, peeling off the once attached polarizing film etc. from the adherend, or new polarizing film etc. Although it is charged in the case of rework that is re-applied, due to pressure changes associated with these peeling and sticking, pseudo-coordination bonds between antistatic agents such as the above ionic compound (C) and aerobic bonding groups Is broken and ion conduction is likely to occur quickly on the conductive path derived from the aerobic bonding group in the vicinity of the adherend interface, so that the antistatic performance is improved. Moreover, since it can improve the heat resistance and heat-and-moisture resistance under conditions severer than before due to the above reasons, it can be preferably used for an optical member.

The pressure-sensitive adhesive composition of the present invention is further suitable as an optical pressure-sensitive adhesive composition. That is, it is preferably used for forming a laminate comprising an optical film as a film-like substrate and an adhesive layer located on at least one surface of the optical film.
The optical pressure-sensitive adhesive film of the present invention can be obtained as follows.
The pressure-sensitive adhesive composition is applied to the release-treated surface of the peelable film and dried, and an optical film that is a film-like substrate is laminated on the surface of the pressure-sensitive adhesive layer, or an optical film that is a film-like substrate An optical pressure-sensitive adhesive film can be obtained by coating and drying the pressure-sensitive adhesive composition on the surface and laminating the release-treated surface of the peelable film on the surface of the pressure-sensitive adhesive layer. The cross-linking reaction between the copolymer (A) and the cross-linking agent (B) is performed by laminating a film-like optical film or a peelable film on the pressure-sensitive adhesive layer surface when the pressure-sensitive adhesive composition is dried. In this case, the process further proceeds after lamination.

Here, a general description of the pressure-sensitive adhesive composition and the pressure-sensitive adhesive film will be given.
The pressure sensitive adhesive composition is used to form a pressure sensitive adhesive film.
The basic lamination structure of the pressure-sensitive adhesive film is as follows: film-like substrate / pressure-sensitive adhesive layer / single-sided pressure-sensitive adhesive film such as peelable film, or peelable film / pressure-sensitive adhesive layer / film-like base It is a double-sided pressure-sensitive adhesive film such as material / pressure-sensitive adhesive layer / peelable film. At the time of use, the peelable film is peeled off and the pressure-sensitive adhesive layer is attached to the adherend. The pressure-sensitive adhesive composition is not only a pressure-sensitive adhesive layer that has a tack at the moment when the pressure-sensitive adhesive layer touches the adherend but also adheres other than the pressure-sensitive adhesive composition. Unlike adhesives (hereinafter simply referred to as adhesives), it is necessary to have cohesive strength to maintain the state of sticking while maintaining tack and moderate hardness without being completely solidified during sticking. It is. The cohesive force greatly depends on the molecular weight.

  Examples of the peelable film include those obtained by subjecting the surface of a film-like substrate such as cellophane, various plastic films, and paper to a release treatment. Moreover, as a film-form base material, the thing of a single layer may be used, and the thing in the multilayer state formed by laminating | stacking a some base material can also be used.

  Various plastic films used for film-like substrates and peelable films are also called various plastic sheets. For example, polyvinyl alcohol film, triacetyl cellulose film, polypropylene, polyethylene, polycycloolefin, ethylene-vinyl acetate copolymer Polyolefin resin film, Polyester resin film such as Polyethylene terephthalate and Polybutylene terephthalate, Polycarbonate resin film, Polynorbornene resin film, Polyarylate resin film, Acrylic acid resin film, Polyphenylene Sulfide resin film, polystyrene resin film, vinyl resin film, polyamide resin film, polyimide resin film, Such as films of epoxy resins.

As the optical member in the present invention, among the various plastic films, an optical film mainly used for optical applications is preferably used. Examples of the optical film include a polarizing film, a retardation film, an elliptically polarizing film, an antireflection film, and a brightness enhancement film.
A polarizing film, also called a polarizing plate, is sandwiched between two triacetyl cellulose protective films (hereinafter referred to as “TAC film”), two cycloolefin films, and an acrylic film on both sides of a polyvinyl alcohol polarizer. It is a multilayer structure film.

After applying the pressure-sensitive adhesive composition to a peelable film or optical film by an appropriate method according to a conventional method, if the pressure-sensitive adhesive composition contains a liquid medium such as an organic solvent or water, heat it. When the liquid medium is removed by a method such as the above, or when the pressure-sensitive adhesive composition does not contain a liquid medium that should be volatilized, the resin layer in a molten state is cooled and solidified, and a peelable film or optical A pressure sensitive adhesive layer can be formed on the film.
The thickness of the pressure sensitive adhesive layer is preferably 0.1 μm to 200 μm, and more preferably 0.1 μm to 100 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.

The method for applying the pressure-sensitive adhesive composition of the present invention to a peelable film or the like is not particularly limited, and may be a Meyer bar, applicator, brush, spray, roller, gravure coater, die coater, lip coater, comma coater, Various coating methods such as a knife coater, a reverse coater, and a spin coater can be used.
There is no restriction | limiting in particular in a drying method, The thing using hot air drying, infrared rays, and the pressure reduction method is mentioned. As drying conditions, although depending on the crosslinked form of the pressure-sensitive adhesive composition, the film thickness, and the selected solvent, heating with hot air at about 60 to 180 ° C. is usually sufficient.

  The pressure-sensitive adhesive film using the pressure-sensitive adhesive composition of the present invention is used as a laminate by sticking to a glass plate such as a liquid crystal cell, a PDP module or a touch screen panel or the above-mentioned various plastic films. Is preferred.

