JP2012102279A - Resin composition for pressure-sensitive adhesive, and pressure-sensitive adhesive using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel resin composition for a pressure-sensitive adhesive, capable of forming an optical pressure-sensitive adhesive film which is for being pasted on optical elements such as glass members for liquid crystal cells, is excellent in repealability from glass members for liquid crystal cells and the contamination of adherends, and is excellent in the durability (heat resistance, wet heat resistance) after pasting; and to provide a pressure-sensitive adhesive.SOLUTION: The resin composition for a pressure-sensitive adhesive is prepared by modifying an active hydrogen group of a resin (A) having the active hydrogen group with a compound (B) having a functional group (b) capable of forming a urethane bond or urea bond by being reacted with the active hydrogen group.

Description

  The present invention relates to a novel resin composition for pressure-sensitive adhesives, a pressure-sensitive adhesive containing the same, and a pressure-sensitive adhesive film for optical use that is suitably used for optical applications, 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 be excellent in transparency, a pressure-sensitive adhesive mainly composed of a propenoic acid 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 polyhydroxyethene polarizer are sandwiched between protective films of triacetyl cellulose or cycloolefin. 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 polyhydroxyethene film in the polarizing film has 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 can be used under high temperature or high temperature and high humidity conditions. If the dimensions of the polarizing film are changed, bubbles may be generated at the interface between the adhesive layer and the glass (foaming phenomenon), or the polarizing film may be lifted from the glass and peeled off (floating / peeling phenomenon).
Therefore, by adjusting the molecular weight of the pressure-sensitive adhesive and the degree of crosslinking of the pressure-sensitive adhesive and increasing the adhesive strength, the polarizing film does not foam, float, or peel even under harsh environments against dimensional changes. An attempt was made to do so.

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

  As described above, the pressure-sensitive adhesive for laminating a polarizing film on a glass member for a liquid crystal cell has good optical properties (transparency), heat resistance and moist heat resistance, good stress relaxation properties, and removability. Etc. are required. Similar performance is also required for pressure sensitive adhesives for laminating retardation films and cover films for various displays.

On the other hand, various pressure-sensitive adhesives have been proposed.
For example, as a pressure-sensitive adhesive for pressure-sensitive adhesive optical films, by adding a low molecular weight material such as a plasticizer to propenoic acid resin, the pressure-sensitive adhesive layer is moderately softened to impart stress relaxation properties. A propenoic acid-based pressure-sensitive adhesive is disclosed (for example, see Patent Document 1).

  In addition, for example, a propenoic acid-based pressure-sensitive adhesive blended with propenoic acid resins having different molecular weights and further containing a crosslinking agent is known (for example, see Patent Document 2).

  Further, for example, in addition to a pressure-sensitive adhesive containing a propenoic acid resin and a cross-linking agent, a propenoic acid resin used in combination with a polyurethane resin is known (see Patent Document 3).

However, an optical pressure-sensitive adhesive film using the pressure-sensitive adhesive described in Patent Documents 1 to 3 is exposed to a high temperature or a high temperature and high humidity condition for a long time after being attached to an adherend. Then, extremely small bubbles made of a low molecular weight propenoic acid resin 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 19 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 1, white spots were not regarded as a problem in a display device of less than 19 inches. However, there is also a problem that white spots are conspicuous in a display device using a high-intensity light source used at 19 inches or more.

  In addition, for example, in order to improve heat resistance, it is disclosed that an amino group and / or amide group-containing monomer is copolymerized (see Patent Document 4), and a heterocycle-containing monomer is copolymerized. A pressure-sensitive adhesive that is disclosed (see Patent Document 5) and does not cause appearance defects such as floating and peeling even in a high humidity and high temperature environment by using the obtained copolymer is disclosed.

  However, the pressure-sensitive adhesive disclosed herein does not cause floating or peeling under a heat aging environment of 80 ° C. or 60 ° C.-90% relative humidity, but under a more severe environment, for example, 120 ° C. In an environment of heat aging or 80 ° C.-relative humidity 90% wet heat aging, the durability is not sufficient, and there is a problem that cracks and foaming easily occur.

  As described above, from the conventional propenoic acid-based pressure-sensitive adhesive using a blend of various resins, re-peelability from the adherend, called “reworkability”, adherend contamination, and high durability after sticking In addition to being able to obtain a pressure-sensitive adhesive optical film that satisfies a good balance of properties, each pressure-sensitive adhesive has a high solution viscosity despite its low non-volatile content, causing problems in coating processability and price .

Japanese Patent No. 3272721 JP 2001-049200 A Japanese Patent No. 3272721 Japanese Patent Laid-Open No. 06-108025 JP 2007-277510 A

  The present invention has an object of providing a pressure-sensitive adhesive for use in a pressure-sensitive adhesive film having excellent heat resistance, moist heat resistance and transparency, and further having good reworkability.

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 compound (B) having a functional group (b) capable of forming a urethane bond or a urea bond by reacting an active hydrogen group of the resin (A) having an active hydrogen group with the active hydrogen group. It is related with the resin composition for pressure sensitive adhesives characterized by being modified | denatured by.

  Moreover, 2nd invention is resin which resin (A) which has an active hydrogen group superposes | polymerizes the monomer component which makes the ethylenically unsaturated monomer (a) which has an active hydrogen group essential. The present invention relates to a pressure-sensitive adhesive resin composition according to the first invention.

  The third invention is the pressure-sensitive adhesive resin composition according to the first or second invention, wherein the active hydrogen group of the resin (A) having an active hydrogen group is a hydroxyl group or an amino group. Related to things.

  The fourth invention relates to the pressure-sensitive adhesive resin composition of any one of the first to third inventions, wherein the functional group (b) is an isocyanate group.

  The fifth invention relates to a pressure-sensitive adhesive comprising the pressure-sensitive adhesive resin composition of any one of the first to fourth inventions and a reactive compound (C) capable of reacting with the resin composition. .

  Moreover, 6th invention is related with the pressure-sensitive adhesive film for optics by which the pressure-sensitive-type adhesive layer which consists of a pressure-sensitive adhesive of 5th invention is provided in the at least one surface of the film-form base material.

  Moreover, 7th invention is related with the adhesive optical member by which the pressure sensitive adhesive layer which consists of a pressure sensitive adhesive of 5th invention is provided in the at least one surface of the optical member.

  Moreover, 8th invention is related with the optical glass laminated body by which the optical member, the adhesive bond layer which consists of a pressure sensitive adhesive of 5th invention, and glass are laminated | stacked one by one.