The laminate and liquid crystal cell member of the present invention will be described.
The laminate of the present invention is, for example, one surface of a so-called sheet (also referred to as film) optical member having various optical properties such as a polarizing film, a retardation film, an elliptically polarizing film, an antireflection film, and a brightness enhancement film. Further, a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive of the present invention is laminated, and a peelable film is further laminated thereon to form the above-described optical pressure-sensitive adhesive film.

The optical pressure-sensitive adhesive film for optical
(A) A pressure-sensitive adhesive is applied to the release treatment surface of the peelable film, dried, and a film-like optical member is laminated on the surface of the adhesive layer.
(A) A film-like optical member can be obtained by directly applying a pressure-sensitive adhesive and drying, and laminating the release-treated surface of the peelable film on the surface of the adhesive layer.
The reaction between the copolymer (A) and the crosslinking agent (B) is performed when the pressure-sensitive adhesive composition is dried and when a film-like optical member or a peelable film is laminated on the surface of the pressure-sensitive adhesive layer. Proceed after lamination.
In addition, the pressure sensitive adhesive film for optics of this invention is not limited to the said aspect, The pressure sensitive adhesive layer may be provided in both surfaces of the optical member.
Moreover, it is not always necessary to use a peelable film.
And it can use as a laminated body which can be used for an optical use by peeling the peelable film which covered the surface of the adhesive bond layer of the pressure-sensitive adhesive film for optics, and sticking to a film member or a glass member. .
In particular, an optical glass laminate having a configuration of optical member / pressure-sensitive adhesive layer / glass member was obtained by sticking the optical pressure-sensitive adhesive film of the present invention to a glass member for a liquid crystal cell. It is called a cell member.

  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 of carbonate group-containing acrylic ester monomer>
(Synthesis Example 1)
In the reaction vessel of the polymerization reactor equipped with a reaction vessel, a stirrer, a thermometer, a reflux condenser, and an air introduction tube, the following ethylenically unsaturated monomer, cyclic ester (f), catalyst and organic solvent are respectively shown below. Prepared in proportion.

[Reaction tank]
2-Hydroxyethyl acrylate (a1) 22.7 parts Pyridine 16.7 parts Toluene 90.0 parts [Drip device]
17.3 parts of methyl chloroformate

  The air in the reaction vessel was replaced with nitrogen gas, and then cooled with ice. The mixture was added dropwise from the dropping apparatus over 30 minutes while stirring, and then reacted for 6 hours, and then washed three times with a solvent composed of distilled water and toluene. Furthermore, it wash | cleaned once with the solvent which consists of a saturated salt solution and toluene, Then, the supernatant liquid was fractionated using the separating funnel. After this fractionated supernatant was treated with magnesium sulfate, volatile components were removed by an evaporator to obtain ethyl acrylate-methyl carbonate, which is a carbonate group-containing acrylate monomer. The yield of the obtained product was 75% by molecular weight measurement.

(Synthesis Example 2)
Ethyl acrylate-butyl carbonate was obtained in the same manner as in the above synthesis method except that 25.0 g of butyl chloroformate was used instead of 17.3 g of methyl chloroformate used in Synthesis Example 1. The yield of the obtained product was 82% by molecular weight measurement.

<Production of copolymer (A)>
(Synthesis Example 3)
Reactor, stirrer, thermometer, reflux condenser, dropping device, reaction vessel and dropping device of polymerization reactor equipped with air introduction pipe, the following, ethylenically unsaturated monomer, initiator and organic solvent respectively The ratio was charged.

[Reaction tank]
N-Butyl acrylate (a3) 49 parts Acrylic acid (a2) 1 part Methyl acetate 30 parts 2,2′-Azobisisobutyronitrile 0.05 part [Drip device]
N-Butyl acrylate (a3) 29 parts Acrylic acid (a2) 1 part Ethylenically unsaturated monomer prepared in Synthesis Example 1 20 parts Ethyl acetate 36 parts 2,2'-Azobisisobutyronitrile 0.05 Part

  After replacing the air in the reaction tank with nitrogen gas, the temperature was raised to 90 ° C. in a nitrogen atmosphere while stirring. Next, the mixture of the ethylenically unsaturated monomer, the initiator, and the organic solvent was dropped from the dropping device over 1 hour. After completion of the dropwise addition, the reaction was continued for 6 hours with further stirring, and then 50 parts of ethyl acetate (hereinafter referred to as EAc) was added and cooled to room temperature to obtain a transparent solution having a concentration of about 40%.

(Synthesis Example 4)
The reaction was conducted in the same manner as in Synthesis Example 2 except that the ethylenically unsaturated monomer (a2) used in Synthesis Example 3 was changed to 2-hydroxyethyl acrylate (a1), and the concentration was about 40% with EAc. The viscosity was slightly increased, but a transparent solution was obtained.

(Synthesis Example 5)
The reaction was conducted in the same manner as in Synthesis Example 3 except that the ethyl acrylate-methyl carbonate prepared in Synthesis Example 1 was changed to the ethyl acrylate-butyl carbonate prepared in Synthesis Example 2, and EAc was used. The concentration was adjusted to about 40% and a slight increase in viscosity was observed, but a transparent solution was obtained.
<Precursor (AP) Production of Copolymer (A) (Step 1)>
(Synthesis Example 6)
Reactor, stirrer, thermometer, reflux condenser, dropping device, reaction vessel and dropping device of polymerization reactor equipped with air introduction pipe, the following, ethylenically unsaturated monomer, initiator and organic solvent respectively The ratio was charged.

[Reaction tank]
N-butyl acrylate (a3) 49 parts 2-hydroxyethyl acrylate (a1) 10 parts acrylic acid (a2) 1 part methyl acetate 30 parts 2,2′-azobisisobutyronitrile 0.05 part ]
N-Butyl acrylate (a3) 29 parts Acrylic acid (a2) 1 part 2-Hydroxyethyl acrylate (a1) 10 parts Ethyl acetate 36 parts 2,2′-Azobisisobutyronitrile 0.05 part

  After replacing the air in the reaction tank with nitrogen gas, the temperature was raised to 90 ° C. in a nitrogen atmosphere while stirring, and the reaction was performed in the same manner as in Synthesis Example 3. After the reaction was completed, the mixture was adjusted to about 40% with ethyl acetate. A clear solution was obtained.

(Synthesis Example 7)
The ethylenically unsaturated monomer used in Synthesis Example 6 was charged with the following changes.

[Reaction tank]
N-butyl acrylate (a3) 43 parts 2-hydroxyethyl acrylate (a1) 10 parts
Methyl acrylate (a3) 5 parts Methyl methacrylate (a3) 2 parts Methyl acetate 30 parts 2,2'-Azobisisobutyronitrile 0.05 part [Drip device]
N-butyl acrylate (a3) 30 parts 2-hydroxyethyl acrylate (a1) 10 parts ethyl acetate 36 parts 2,2′-azobisisobutyronitrile 0.05 part

  After the air in the reaction vessel was replaced with nitrogen gas, the temperature was raised to 90 ° C. in a nitrogen atmosphere while stirring, and the reaction was performed in the same manner as in Synthesis Example 6. A clear solution was obtained.

(Synthesis Example 8)
The ethylenically unsaturated monomer used in Synthesis Example 6 was charged with the following changes.

[Reaction tank]
Acrylic acid n-butyl (a3) 40 parts Acrylic acid (a2) 5 parts
Methyl acrylate (a3) 5 parts Methyl acetate 30 parts 2,2'-Azobisisobutyronitrile 0.05 part [Drip device]
N-Butyl acrylate (a3) 45 parts Acrylic acid (a2) 5 parts Ethyl acetate 36 parts 2,2'-Azobisisobutyronitrile 0.05 part

  After replacing the air in the reaction tank with nitrogen gas, the temperature was raised to 90 ° C. in a nitrogen atmosphere while stirring, and the reaction was performed in the same manner as in Synthesis Example 6. After the reaction was completed, the mixture was adjusted to about 40% with ethyl acetate. A clear solution was obtained.

<Production of copolymer (A) by ring-opening addition of cyclic ester (f) (step 2)>
(Synthesis Example 9)
A polymerization reactor equipped with a stirrer, thermometer, reflux condenser, dropping device and nitrogen introducing tube is prepared, and the precursor (AP) solution, cyclic compound (f), catalyst and organic solvent are added to the reaction vessel and the dropping device. Each was charged at the following ratio.

[Reaction tank]
200 parts of the precursor (AP) solution obtained in Synthesis Example 6 [Drip device]
Ethylene carbonate (f2) 44 parts p-Toluenesulfonic acid (catalyst) 0.5 part Ethyl acetate 30 parts

After the air in the reaction vessel was replaced with nitrogen gas, the resin solution was stirred, and the temperature was raised to 90 ° C. over 1 hour while removing the solvent from the system.
Subsequently, the cyclic compound (f) mixture was dropped at a constant rate over 1 hour from the dropping device. Furthermore, after reacting and aging for 12 hours with stirring, ethyl acetate was added and cooled to room temperature to complete the reaction, whereby a transparent solution containing the copolymer (A) was obtained.

(Synthesis Examples 10-14)
44 parts of ethylene carbonate (f2), which is the cyclic compound used in Synthesis Example 9, was replaced with 51 parts of propylene carbonate (Synthesis Example 10), 59 parts of glycerin carbonate (Synthesis Example 11), and 37 parts of 1,3-dioxolane (Synthesis Example 12). ), 44 parts of 1,3-dioxane (Synthesis Example 13) and 45 parts of 1,3,5-trioxane (Synthesis Example 14), respectively. Was adjusted to about 40% to obtain a clear solution.

(Synthesis Examples 15 and 16)
200 parts of the precursor (AP) solution used in Synthesis Example 9 were mixed with the precursor (AP) solution obtained in Synthesis Example 7 (Synthesis Example 15) and the precursor (AP) solution obtained in Synthesis Example 8 (Synthesis). A reaction was carried out in the same manner as in Synthesis Example 9 except that each was changed to Example 16), and the concentration was adjusted to about 40% with EAc to obtain a transparent solution.

<Sealing reaction with sealant (D) of copolymer (A) (step 4)>
(Synthesis Example 17)
A reactor equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introducing tube is prepared, and a resin solution containing the copolymer (A) obtained in Synthesis Example 12 is added to the reaction vessel and the dropping device, monoisocyanate The compound (d3) and the organic solvent were charged at the following ratios.

[Reaction tank]
200 parts of the copolymer (A) solution obtained in Synthesis Example 9 [Drip device]
p-Toluenesulfonyl isocyanate (d3) 3 parts ethyl acetate 10 parts

  After the air in the reaction vessel was replaced with nitrogen gas, the temperature was raised to 90 ° C. while stirring the solution. Subsequently, the monoisocyanate compound (d3) mixture was added dropwise to the stirring solution from the dropping device at a constant rate over 1 hour. After completion of the dropwise addition, the mixture was further aged for 6 hours with stirring, and then cooled to room temperature by adding ethyl acetate to obtain a transparent solution having a concentration of about 40% containing the copolymer (A ′) with adjusted hydroxyl value. .