  The ninth invention relates to a compound (B) having a functional group (b) capable of forming a urethane bond or a urea bond by reacting an active hydrogen group of the resin (A) having an active hydrogen group with the active hydrogen group. And a method for producing a resin composition for a pressure-sensitive adhesive, which comprises a step of modifying the composition.

  By using the new pressure-sensitive adhesive resin composition of the present invention, it is excellent in removability from the glass member for liquid crystal cells and adherend contamination, and durability after sticking (heat resistance, heat and moisture resistance) It is now possible to provide a pressure-sensitive adhesive capable of forming an optical pressure-sensitive adhesive film excellent in.

The matters necessary for carrying out the present invention are specifically described below.
The pressure-sensitive adhesive of the present invention comprises a compound (B) having a functional group (b) capable of reacting an active hydrogen group of a resin (A) having an active hydrogen group with an active hydrogen group to form a urethane bond or a urea bond. And a reactive compound (C) capable of reacting with the resin composition.
The pressure-sensitive adhesive having the above structure has a urethane bond or urea bond in the side chain of the resin composition for pressure-sensitive adhesive, so that a number of heat-resistant units derived from the urethane bond or urea bond are pendant to the polymer. It is presenting. Therefore, for example, when the pressure-sensitive adhesive is used for laminating a polarizing plate, since many heat-resistant units cover the entire resin even in a high humidity and high temperature environment, appearance defects such as floating and foaming do not occur. I guess.

The resin (A) having an active hydrogen group used in the present invention is preferably a resin obtained by polymerizing a monomer component essentially comprising an ethylenically unsaturated monomer (a) having an active hydrogen group, The active hydrogen group is preferably a hydroxyl group, a carboxyl group, a sulfonyl group, a phosphonyl group, an amino group, an amide group, a maleimide group or the like, but is not particularly limited as long as it is a functional group capable of reacting with the reactive compound (C) described later. There is no. Among them, it is preferable to contain at least one of a hydroxyl group and an amino group in order to form a urethane bond or a urea bond by reaction with the compound (B) described later.
Examples of the ethylenically unsaturated monomer constituting the active hydrogen group-containing resin (A) used in the present invention include propenoic acid, 2-methylpropenoic acid, propenoic acid derivatives, 2-methylpropenoic acid derivatives, and other alkenyls. Among the group-containing compounds, compounds having an active hydrogen group can be exemplified.

  It is preferable that 0.01 to 50% by weight of the ethylenically unsaturated monomer (a) having an active hydrogen group is contained in 100% by weight of the monomer used for obtaining the resin (A) having an active hydrogen group. Although it can be used outside the above numerical range, it may be difficult to solve the problems of the present invention such as transparency, heat resistance, and heat and humidity resistance.

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

  The weight average molecular weight (Mw) of the resin (A) having an active hydrogen group is preferably 50,000 to 2,000,000, and more preferably 200,000 to 1,500,000. When Mw exceeds 2,000,000, the fluidity of the resin (A) is lowered, and the coating property of the pressure-sensitive adhesive may be deteriorated. On the other hand, when Mw is less than 50,000, the cohesive force of the adhesive layer may be insufficient.

As described above, the ethylenically unsaturated monomer (a) having an active hydrogen group is, for example, a monomer containing a hydroxyl group, a carboxyl group, a sulfonyl group, a phosphonyl group, an amino group, an amide group, or a maleimide group. Can be mentioned.
As a monomer containing a hydroxyl group, for example,
2-hydroxyethyl (2-methyl) propenoate [2-hydroxyethyl propenoate and 2-hydroxyethyl 2-methylpropenoate are collectively referred to as “(2-methyl) propenoic acid 2-hydroxyethyl”. The same applies below. ], 2-hydroxypropyl (2-methyl) propenoate, 2-hydroxypropyl (2-methyl) propenoate, 2-hydroxybutyl (2-methyl) propenoate, 4-hydroxybutyl (2-methyl) propenoate, (2-methyl) propenoic acid 4-hydroxyphenyl, (2-methyl) propenoic acid 2-hydroxycyclohexyl, (2-methyl) propenoic acid 2-hydroxy-3-phenoxypropyl, 3- (4-hydroxyphenyl) propenoic acid Hydroxyl-containing (2-methyl) propenoic acid esters such as methyl, 2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl (2-methyl) propenoate Kind;

α-hydroxymethyl (2-methyl) propenoate methyl, α-hydroxymethyl (2-methyl) propenoate ethyl, α-hydroxymethyl (2-methyl) propenoate propyl, α-hydroxymethyl (2-methyl) propenoate Isopropyl, butyl α-hydroxymethyl (2-methyl) propenoate, isobutyl α-hydroxymethyl (2-methyl) propenoate, tert-butyl α-hydroxymethyl (2-methyl) propenoate, α-hydroxymethyl (2- Methyl) pentyl propenoate, α-hydroxymethyl (2-methyl) propenoate hexyl, α-hydroxymethyl (2-methyl) propenoate 2-ethylhexyl, α-hydroxymethyl (2-methyl) propenoate phenyl, α-hydroxy Benzyl methyl (2-methyl) propenoate, α- (1 Hydroxyethyl) (2-methyl) methyl propenoate, α- (1-hydroxyethyl) (2-methyl) ethyl propenoate, α- (1-hydroxyethyl) (2-methyl) propenoate butyl, α- (1 Α-hydroxyalkyl (2-methyl) propenoic acid esters such as 2-hydroxyethyl) (2-methyl) propenoic acid 2-ethylhexyl;

2- (2′-hydroxy-5 ′-(2-methyl) propane-2-enoyloxyethylphenyl) -2H-benzotriazole, 2- (2′-hydroxy-5 ′-(2-methyl) propane- 2-enoyloxyethylphenyl) -5-chloro-2H-benzotriazole, 2- (2′-hydroxy-5 ′-(2-methyl) propane-2-enoyloxypropylphenyl) -2H-benzotriazole, 2- (2′-hydroxy-5 ′-(2-methyl) propane-2-enoyloxypropylphenyl) -5-chloro-2H-benzotriazole, 2- (2′-hydroxy-3′-tert-butyl) -5 '-(2-methyl) propane-2-enoyloxyethylphenyl) -2H-benzotriazole, 2- (2'-hydroxy-3'-te t- butyl-5 '- (2-methyl) propane-2-d, such as alkanoyloxy ethylphenyl) -5-chloro -2H- benzotriazole hydroxyl group-containing benzotriazole-based (2-methyl) propenoic acid derivatives;