(Synthesis Example 18)
The hydroxyl value was adjusted by adding ethyl acetate in the same manner as in Synthesis Example 17 except that the monoisocyanate compound (d3) used in Synthesis Example 17 was changed to 2 parts of trimethylsilanol as the silane compound (d1). A transparent solution having a concentration of about 40% containing the copolymer (A ′) obtained was obtained.

(Synthesis Example 19)
Prepared by adding ethyl acetate in the same manner as in Synthesis Example 17 except that the monoisocyanate compound (d3) used in Synthesis Example 17 was changed to 2.5 parts of maleic anhydride as the acid anhydride group-containing compound (d2). And a transparent solution having a concentration of about 40% containing the copolymer (A ′) having an adjusted hydroxyl value was obtained.

(Synthesis Example 20)
The resin solution obtained in Synthesis Example 17 was added with 3 parts of ethylamine as an amine compound (d4), reacted in the same manner as in Synthesis Example 17, and prepared by adding ethyl acetate to adjust the acid value. A clear solution containing the copolymer (A ′) having a concentration of about 40% was obtained.

<Production of copolymer (A) that simultaneously undergoes ring-opening addition reaction (step 3)>
(Synthesis Example 21)
A reaction vessel, a stirrer, a thermometer, a reflux condenser, a dropping device, a reaction vessel and a dropping device of a polymerization reaction device equipped with an air introduction pipe, the following ethylenically unsaturated monomer, cyclic ester, initiator, catalyst and The organic solvents were charged at the following ratios.

[Reaction tank]
N-butyl acrylate (a5) 49 parts 2-hydroxyethyl acrylate (a1) 10 parts acrylic acid (a2) 1 part methyl acetate 30 parts 2,2′-azobisisobutyronitrile 0.05 part [drip apparatus ]
N-butyl acrylate (a5) 29 parts acrylic acid (a2) 1 part 2-hydroxyethyl acrylate (a1) 10 parts ethyl acetate 43 parts ethylene carbonate (f) 44 parts 2,2'-azobisisobutyronitrile 0.1 part p-toluenesulfonic acid (catalyst) 0.6 part

After replacing the air in the reaction tank with nitrogen gas, the temperature was raised to 90 ° C. in a nitrogen atmosphere while stirring.
Subsequently, the mixture containing cyclic ester (f) was dripped at this at constant speed over 2 hours from the dripping apparatus. Furthermore, after reacting and aging for 10 hours with stirring, the reaction mixture was adjusted to about 40% with ethyl acetate and cooled to room temperature to complete the reaction, whereby a transparent solution containing the copolymer (A) was obtained.

<Sealing reaction of copolymer (A) with sealant (D) (Step 5)>
(Synthesis Example 22)
A reactor equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introducing tube was prepared. The compound (d3) and the organic solvent were charged at the following ratios.

[Reaction tank]
200 parts of copolymer (A) solution obtained in Synthesis Example 21 [Drip device]
Phenyl isocyanate (d3) 3 parts Ethyl acetate 10 parts

  After the air in the reaction vessel was replaced with nitrogen gas, the temperature was raised to 90 ° C. while stirring the solution. Subsequently, the monoisocyanate compound (d3) mixture was added dropwise to the stirring solution from the dropping device at a constant rate over 1 hour. After completion of the dropwise addition, the mixture was further aged for 6 hours with stirring, and then cooled to room temperature by adding ethyl acetate to obtain a transparent solution having a concentration of about 40% containing the copolymer (A ′) with adjusted hydroxyl value. .

<Production of ammonium salt compound (C1)>
(Synthesis Examples 23 to 114)
According to JP 2009-84541 A, ammonium salt compounds (C1-1) to (C1-92) described in Tables 1 to 6 were synthesized.

<Production of metal salt compound (C2)>
(Synthesis Examples 115 to 124)
According to a conventional method, ammonium salt compounds (C2-1) to (C2-10) shown in Table 7 were synthesized.

<Production of ammonium salt compound (C3)>
(Synthesis Examples 125 to 230)
According to US Pat. No. 6,372,829, ammonium salt compounds (C3-1) to (C3-106) shown in Tables 8 to 14 were synthesized.

For the ethylenically unsaturated monomer having an aerobic bonding group obtained in Synthesis Examples 1 and 2, the appearance, yield, and acid value were determined according to the following methods, and the results are shown in Table 15.

"appearance"
The appearance of the ethylenically unsaturated monomer was visually evaluated.
"yield"
The yield was confirmed by measuring the weight average molecular weight (Mw) of the ethylenically unsaturated monomer (a4). Mw used Showa Denko GPC (gel permeation chromatography) "ShodexGPC System-21". GPC is liquid chromatography that separates and quantifies substances dissolved in a solvent based on the difference in molecular size, and the weight average molecular weight (Mw) is determined in terms of polystyrene.

<Measurement of acid value (AV)>
About 1 g of each sample was accurately weighed in a stoppered Erlenmeyer flask and dissolved by adding 100 ml of a toluene / ethanol (volume ratio: toluene / ethanol = 2/1) mixed solution. 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 formula.
Acid value (mgKOH / g) = {(5.611 × a × F) / S}
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

The symbols shown in Table 15 are as follows.
HEA: 2-hydroxyethyl acrylate, EC: ethylene carbonate, ND: not detected.

  About the solution of the copolymer (A) obtained in Synthesis Examples 3 to 22 and the solution of the copolymer (A ′) adjusted for the hydroxyl value, the solution appearance, nonvolatile concentration (TS,%), solution viscosity ( Vis, mPa · s), acid value (AV, mgKOH / g), hydroxyl value (OHV, mgKOH / g), weight average molecular weight (Mw), and glass transition temperature (Tg, ° C.) were determined according to the following methods. The results are shown in Table 16.