2-hydroxy-4- {2- (2-methyl) propane-2-enoyloxy} ethoxydiphenylmethanone, 2-hydroxy-4- {2-((2-methyl) propane-2-enoyloxy} butoxydiphenylmethanone 2,2′-dihydroxy-4- {2- (2-methyl) propane-2-enoyloxy} ethoxydiphenylmethanone, 2-hydroxy-4- {2- (2-methyl) propane-2-enoyloxy} ethoxy Hydroxyl group-containing diphenylmethanone-based (2-methyl) propenoic acid derivatives such as -4 ′-(2-hydroxyethoxy) diphenylmethanone;

2,4-diphenyl-6- [2-hydroxy-4- (2- (2-methyl) propane-2-enoyloxyethoxy)]-S-triazine, 2,4-bis (2-methylphenyl)- 6- [2-Hydroxy-4- (2- (2-methyl) propane-2-enoyloxyethoxy)]-S-triazine, 2,4-bis (2-methoxyphenyl) -6- [2- Hydroxy-4- (2- (2-methyl) propane-2-enoyloxyethoxy)]-S-triazine, 2,4-bis (2-ethylphenyl) -6- [2-hydroxy-4- (2 -(2-Methyl) propane-2-enoyloxyethoxy)]-S-triazine, 2,4-bis (2-ethoxyphenyl) -6- [2-hydroxy-4- (2- (2-methyl) Propane-2-enoyloxyethoxy)]-S-to Lyazine, 2,4-bis (2,4-dimethoxyphenyl) -6- [2-hydroxy-4- (2- (2-methyl) propane-2-enoyloxyethoxy)]-S-triazine, 2, 4-bis (2,4-dimethylphenyl) -6- [2-hydroxy-4- (2- (2-methyl) propane-2-enoyloxyethoxy)]-S-triazine, 2,4-bis ( 2,4-diethoxylphenyl) -6- [2-hydroxy-4- (2- (2-methyl) propane-2-enoyloxyethoxy)]-S-triazine, 2,4-bis (2,4 -Diethylphenyl) -6- [2-hydroxy-4- (2- (2-methyl) propane-2-enoyloxyethoxy)]-S-triazine, 2,4-diamino-6-2-methylprop-2 -Enoyloxyethyl-s-tria Of emissions such as the hydroxyl group-containing triazine (2-methyl) propenoic acid derivatives;

(2-methyl) propenoic acid derivatives containing a alkene oxide having a hydroxyl group at the terminal, such as an oxirane adduct of (2-methyl) propenoic acid;

Aliphatic amide group-containing ethenyl monomers having a hydroxyl group such as N-hydroxyethyl (2-methyl) 2-propenamide;

And maleimide derivatives having a hydroxyl group such as Np-hydroxyphenylmaleimide.

  These may use only 1 type or may use multiple types together. In addition to the above, if it contains a hydroxyl group, it is included in the ethylenically unsaturated monomer having a hydroxyl group, and an ethylenically unsaturated monomer containing a primary hydroxyl group is particularly preferred.

  Examples of the monomer containing a carboxyl group include propenoic acid, 2-methylpropenoic acid, 2-carboxyethyl propenoate, 2-methylidenebutanedioic acid, cis-butenedioic acid, trans-butenedioic acid, and penta-2. -Unsaturated carboxylic acids such as enedioic acid and 2-methyl (E) -2-butenedioic acid;

Unsaturated carboxylic acid anhydrides such as 2,5-dihydrofuran-2,5-dione, 3-methylidenetetrahydrofuran-2,5-dione and 3-methyl-2,5-dihydrofuran-2,5-dione ;
These may be used, and these may be used alone or in combination of two or more.

As a monomer containing a sulfonyl group, for example, sulfomethyl (2-methyl) propenoate [sulfomethyl propenoate and sulfomethyl 2-methylpropenoate are collectively referred to as “(2-methyl) propenoate sulfomethyl”. The same applies below. ], 2-sulfoethyl (2-methyl) propenoate, 2-sulfopropyl (2-methyl) propenoate, 3-sulfopropyl (2-methyl) propenoate, 2-sulfobutyl (2-methyl) propenoate, (2 -Methyl) propenoate 4-sulfobutyl, (2-methyl) propenoate 2-sulfobutyl, (2-methyl) propenoate 6-sulfohexyl, (2-methyl) propenoate sulfooctyl, (2-methyl) propenoate sulfodecyl Sulfonyl group-containing (2-methyl) propenoic acid alkyl esters such as (2-methyl) propenoic acid sulfolauryl, (2-methyl) propenoic acid sulfostearyl, (2-methyl) propenoic acid sulfophenoxyethyl, (2 (2-Methyl) propenoic acid containing a sulfonyl group such as -methyl) propenoic acid sulfocyclohexyl Jo esters;
These may be used, and these may be used alone or in combination of two or more.

Examples of the monomer containing a phosphonyl group include (2-methyl) propenoic acid phosphooxyethyl, (2-methyl) propenoic acid phosphooxypropyl, (2-methyl) propenoic acid phosphooxybutyl, 2-methyl) propenoic acid-3-chloro-2-acid phosphooxyethyl, 2-methyl) propenoic acid-3-chloro-2-acid phosphooxypropyl, 2-methyl) propenoic acid-3-chloro-2-acid Phosphooxybutyl, (2-methyl) propenoic acid acid phosphooxyethene oxide (ethene oxide addition mole number: 4 to 10), (2-methyl) propenoic acid acid phosphooxypropene oxide (propene oxide addition mole number: 4 to 10) ) And other unsaturated phosphonic acids;
These may be used, and these may be used alone or in combination of two or more.

Examples of the monomer containing an amino group include N-methylaminoethyl (2-methyl) propenoate, N-tributylaminoethyl (2-methyl) propenoate, and N, N- (2-methyl) propenoate. Containing amino groups such as dimethylaminoethyl, N, N-diethylaminoethyl (2-methyl) propenoate, pentamethylpiperidinyl (2-methyl) propenoate, tetramethylpiperidinyl (2-methyl) propenoate (2 -Methyl) propenoic acid esters;
These may be used, and these may be used alone or in combination of two or more.

Examples of the monomer containing an amide group include 2-propenamide, 2-methylprop-2-enoylamine, N, N-dimethyl-2-propenamide, N, N-diethyl-2-propenamide, N- [3- (N ′, N′-dimethylamino) propyl] -2-propenamide, N-isopropyl-2-propenamide, N-ethenylmethaneamide, N-ethenylacetamide, N-methoxymethyl (2- Methyl) 2-propenamide, N-methoxyethyl (2-methyl) 2-propenamide, N-methoxypropyl (2-methyl) 2-propenamide, N-methoxybutyl (2-methyl) 2-propenamide, N -Methoxyhexyl (2-methyl) 2-propenamide, N-methoxyoctyl (2-methyl) 2-propenamide, N-methoxy Sil (2-methyl) 2-propenamide, N-methoxydodecyl (2-methyl) 2-propenamide, N-methoxyoctadecyl (2-methyl) 2-propenamide, N-ethoxymethyl (2-methyl) 2- Propenamide, N-ethoxyethyl (2-methyl) 2-propenamide, N-ethoxypropyl (2-methyl) 2-propenamide, N-ethoxybutyl (2-methyl) 2-propenamide, N-ethoxyhexyl ( 2-methyl) 2-propenamide, N-ethoxyoctyl (2-methyl) 2-propenamide, N-isopropoxymethyl (2-methyl) 2-propenamide, N-isopropoxyethyl (2-methyl) 2- Propenamide, N-isopropoxypropyl (2-methyl) 2-propenamide, N-isopropoxybuty (2-methyl) 2-propenamide, N-isopropoxyhexyl (2-methyl) 2-propenamide, N-isopropoxyoctyl (2-methyl) 2-propenamide, N-butoxymethyl (2-methyl) 2-propenamide, N-butoxyethyl (2-methyl) 2-propenamide, N-butoxypropyl (2-methyl) 2-propenamide, N-butoxybutyl (2-methyl) 2-propenamide, N-butoxy Hexyl (2-methyl) 2-propenamide, N-butoxyoctyl (2-methyl) 2-propenamide, N-isobutoxymethyl (2-methyl) 2-propenamide, N-isobutoxyethyl (2-methyl) 2-propenamide, N-isobutoxypropyl (2-methyl) 2-propenamide, N-isobutoxybutyl 2-methyl) 2-propenamide, N-isobutoxyhexyl (2-methyl) 2-propenamide, N-isobutoxyoctyl (2-methyl) 2-propenamide, N- (pentoxymethyl) (2-methyl ) 2-propenamide, N-1-methyl-2-methoxyethyl (2-methyl) 2-propenamide, N- (oxetan-2-ylmethoxymethyl) (2-methyl) 2-propenamide, N- ( Oxetane-3-ylmethoxymethyl) (2-methyl) 2-propenamide, N, N-di (methoxymethyl) (2-methyl) 2-propenamide, N, N-di (ethoxymethyl) (2-methyl) ) Ethenyl monomers containing aliphatic amide groups such as 2-propenamide;
2-propenamide, 2-methylprop-2-enoylamine, N, N-dimethyl-2-propenamide, N, N-diethyl-2-propenamide, N- [3- (N ′, N′-dimethylamino) Propyl] -2-propenamide, N-isopropyl-2-propenamide, N-ethenylmethaneamide, N-ethenylacetamide, N-methoxymethyl (2-methyl) 2-propenamide, N-methoxyethyl (2 -Methyl) 2-propenamide, N-methoxypropyl (2-methyl) 2-propenamide, N-methoxybutyl (2-methyl) 2-propenamide, N-methoxyhexyl (2-methyl) 2-propenamide, N-methoxyoctyl (2-methyl) 2-propenamide, N-methoxydecyl (2-methyl) 2-propenamide, N Methoxydodecyl (2-methyl) 2-propenamide, N-methoxyoctadecyl (2-methyl) 2-propenamide, N-ethoxymethyl (2-methyl) 2-propenamide, N-ethoxyethyl (2-methyl) 2 -Propenamide, N-ethoxypropyl (2-methyl) 2-propenamide, N-ethoxybutyl (2-methyl) 2-propenamide, N-ethoxyhexyl (2-methyl) 2-propenamide, N-ethoxyoctyl (2-methyl) 2-propenamide, N-isopropoxymethyl (2-methyl) 2-propenamide, N-isopropoxyethyl (2-methyl) 2-propenamide, N-isopropoxypropyl (2-methyl) 2-propenamide, N-isopropoxybutyl (2-methyl) 2-propenamide, N-i Sopropoxyhexyl (2-methyl) 2-propenamide, N-isopropoxyoctyl (2-methyl) 2-propenamide, N-butoxymethyl (2-methyl) 2-propenamide, N-butoxyethyl (2-methyl) ) 2-propenamide, N-butoxypropyl (2-methyl) 2-propenamide, N-butoxybutyl (2-methyl) 2-propenamide, N-butoxyhexyl (2-methyl) 2-propenamide, N- Butoxyoctyl (2-methyl) 2-propenamide, N-isobutoxymethyl (2-methyl) 2-propenamide, N-isobutoxyethyl (2-methyl) 2-propenamide, N-isobutoxypropyl (2- Methyl) 2-propenamide, N-isobutoxybutyl (2-methyl) 2-propenamide, N-iso Toxihexyl (2-methyl) 2-propenamide, N-isobutoxyoctyl (2-methyl) 2-propenamide, N- (pentoxymethyl) (2-methyl) 2-propenamide, N-1-methyl-2 -Methoxyethyl (2-methyl) 2-propenamide, N- (oxetane-2-ylmethoxymethyl) (2-methyl) 2-propenamide, N- (oxetane-3-ylmethoxymethyl) (2-methyl) Contains aliphatic amide groups such as 2-propenamide, N, N-di (methoxymethyl) (2-methyl) 2-propenamide, N, N-di (ethoxymethyl) (2-methyl) 2-propenamide Ethenyl monomers;

Cyclic amide group-containing ethenyl monomers such as 4-propenoylmorpholine, N-ethenyl-2-pyrrolidone, N-ethenyl-2-azehan-2-one;
These may be used, and these may be used alone or in combination of two or more.

Examples of the monomer containing a maleimide group include maleimide derivatives such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, and cyclohexylmaleimide;
These may be used, and these may be used alone or in combination of two or more.

  The following can be illustrated as another monomer copolymerizable with the ethylenically unsaturated monomer (a) which has an active hydrogen group.