<< Solution appearance >>
The appearance of the solution of the copolymer (A) and the solution of the copolymer (A ′) whose hydroxyl value was adjusted were visually evaluated.
<Measurement of nonvolatile content concentration (NV)>
About 1 g of the solution of the solution of copolymer (A) and the solution of copolymer (A ′) whose hydroxyl value is adjusted, are weighed in a metal container, dried in an oven at 150 ° C. for 20 minutes, and the residue Weighed and calculated the residual rate to obtain the non-volatile concentration (%).

<< Measurement of solution viscosity (Vis) >>
Use the # 3 rotor in a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd.) for the solution of copolymer (A) and the solution of copolymer (A ′) with adjusted hydroxyl value in an atmosphere of 23 ° C. The solution viscosity (mPa · s) was measured at 12 rpm for 1 minute.
<< Measurement of weight average molecular weight (Mw) >>
The weight average molecular weight (Mw) of the copolymer (A) and the copolymer (A ′) with adjusted hydroxyl value is measured using GPC (gel permeation chromatography) “Shodex GPC System-21” manufactured by Showa Denko K.K. It was. GPC is liquid chromatography that separates and quantifies substances dissolved in a solvent based on the difference in molecular size, and the weight average molecular weight (Mw) is determined in terms of polystyrene.

<Measurement of acid value (AV)>
About 1 g of a sample was accurately weighed in a stoppered Erlenmeyer flask, and 100 ml of a toluene / ethanol (volume ratio: toluene / ethanol = 2/1) mixed solution was added and dissolved. 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 / 100)
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 hydroxyl value (OHV) >>
About 1 g of a sample is accurately weighed in a stoppered Erlenmeyer flask and dissolved by adding 100 ml of a toluene / ethanol (volume ratio: toluene / ethanol = 2/1) mixed solution. Further, 5 ml of an acetylating agent (a solution in which 25 g of ethane acid anhydride was dissolved in pyridine to make a volume of 100 ml) was added and stirred for about 1 hour. 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 hydroxyl value was determined by the following formula. The hydroxyl value was a numerical value in the dry state of the resin (unit: mgKOH / g).
Hydroxyl value (mgKOH / g) = [{(ba) × F × 28.25} / S] / (Non-volatile 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)

<< Measurement of glass transition temperature (Tg) >>
An “SSC5200 disk station” (manufactured by Seiko Instruments Inc.) was connected to a robot DSC (differential scanning calorimeter, “RDC220” manufactured by Seiko Instruments Inc.) and used for measurement.
The solution of the copolymer (A) obtained in each synthesis example and the solution of the copolymer (A ′) whose hydroxyl value was adjusted were applied to the release-treated polyester film and dried, and the dried resin About 10 mg is scraped, put into an aluminum pan as a sample, weighed and set in a differential scanning calorimeter, heated for 5 minutes at a temperature of 100 ° C. using the same type of aluminum pan without sample as a reference, and then using liquid nitrogen Then, it was rapidly cooled to -120 ° C. Thereafter, the temperature was raised at 10 ° C./min, and the glass transition temperature (Tg, unit: ° C.) was determined from the DSC chart obtained during the temperature elevation.

The symbols shown in Table 16 are as follows.
BA: n-butyl acrylate, MA: methyl acrylate, AA: acrylic acid, HEA: 2-hydroxyethyl acrylate, MMA: methyl methacrylate, EC: ethylene carbonate, PC: propylene carbonate, GC: glycerine carbonate, OXO : 1,3-dioxolane, DOX: 1,3-dioxane, TOX: 1,3,5-trioxane, PTSI: p-toluenesulfonyl isocyanate, PhNCO: phenyl isocyanate, TMS: trimethylsilanol, EA: ethylamine, MAnh: anhydrous Maleic acid, EAc: ethyl acetate, AIBN: 2,2′-azobisisobutyronitrile, PTS: p-toluenesulfonic acid.

Example 1
With respect to 100 parts of the solution of the copolymer (A) obtained in Synthesis Example 9, 0.5 part of the ammonium salt compound (C1) and further as a crosslinking agent (B), Tone was added and stirred well so that 5 parts of a trimethylolpropane adduct of cinnate) and a coating viscosity of 2000 to 3000 mPa · s were obtained to obtain a pressure-sensitive adhesive composition.
This was coated on a peeled polyester film (hereinafter referred to as “peelable film”) so that the thickness after drying was 25 μm, and dried at 100 ° C. for 2 minutes to form a pressure-sensitive adhesive layer. did.
After drying, one side of a polarizing film with a multilayer structure in which both sides of a polyvinyl alcohol (PVA) polarizer are sandwiched between triacetyl cellulose (TAC) protective films is bonded to a pressure-sensitive adhesive layer. A laminated film having a configuration of “pressure adhesive layer / TAC film / PVA / TAC film” was obtained.
Next, the obtained laminated film was aged (dark reaction) for one week under the condition of a temperature of 23 ° C. and a relative humidity of 50%, and the reaction of the pressure-sensitive adhesive layer was advanced to obtain a pressure-sensitive adhesive film for optical use.

(Comparative Examples 1-6)
In the same manner as in Example 1 except that the resin solution prepared in Synthesis Examples 3 to 8 was used instead of the copolymer (A) solution obtained in Synthesis Example 9 used in Example 1, the optical A pressure-sensitive adhesive film was obtained.

(Examples 2 to 14)
Example except that the solution of the copolymer (A) obtained in Synthesis Examples 10 to 22 was used instead of the solution of the copolymer (A) prepared in Synthesis Example 9 used in Example 1. In the same manner as in Example 1, an optical pressure-sensitive adhesive film was produced.