Among ethylenically unsaturated monomers, as propenoic acid derivatives or 2-methylpropenoic acid derivatives,
For example, methyl (2-methyl) propenoate [methyl propenoate and methyl 2-methylpropenoate are collectively referred to as “methyl (2-methyl) propenoate”. The same applies below. ], (2-methyl) propenoic acid ethyl, (2-methyl) propenoic acid 1-propyl, (2-methyl) propenoic acid 2-propyl, (2-methyl) propenoic acid n-butyl, (2-methyl) propene Sec-butyl acid, iso-butyl (2-methyl) propenoate, tert-butyl (2-methyl) propenoate, n-amyl (2-methyl) propenoate, iso-amyl (2-methyl) propenoate, 2-methyl) propenoic acid n-hexyl, (2-methyl) propenoic acid 2-ethylhexyl, (2-methyl) propenoic acid n-octyl, (2-methyl) propenoic acid iso-octyl, (2-methyl) propenoic acid n-nonyl, iso-nonyl (2-methyl) propenoate, decyl (2-methyl) propenoate, dodecyl (2-methyl) propenoate, (2-methyl) propyl Pensan octadecyl, (2-methyl) propenoic acid lauryl, (2-methyl) (2-methyl) such as propenoic acid stearyl propenoic acid alkyl esters;

Cyclohexyl (2-methyl) propenoate, benzyl (2-methyl) propenoate, iso-bonyl (2-methyl) propenoate, phenyl (2-methyl) propenoate, 2-phenoxyethyl (2-methyl) propenoate, (2-methyl) propenoic acid cyclic esters such as 2-oxo-1,2-phenylethyl (2-methyl) propenoate and 2-oxo-1,2-diphenylethyl (2-methyl) propenoate;

(2-methyl) propenoic acid 2-propenyl, (2-methyl) propenoic acid 1-methyl-2-propenyl, (2-methyl) propenoic acid 2-methyl-2-propenyl, (2-methyl) propenoic acid 1- Butenyl, 2-butenyl (2-methyl) propenoate, 3-butenyl (2-methyl) propenoate, 1,3-methyl-3-butenyl (2-methyl) propenoate, (2-methyl) propenoate 2- Chlor-2-propenyl, (2-methyl) propenoate 3-chloro-2-propenyl, (2-methyl) propenoate-o-2-propenylphenyl, (2-methyl) propenoate 2- (2-propenyloxy) ethyl , (2-methyl) propenoic acid 2-propenyl lactyl, (2-methyl) propenoic acid 3,7-dimethyloct-6-en-1-yl, (2-methyl) propenoic acid E) Further, such as 3,7-dimethylocta-2,6-dien-1-yl, rosinyl (2-methyl) propenoate, cinnamyl (2-methyl) propenoate, ethenyl (2-methyl) propenoate, etc. (2-methyl) propenoates containing saturated groups;

(2-methyl) propenoic acid perfluoromethyl, (2-methyl) propenoic acid perfluoroethyl, (2-methyl) propenoic acid perfluoropropyl, (2-methyl) propenoic acid perfluorobutyl, (2-methyl) propene Perfluorooctyl acid, (2-methyl) propenoic acid trifluoromethylmethyl, (2-methyl) propenoic acid 2-trifluoromethylethyl, (2-methyl) propenoic acid diperfluoromethylmethyl, (2-methyl) propene Acid 2-perfluoroethylethyl, (2-methyl) propenoic acid 2-perfluoromethyl-2-perfluoroethylmethyl, (2-methyl) propenoic acid triperfluoromethylmethyl, (2-methyl) propenoic acid 2- Perfluoroethyl-2-perfluorobutylethyl, (2-methyl) propene 2-perfluorohexyl ethyl, (2-methyl) propenoic acid 2-perfluorodecyl ethyl, (2-methyl) such as propenoic acid 2-perfluoroalkyl-hexadecyl ethyl (2-methyl) propenoic acid perfluoroalkyl esters;

(2-Methyl) propenoic acid glycidyl, (2-methyl) propenoic acid (3,4-epoxycyclohexyl) methyl, (2-methyl) propenoic acid (3-methyl-3-oxetanyl) methyl, (2-methyl) propene Oxygen-containing heterocycle-containing (2-methyl) propenoates such as tetrahydrofurfuryl acid;

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

Alkenoxide-containing (2-methyl) propenoic acid derivatives such as an oxirane adduct of (2-methyl) propenoic acid;

  Di (2-methyl) propenoic acid ethene oxide, di (2-methyl) propenoic acid triethene oxide, di (2-methyl) propenoic acid tetraethene oxide, di (2-methyl) propene Acid polyethene oxide, di (2-methyl) propenoic acid propene oxide, di (2-methyl) propenoic acid dipropene oxide, di (2-methyl) propenoic acid tripropene oxide, di (2-methyl) propenoic acid polypropene Oxide, Di (2-methyl) propenoic acid butene oxide, Di (2-methyl) propenoic acid pentenoxide, Di (2-methyl) propenoic acid 2,2-dimethylpropyl, Di (2-methyl) propenoic acid hydroxypivalyl Hydroxypivalate (commonly called manda), di (2-methyl) propenoic acid hydroxypi Ryl hydroxypivalate dicaprolactonate, 1,6-hexanediol di (2-methyl) propenoate, 1,2-hexanediol di (2-methyl) propenoate, 1,5 di (2-methyl) propenoate -Hexanediol di, di (2-methyl) propenoic acid 2,5-hexanediol, di (2-methyl) propenoic acid 1,7-heptanediol, di (2-methyl) propenoic acid 1,8-octanediol, Di (2-methyl) propenoic acid 1,2-octanediol, di (2-methyl) propenoic acid 1,9-nonanediol di, di (2-methyl) propenoic acid 1,2-decanediol, di (2- Methyl) propenoic acid 1,10-decanediol, di (2-methyl) propenoic acid 1,2-decanediol, di (2-methyl) propenoic acid 1,12-dodecanedio Di (2-methyl) propenoic acid 1,2-dodecanediol, di (2-methyl) propenoic acid 1,14-tetradecanediol, di (2-methyl) propenoic acid 1,2-tetradecanediol, di (2 -Methyl) propenoic acid 1,16-hexadecanediol, di (2-methyl) propenoic acid 1,2-hexadecanediol, di (2-methyl) propenoic acid 2-methyl-2,4-pentanediol, di (2- Methyl) propenoate 3-methyl-1,5-pentanediol, di (2-methyl) propenoate 2-methyl-2-propyl-1,3-propanediol, di (2-methyl) propenoate 2,4- Dimethyl-2,4-pentanediol, di (2-methyl) propenoic acid 2,2-diethyl-1,3-propanediol, di (2-methyl) propenoic acid 2,2,4 Trimethyl-1,3-pentanediol, dimethyloloctane di (2-methyl) propenoate, 2-ethyl-1,3-hexanediol di (2-methyl) propenoate, di (2-methyl) propenoic acid 2, 5-dimethyl-2,5-hexanediol, 2-methyl-1,8-octanediol di (2-methyl) propenoate, 2-butyl-2-ethyl-1,3-di (2-methyl) propenoate Propanediol, di (2-methyl) propenoic acid 2,4-diethyl-1,5-pentanediol, di (2-methyl) propenoic acid 1,2-hexanediol, di (2-methyl) propenoic acid 1,5 -Hexanediol, di (2-methyl) propenoic acid 2,5-hexanediol, di (2-methyl) propenoic acid 1,7-heptanediol, di (2-methyl) propenoic acid 1,8-o Kutandiol, di (2-methyl) propenoic acid 1,2-octanediol, di (2-methyl) propenoic acid 1,9-nonanediol, di (2-methyl) propenoic acid 1,2-decanediol, di (2 -Methyl) propenoic acid 1,10-decanediol, di (2-methyl) propenoic acid 1,2-decanediol, di (2-methyl) propenoic acid 1,12-dodecanediol, di (2-methyl) propenoic acid 1,2-dodecanediol, di (2-methyl) propenoic acid 1,14-tetradecanediol, di (2-methyl) propenoic acid 1,2-tetradecanediol, di (2-methyl) propenoic acid 1,16-hexadecane Diol, di (2-methyl) propenoic acid 1,2-hexadecanediol, di (2-methyl) propenoic acid 2-methyl-2,4-pentane, di (2 Methyl) propenoate 3-methyl-1,5-pentanediol, di (2-methyl) propenoate 2-methyl-2-propyl-1,3-propanediol, di (2-methyl) propenoate 2,4- Dimethyl-2,4-pentanediol, 2,2-diethyl-1,3-propanediol di (2-methyl) propenoate, 2,2,4-trimethyl-1,3-di (2-methyl) propenoate Pentanediol, di (2-methyl) propenoic acid dimethyloloctane, di (2-methyl) propenoic acid 2-ethyl-1,3-hexanediol, di (2-methyl) propenoic acid 2,5-dimethyl-2, 5-hexanediol, di (2-methyl) propenoate 2-butyl-2-ethyl-1,3-propanediol, di (2-methyl) propenoate 2,4-diethyl-1,5-pentane All, di (2-methyl) propenoic acid 1,1,1-trishydroxymethylethane, di (2-methyl) propenoic acid tricyclodecane dihydroxymethyl, di (2-methyl) propenoic acid tricyclodecane dihydroxymethyl dicapro Lactonate, tetraethene oxide adduct of di (2-methyl) -2,2-bis (hydroxyphenyl) propane, tetraethene oxide addition of 2,2-bis (hydroxyphenyl) methane di (2-methyl) propenoate , Tetraethene oxide adduct of di (2-methyl) propenoic acid-4,4′-sulfonyldiphenol, tetraethene of di (2-methyl) propenoic acid-water added 2,2-bis (hydroxyphenyl) propane Oxide adduct, di (2-methyl) propenoic acid-water added 2,2-bis (hydroxyphene) 4) Tetraethene oxide adduct of methane, di (2-methyl) propenoic acid-water-added 2,2-bis (hydroxyphenyl) propane, di (2-methyl) propenoic acid-water-added 2,2-bis (hydroxy Phenyl) methane, di (2-methyl) propenoic acid-2,2-bis (hydroxyphenyl) propane tetraethylene oxide adduct-dicaprolactonate, di (2-methyl) propenoic acid-2,2-bis ( (2-methyl) propenoic acid-based bifunctional derivatives such as hydroxyphenyl) methane tetraethene oxide adduct-dicaprolactonate;

  Tri (2-methyl) propenoic acid 1,2,3-propanetriol, tri (2-methyl) propenoic acid 2-methylpentane-2,4-diol, tri (2-methyl) propene as trifunctional monomers Acid 2-methylpentane-2,4-diol tricaprolactonate, tri (2-methyl) propenoic acid 2,2-dimethylpropane-1,3-diol, tri (2-methyl) propenoic acid trimethylolhexane, tri (2-methyl) propenoic acid trimethyloloctane, tri (2-methyl) propenoic acid 2,2-bis (hydroxymethyl) 1,3-propanediol, tri (2-methyl) propenoic acid 1,1,1-tris Trifunctional (2-methyl) propene such as hydroxymethylethane, tri (2-methyl) propenoic acid 1,1,1-trishydroxymethylpropane Esters;

  Tetra (2-methyl) propenoic acid 2,2-bis (hydroxymethyl) 1,3-propanediol, tetra (2-methyl) propenoic acid 2,2-bis (hydroxymethyl) 1,3-propanediol tetracaprolactonate, tetra (2-methyl) propenoic acid di1,2,3-propanetriol, tetra (2-methyl) propenoic acid di-2-methylpentane-2,4-diol, Tetra (2-methyl) propenoic acid di-2-methylpentane-2,4-diol tetracaprolactonate, tetra (2-methyl) propenoic acid di-2,2-dimethylpropane-1,3-diol, tetra (2 -Methyl) ditrimethylolbutane propenoate, ditrimethylolhexane tetra (2-methyl) propenoate, tetra (2-methyl) propene Acid ditrimethyloloctane, tetra (2-methyl) propenoate di-2,2-bis (hydroxymethyl) 1,3-propanediol, hexa (2-methyl) propenoate di-2,2-bis (hydroxymethyl) 1, 3-propanediol, hexa (2-methyl) propenoate tri-2,2-bis (hydroxymethyl) 1,3-propanediol, hepta (2-methyl) propenoate tri-2,2-bis (hydroxymethyl) 1, 3-propanediol, tri (2-methyl) propenoate tri-2,2-bis (hydroxymethyl) 1,3-propanediol, hepta (2-methyl) propenoate di-2,2-bis (hydroxymethyl) 1, Polyfunctional (2-methyl) propenoic acid esters such as 3-propanediol polyalkene oxide;

Di (2-methyl) propenoic acid ethane 1,2-diol, di (2-methyl) propenoic acid, 2,2'-oxyethane-1-ol, di (2-methyl) propenoic acid 3,6-dioxaoctane -1,8-diol, di (2-methyl) propenoic acid 3,6,9-trioxaundecane-1,11-diol, di (2-methyl) propenoic acid 3,6,9,12-tetraoxatetradecane -1,14-diol, tri (2-methyl) propenoic acid 2-ethyl-2- (hydroxymethyl) propane-1,3-diol, tri (2-methyl) propenoic acid 2,2-bis (hydroxymethyl) Propane-1,3-diol, di (2-methyl) propenoic acid 1,1,1-trishydroxymethylethane, tri (2-methyl) propenoic acid 1,1,1-trishydroxymethylethane Emissions, such as tri (2-methyl) polyfunctional (2-methyl) propenoic acid esters such as propenoic acid 1,1,1-tris hydroxymethyl propane.