(Examples 15 to 17)
Instead of the ionic compound (C) used in Example 1, (C1-26) (Example 15), (C1-64) (Example 16), (C-89) (Example 17) were respectively used. An optical pressure-sensitive adhesive film was produced in the same manner as in Example 1 except that it was used.

(Examples 18 to 20)
Instead of the ionic compound (C) used in Example 1, (C3-39) (Example 18), (C3-83) (Example 19), (C3- 84) An optical pressure-sensitive adhesive film was prepared in the same manner as in Example 1 except that (Example 20) was used.
(Examples 21 to 22)
Instead of TDI / TMP of the crosslinking agent (B) used in Example 1, XDI / TMP (trimethylolpropane adduct of xylylene diisocyanate) was used in Example 21, and HMDI / burette (hexa) was used in Example 22. A pressure-sensitive adhesive film was produced in the same manner as in Example 1 except that 5 parts each of methylene diisocyanate bullet adducts) were added.

(Examples 23 to 26)
Instead of TDI / TMP as the crosslinking agent (B) used in Example 1, in Example 23, HBAP (2,2′-bishydroxymethylbutanol tris [3- (1-aziridinyl) propionate]) 0.1 Parts, in Example 24, 5 parts of TGMXDA (N, N, N ′, N′-tetraglycidyl-m-xylylenediamine), in Example 25, V-05 (“carbodilite V-05” which is a carbodiimide compound): Nisshinbo 5 parts, manufactured by Kogyo Co., Ltd. In Example 26, 1 part of Al chelate (aluminum tris (2,4-pentadionate)) was added in the same manner as in Example 1 except that 1 part was added. A pressure sensitive adhesive film was prepared. In Example 26, the solvent was changed from methyl ethyl ketone to isopropyl alcohol (IPA).

(Examples 27 and 28)
Instead of TDI / TMP of the crosslinking agent (B) used in Example 14, XDI / TMP (trimethylolpropane adduct of xylylene diisocyanate) was used in Example 27, and HMDI / burette (hexa) was used in Example 28. A pressure-sensitive adhesive film was produced in the same manner as in Example 1 except that 5 parts each of methylene diisocyanate bullet adducts) were added.

(Examples 29 to 32)
Instead of TDI / TMP as the crosslinking agent (B) used in Example 14, in Example 29, HBAP (2,2′-bishydroxymethylbutanol tris [3- (1-aziridinyl) propionate]) 0.1 Parts, in Example 30, 5 parts TGMXDA (N, N, N ′, N′-tetraglycidyl-m-xylylenediamine), in Example 31, V-05 (“carbodilite V-05” which is a carbodiimide compound): Nisshinbo 5 parts, made in Example 32, and in Example 32, 1 part of Al chelate (aluminum tris (2,4-pentadionate)) was added in the same manner as in Example 1 except that 1 part was added. A pressure sensitive adhesive film was prepared. In Example 32, the solvent was changed from methyl ethyl ketone to isopropyl alcohol (IPA).

(Examples 33 to 118)
Similar to Example 1 except that (C1-1) to (C1-3) and (C1-5) to (C1-92) were used instead of the ionic compound (C) used in Example 1, respectively. Thus, an optical pressure-sensitive adhesive film was produced.

(Examples 119 to 128)
An optical pressure-sensitive adhesive film was produced in the same manner as in Example 1 except that (C2-1) to (C2-10) were used instead of the ionic compound (C) used in Example 1. .

(Examples 129 to 234)
An optical pressure-sensitive adhesive film was prepared in the same manner as in Example 1 except that (C3-1) to (C3-106) were used instead of the ionic compound (C) used in Example 1. .

The pot life and coating properties of the pressure-sensitive adhesive compositions obtained in each Example and each Comparative Example were evaluated by the following methods. Various performances of the optical pressure-sensitive adhesive film obtained in the same manner were evaluated by the following methods. Each result is shown to Tables 17-23. In the present specification, Examples 1 to 8, 13, 15 to 26, 31, 33 to 234 are reference examples .

<Evaluation method of pot life>
About the obtained pressure-sensitive adhesive composition, after addition of a crosslinking agent (B), the viscosity at 25 ° C. is used every 12 hours until 10 hours, using a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd.) at 12 rpm for 1 minute. It measured on the conditions of rotation and evaluated the pot life (pot life) in three steps.
○: “Viscosity increase rate up to 8 hours is less than twice. No problem at all”
Δ: “Viscosity increase rate up to 5 hours is less than 2 times. Practical use is possible.”
X: “Gelation in less than 5 hours.

<Evaluation method of coatability>
The obtained pressure-sensitive adhesive composition was applied to a peelable film with a comma coater at a speed of 2 m / min, dried in a 100 ° C. oven to form a pressure-sensitive adhesive layer having a thickness of 25 μm, and bonded. A pressure-sensitive adhesive film was prepared by laminating a 50 μm thick polyester film on the surface of the agent layer. And the state of the adhesive bond layer surface (coating surface) after peeling a peeling film was observed visually, and evaluated in three steps.
○: “Smooth coated surface was obtained. No problem at all”
Δ: “Slight repellency and foaming are recognized at the end of the coated surface, but there is no practical problem.”
×: “Repelling, foaming and streaking are recognized on the coated surface, and there are practical problems.”

<< Evaluation method of optical characteristics >>
The pressure-sensitive adhesive composition obtained in each Example and Comparative Example was applied to a peelable film with a comma coater at a speed of 2 m / min, dried in a 100 ° C. oven, and a pressure-sensitive adhesive having a thickness of 25 μm. An adhesive layer was formed, a peelable film was bonded to the surface of the adhesive layer, and a pressure-sensitive adhesive film held between the peelable films was produced.
After aging for one week at a temperature of 23 ° C. and a relative humidity of 50%, both peelable films were removed, the appearance of the pressure-sensitive adhesive layer alone was visually judged, and HAZE was determined as “NDH-300A” [ Made by Nippon Denshoku Industries Co., Ltd.].
○: No problem in practical use and very good. HAZE: Less than 0.5.
(Triangle | delta): Cloudiness etc. are not recognized and HAZE: 0.5 or more and less than 2, it can be used without a problem practically.
X: Some cloudiness is recognized or HAZE: 2 or more. There are practical problems.

<Evaluation method of removability (reworkability)>
The pressure-sensitive adhesive film for optics obtained in each example and comparative example is cut into a size of 25 mm × 150 mm, the peelable film is peeled off, and is attached to a float glass plate having a thickness of 1.1 mm using a laminator. The laminate of the polarizing film and the glass plate was obtained by holding it in an autoclave at 50 ° C. and 5 atm for 20 minutes.
The laminate was allowed to stand at 23 ° C. and a relative humidity of 50% for 1 week, and then peeled off at a speed of 300 mm / min in the direction of 180 °. The haze on the glass surface after peeling was visually observed and evaluated in three stages.
○: No fogging, no problem in practical use, very good.
Δ: Some fogging is observed, but no problem in practical use and good.
X: Transfer of the pressure-sensitive adhesive composition is recognized over the entire surface, and is not practical.

《Durability (heat resistance, wet heat resistance) evaluation method》
The pressure-sensitive adhesive film for optics obtained in each example and comparative example was cut into a size of 150 mm × 80 mm, the peelable film was peeled off, and the polarized light was applied to both surfaces of a 1.1 mm thick float glass plate. The film was stuck using a laminator so that the absorption axis of the film was orthogonal. Subsequently, the glass plate to which the polarizing film was attached was held in an autoclave at 50 ° C. and 5 atm for 20 minutes to obtain a liquid crystal cell member in a laminate of the polarizing film and the glass plate.
As evaluation of heat resistance, floating peeling after leaving the laminate at 95 ° C. for 1000 hours, and light leakage (white spots) when light was transmitted through the laminate were visually observed.
In addition, as an evaluation of the heat and moisture resistance, the above laminate was floated after being left for 1000 hours at 80 ° C. and a relative humidity of 90%, and light leakage (white spots) when light was transmitted through the laminate was visually observed. did.
The heat resistance and moist heat resistance were evaluated based on the following four-stage evaluation criteria.
A: No floating peeling, foaming, whitening, or displacement was observed, and there was no problem in practical use.
○: No floating peeling, foaming, or whitening was observed, and the deviation was less than 0.2 mm.
Δ: Slightly floating peeling, foaming, and whitening are observed, but the deviation is less than 0.2 to 0.5 mm, and there is no problem in practical use. ×: Fully floating peeling, foaming, and whitening are present It is impractical.

<Evaluation method of antistatic performance (surface resistance value: SR)>
The peel-off film of the pressure-sensitive adhesive film is peeled off, and the surface resistance value of the exposed adhesive layer surface is measured under the conditions of 23 ° C.-35, 45, 55% RH (manufactured by Mitsubishi Chemical Corporation). : MCT-HT450) (unit: Ω / □), and the antistatic performance evaluation of the initial value and the time-lapse value was made.
(Initial value evaluation)
A peelable film is coated with a comma coater at a speed of 2 m / min, dried in a 100 ° C. oven to form a pressure-sensitive adhesive layer having a thickness of 25 μm, and a polyester film having a thickness of 50 μm on the surface of the adhesive layer. Were bonded together to prepare a pressure-sensitive adhesive film. After aging for one week under the conditions of a temperature of 23 ° C. and a relative humidity of 50%, the antistatic performance was evaluated by the above method and set as an initial value.
(Evaluation over time)
The pressure-sensitive adhesive film aged for 1 week is allowed to stand for 7 days under conditions of a temperature of 60 ° C. and a relative humidity of 95%, and then for 24 hours under conditions of a temperature of 23 ° C. and a relative humidity of 50%. The antistatic performance was evaluated by the above method, and the time-dependent value was obtained.
○: “Surface resistance value is less than 1.0 × 10 ¹⁰ ”
Δ: “Surface resistance value is 1.0 × 10 ¹⁰ or more and less than 1.0 × 10 ¹¹ ”
×: “Surface resistance value is 2.0 × 10 ¹¹ or more.”

<< Evaluation method of antistatic performance (peeling withstand voltage: EV) >>
The release film of the pressure-sensitive adhesive film is peeled off, and the exposed adhesive layer is attached to a Teflon (registered trademark) sheet (thickness 1 mm) under the conditions of a temperature of 23 ° C. and a relative humidity of 50%, and crimped with a hand roll. did. After 24 hours from the press bonding, after static electricity was removed on a glass plate with a static eliminator (“SJ-F010” manufactured by Keyence Corporation), the pressure-sensitive adhesive film was peeled from the Teflon (registered trademark) sheet, and Teflon ( The static electricity on the sheet surface of (registered trademark) was measured at 10 locations with a static electricity measuring instrument (“STATION DZ3” manufactured by Sishido static electricity Co., Ltd.), and the value having the maximum absolute value was defined as peeling charge (unit: kV).
○: “Peeling withstand voltage is less than ± 0.1 kV”
Δ: “Peeling withstand voltage is ± 0.1 kV or more and less than ± 0.5 kV”
×: “Peeling withstand voltage is ± 0.5 kV or more.”