  Moreover, the following can be illustrated as ethylenically unsaturated monomers other than a propenoic acid derivative or a 2-methylpropenoic acid derivative.

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

Ethenyl phenyl pentyl ether, ethenyl phenyl hexyl ether, ethenyl phenyl heptyl ether, ethenyl phenyl octyl ether, ethenyl phenyl nonyl ether, ethenyl phenyl decyl ether, ethenyl phenyl undecyl ether, ethenyl phenyl dodecyl ether, Tenenyl phenyl tridecyl ether, ethenyl phenyl tetradecyl ether, ethenyl phenyl pentadecyl ether, ethenyl phenyl hexadecyl ether, ethenyl phenyl heptadecyl ether, ethenyl phenyl octadecyl ether, ethenyl phenyl nonadecyl ether, ethenyl phenyl Eicosyl ether, ethenyl phenyl hen eicosyl ether, ethenyl phenyl docosyl ether, ethenyl phenyl methyl group Ether, ethenyl phenyl methyl pentyl ether, ethenyl phenyl methyl hexyl ether, ethenyl phenyl methyl heptyl ether, ethenyl phenyl methyl octyl ether, ethenyl phenyl methyl nonyl ether, ethenyl phenyl methyl decyl ether, ethenyl phenyl methyl undecyl Ether, ethenyl phenylmethyl dodecyl ether, ethenyl phenyl methyl tridecyl ether, ethenyl phenyl methyl tetradecyl ether, ethenyl phenyl methyl pentadecyl ether, ethenyl phenyl methyl hexadecyl ether, ethenyl phenyl methyl heptadecyl ether, ether Tenenylphenylmethyloctadecyl ether, ethenylphenylmethylnonadecyl ether, ethenylphenylmethyleicoside Ethers, ethenylphenyl methyl hen eicosyl ether, aromatic ethenyl ether monomer having a long-chain alkyl groups such as ethenyl phenylmethyl docosyl ether;

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 Phenylmethylundecyl ether, isopropenyl phenylmethyl dodecyl ether, isopropenyl phenylmethyl tridecyl ether, isopropenyl phenylmethyl tetradecyl ether, isopropenyl phenylmethyl pentadecyl ether, isopropenyl phenylmethyl hexadecyl ether, isopropenyl phenyl methyl hepta Decyl ether, isopropyl Isopropenyl phenyl having a long-chain alkyl group such as phenyl phenyl methyl octadecyl ether, isopropenyl phenyl methyl nonadecyl ether, isopropenyl phenyl methyl eicosyl ether, isopropenyl phenyl methyl henecosyl ether, isopropenyl phenyl methyl docosyl ether System monomers;

Hexyl 4-ethenylbenzenecarboxylate, octyl 4-ethenylbenzenecarboxylate, nonyl 4-ethenylbenzenecarboxylate, decyl 4-ethenylbenzenecarboxylate, dodecyl 4-ethenylbenzenecarboxylate, 4-ethenylbenzene Tetradecyl carboxylate, hexadecyl 4-ethenylbenzenecarboxylate, octadecyl 4-ethenylbenzenecarboxylate, eicosyl 4-ethenylbenzenecarboxylate, docosyl 4-ethenylbenzenecarboxylate, hexyl 4-isopropenylbenzenecarboxylate, 4 -Octyl isopropenylbenzenecarboxylate, nonyl 4-isopropenylbenzenecarboxylate, decyl 4-isopropenylbenzenecarboxylate, dodecyl 4-isopropenylbenzenecarboxylate, 4-isopropenylbenzenecarboxyl Ethenylbenzene having a long-chain alkyl group such as tetradecyl acid, hexadecyl 4-isopropenylbenzenecarboxylate, octadecyl 4-isopropenylbenzenecarboxylate, eicosyl 4-isopropenylbenzenecarboxylate, docosyl 4-isopropenylbenzenecarboxylate Carboxylate ester or isopropenylbenzene carboxylate monomers;

Tetra (ethene oxide) ethenylphenyl ether, methyltetra (etheneoxide) ethenylphenylether, ethyltetra (etheneoxide) ethenylphenylether, propyltetra (etheneoxide) ethenylphenylether, n-butyltetra (etheneoxide) eth Tenenyl phenyl ether, n-pentyl tetra (ethene oxide) ethenyl phenyl ether, tetra (propene oxide) ethenyl phenyl ether, methyl tetra (propene oxide) ethenyl phenyl ether, ethyl tetra (propene oxide) ethenyl phenyl ether, propoxy tetra (Propene oxide) ethenyl phenyl ether, n-butyltetra (propene oxide) ethenyl phenyl ether, n-penta Citetra (propene oxide) ethenyl phenyl ether, poly (ethene oxide) ethenyl phenyl ether, methyl poly (ethene oxide) ethenyl phenyl ether, ethyl poly (ethene oxide) ethenyl phenyl ether, poly (propene oxide) ethenyl phenyl ether, Methyl poly (propene oxide) ethenyl phenyl ether, ethyl poly (propene oxide) ethenyl phenyl ether, poly (ethene oxide) ethenyl benzyl ether, methyl poly (ethene oxide) ethenyl benzyl ether, ethyl poly (ethene oxide) ethenyl benzyl ether, Poly (propene oxide) ethenyl benzyl ether, methyl poly (propene oxide) ethenyl benzyl ether, ethyl Li (propene oxide) ethenyl benzyl ether, poly (ethene oxide) ethenyl phenyl ethyl ether, methyl poly (ethene oxide) ethenyl phenyl ethyl ether, ethyl poly (ethene oxide) ethenyl phenyl ethyl ether, poly (oxypropylene) vinyl phenyl An ethenylbenzene monomer having a long-chain polyalkene oxide moiety such as ethyl ether, methyl poly (propene oxide) ethenylphenyl ethyl ether, ethyl poly (propene oxide) ethenylphenyl ethyl ether;

Poly (ethene oxide) isopropenyl phenyl ether, methyl poly (ethene oxide) isopropenyl phenyl ether, ethyl poly (ethene oxide) isopropenyl phenyl ether, poly (propene oxide) isopropenyl phenyl ether, methyl poly (propene oxide) isopropenyl phenyl ether, Ethyl poly (propene oxide) isopropenyl phenyl ether, poly (ethene oxide) isopropenyl benzyl ether, methyl poly (ethene oxide) isopropenyl benzyl ether, ethyl poly (ethene oxide) isopropenyl benzyl ether, poly (propene oxide) isopropenyl benzyl ether, Methyl poly (propene oxide) isopropenyl benzyl ether Isopropenyl monomer having any polyalkene oxide moiety;