The symbols shown in Tables 17 to 23 are as follows.
TDI / TMP: trimethylolpropane adduct of tolylene diisocyanate, XDI / TMP: trimethylolpropane adduct of xylylene diisocyanate, HMDI / burette: burette adduct of hexamethylene diisocyanate, HBAP: 2,2 ′ -Bishydroxymethylbutanol tris [3- (1-aziridinyl) propionate], TGMXDA: N, N, N ', N'-tetraglycidyl-m-xylylenediamine, V-05: "carbodilite V- which is a carbodiimide compound 05 ", Al chelate: aluminum tris (2,4-pentadionate), IPA: isopropyl alcohol, Tol: toluene.

As described above, it can be seen that the pressure-sensitive adhesive composition of the present invention is excellent in heat resistance, moist heat resistance, optical characteristics, reworkability, and antistatic performance.
On the other hand, in Comparative Examples 1 to 3 copolymerized with an ethylenically unsaturated monomer component having a carbonate group, since the polymerization stability is not so good, the coating property is adversely affected, so the durability is poor. Moreover, the antistatic performance as expected is not obtained. Further, in Comparative Examples 3 to 6 that do not contain a carbonate group in the side chain, it is recognized that the conductive path is not formed, so that almost no antistatic performance is exhibited, and after being attached to a glass plate, under high temperature or high temperature and high humidity. When placed underneath for a long period of time, foaming or peeling off, which seems to be migration of the antistatic agent, occurs, and it is recognized that the durability is inferior.

Claims (11)

A part of a terminal functional group formed by ring-opening addition of a cyclic compound (f) having four or more members having a hydroxyl group and / or a carboxyl group as a functional group and further having two or more oxygen atoms in the side chain A copolymer (A) having a glass transition temperature of −60 to 0 ° C., which is reacted with the sealing compound (D), and a crosslinking agent having a functional group capable of reacting with a functional group in the copolymer (A) ( B) and an ionic compound (C) selected from the following general formula (1), (2) or (3) ,
The pressure sensitive adhesive composition, wherein the copolymer (A) has a hydroxyl value of 0.01 to 50 mgKOH / g and / or an acid value of 0.01 to 50 mgKOH / g .
General formula (1)

[In General Formula (1), R ^{1 to} R ⁸ may each independently have a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or a substituent. Represents a good alkynyl group, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent, and R ^{5 to} R ⁸ may form a ring with adjacent substituents; Good. ]
General formula (2)

[In General Formula (2), R ^{1 to} R ⁴ may each independently have a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or a substituent. A good alkynyl group, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent, and A ⁺ represents an alkali metal ion. ]
General formula (3)

[In General Formula (3), R ^{5 to} R ⁸ may each independently have a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or a substituent. It represents a good alkynyl group, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent, and adjacent substituents may form a ring.
R ⁹ represents a scan Ruhoniru binding group.
R ¹⁰ represents a fluoromethyl group or a fluorine group .
R ¹¹ represents a trifluoromethanecarbonyl group or —R ⁹ R ¹⁰ . ]   The copolymer (A) comprises an ethylenically unsaturated monomer (a1) having a hydroxyl group as a functional group and / or an ethylenically unsaturated monomer (a2) having a carboxyl group, and (a1) if necessary. , A copolymer (A) obtained by copolymerizing an ethylenically unsaturated monomer (a3) other than (a2), and further 100 parts by weight of a precursor (AP) of the copolymer (A) The pressure-sensitive adhesive composition according to claim 1, wherein the pressure-sensitive adhesive composition contains 1 to 40 parts by weight of (a1) and / or (a2).   A linking group formed by ring-opening addition of a cyclic compound having four or more members having two or more oxygen atoms to the side chain of the copolymer (A) is a copolymer (having a hydroxyl group and / or a carboxyl group). It is produced by a reaction between a hydroxyl group and / or a carboxyl group in the precursor (AP) of (A) and a cyclic compound (f) having four or more members having two or more oxygen atoms. The pressure-sensitive adhesive composition according to claim 1 or 2.   The cyclic compound (f) having at least four members having two or more oxygen atoms is cyclic formal (f-1) and / or cyclic carbonate (f-2). Pressure sensitive adhesive composition.   The pressure-sensitive adhesive composition according to claim 4, wherein the cyclic formal (f-1) is at least one selected from dioxolanes, dioxanes, and trioxanes.   The copolymer (A) is a 4-membered or higher cyclic compound (f) having 1 to 150 parts by weight having two or more oxygen atoms with respect to 100 parts by weight of the precursor (AP) of the copolymer (A). The pressure-sensitive adhesive composition according to claim 4 or 5, wherein the pressure-sensitive adhesive composition is used.   The pressure-sensitive adhesive composition according to any one of claims 1 to 6, comprising 0.01 to 10 parts by weight of the ionic compound (C) with respect to 100 parts by weight of the copolymer (A).   The pressure-sensitive adhesive composition according to any one of claims 1 to 7, wherein the crosslinking agent (B) is a polyisocyanate compound (b1).   The crosslinking agent (B) is any one of an epoxy compound (b2), an aziridine compound (b3), a carbodiimide compound (b4), an oxazoline compound (b5), or a metal chelate compound (b6). The pressure-sensitive adhesive composition according to any one of -7.   The laminated body by which an optical member is laminated | stacked on the pressure sensitive adhesive layer formed from the pressure sensitive adhesive composition in any one of Claims 1-9.   A liquid crystal cell member comprising a glass member for a liquid crystal cell, a pressure sensitive adhesive layer formed from the pressure sensitive adhesive composition according to claim 1, and an optical member.