Mono long chain alkyl ester series of dicarboxylic acids such as ethenylphenylnonyl butanedioate, ethenylphenylmethyldecyl hexahydrobenzene-1,2-dicarboxylate, ethenylphenylethyldodecyl benzene-1,4-dicarboxylate body;

Butanedioic acid ethenyl phenyl poly (ethene oxide), hexahydrobenzene-1,2-dicarboxylic acid ethenyl phenyl methyl poly (ethene oxide), benzene-1,4-dicarboxylic acid ethenyl phenyl ethyl poly (ethene oxide), etc. Mono-alkene oxide esters of dicarboxylic acids, methyl 4-ethenylbenzenecarboxylate poly (ethene oxide), ethyl 4-ethenylbenzenecarboxylate poly (ethene oxide), methyl 4-isopropenylbenzenecarboxylate poly (propene oxide), 4- Ethenyl benzene carboxylic acid ester-based monomer or isopropenyl benzene carboxylic acid ester-based monomer having a polyalkene oxide moiety such as ethyl isopropenyl benzene carboxylate poly (propene oxide)

Fluorine-containing ethenyl monomers such as perfluoroethene, perfluoropropene, perfluoro (propyl ethenyl ether), etenylidene fluoride;

Trialkyloxysilyl group-containing ethenyl monomers such as ethenyltrimethoxysilane and ethenyltriethoxysilane;

cis-butenedioic acid di-2-propenyl, 2-methylidenebutanedioic acid diallyl, (E) -but-2-enoic acid ethenyl, (Z) -octadec-9-enoic acid ethenyl, (9Z, 12Z, 15Z) -octadeca Ethenyl ester-based monomers further containing an unsaturated bond such as -9,12,15-trienoic acid ethenyl;

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

Nitrogen atom-containing heterocycles such as 2-ethenylpyridine, 4-ethenylpyridine, 2-ethenylpiperazine, N-ethenylimidazole, 4-ethenylpiperazine, 2,4-diamino-6-ethenyl-s-triazine Ethenyl monomer;

Ethenyl esters such as ethenyl ethanoate, ethenyl propanoate, ethenyl pivalate, ethenyl benzenecarboxylate, ethenyl 3-phenyl-2-propenoate;

For example, ammonium ethenylbenzenesulfonate, monomethylammonium ethenylbenzenesulfonate, dimethylammonium ethenylbenzenesulfonate, trimethylammonium ethenylbenzenesulfonate, tetramethylammonium ethenylbenzenesulfonate, ethylammonium ethenylbenzenesulfonate Diethylammonium ethenylbenzenesulfonate, triethylammonium ethenylbenzenesulfonate, tetraethylammonium ethenylbenzenesulfonate, propylammonium ethenylbenzenesulfonate, dipropylammonium ethenylbenzenesulfonate, tripropylammonium ethenylbenzenesulfonate , Butylammonium ethenylbenzenesulfonate, Ammonium salts of chill ammonium or ethenyl alkenyl group containing ethenylbenzene sulfonic acids such as benzenesulfonic acid hexyl ammonium;
Ethenyl benzene sulfones containing alkenyl groups such as sodium ethenyl benzene sulfonate, potassium ethenyl benzene sulfonate, lithium ethenyl benzene sulfonate, magnesium ethenyl benzene sulfonate, zinc ethenyl benzene sulfonate and iron ethenyl benzene sulfonate Metal salts of acids;
Metal salts and ammonium salts such as ammonium ethenyl sulfonate, sodium ethenyl sulfonate, potassium ethenyl sulfonate, sodium ethenyl alkyl sulfosuccinate;
Metal salts and ammonium salts of alkenyl group-containing ethenyloxybenzene sulfonates such as ammonium ethenyloxybenzene sulfonate, sodium ethenyloxybenzene sulfonate, and potassium ethenyloxybenzene sulfonate;
Metal salts of 2-methyl-2-propenyl sulfonic acid containing alkenyl groups such as ammonium 2-methyl-2-propenyl sulfonate, sodium 2-methyl-2-propenyl sulfonate, potassium 2-methyl-2-propenyl sulfonate, etc. Ammonium salts;
Alkenyl group-containing 2-methyl-2-propenyl such as ammonium 2-methyl-2-propenyloxybenzenesulfonate, sodium 2-methyl-2-propenyloxybenzenesulfonate, potassium 2-methyl-2-propenyloxybenzenesulfonate Metal salts and ammonium salts of oxybenzenesulfonic acid;
Moreover, (2-methyl) propenoyloxydimethylethylammonium ethyl sulfate, (2-methyl) propenoylaminopropyltrimethylammonium sulfate, (2-methyl) propenoylaminopropyltriethylammonium sulfate-containing (2- Methyl) metal salts and ammonium salts of propenoic acid alkyl esters;
(2-methyl) propenoic acid sulfobenzyl, (2-methyl) propenoyloxyethyldimethylbenzylammonium-p-toluenesulfonate, (2-methyl) propenoyloxyethyltrimethylammonium-p-toluenesulfonate, (2-methyl) Metal salts and ammonium salts of (2-methyl) propenoic acid cyclic esters containing a sulfonyl group such as propenoylaminopropyltrimethylammonium-p-toluenesulfonate;

Glycidyl group-containing ethenyl esters such as glycidyl cinnamate, 2-propenyl glycidyl ether, ethenylcyclohexene monooxirane, 1,3-butadiene monooxirane;

Ethenyl esters such as chloroethene, 1,1-dichloroethene, 2-propenyl chloride, 2-propenyl alcohol;

Ethene, propene, 1-butene, 2-butene, 2-methylpropene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 1 -Docosene, 1-tetracocene, 1-hexacosene, 1-octacosene, 1-triacontene, 1-dotriacontene, 1-tetratoacontene, 1-hexatriacontene, 1-octatriacontene, 1-tetracontene etc. Alkenes such as the mixture and polybutene-1, polypentene-1, poly-4-methylpentene-1;

  Examples include dienes such as allene, 1,2-butadiene, 1,3-butadiene, 2-methyl-1,3-butadiene, and 2-chloro-1,3-butadiene.

  Further, for example, the above-mentioned monomer copolymer, a high molecular weight type polymerizable copolymer having an ethylenically unsaturated double bond at the copolymer terminal, a so-called macromonomer is also included.

  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 alkylethenylbenzene and a long-chain alcohol, poly ( Ethene oxide) and / or a copolymerizable ethylenically unsaturated monomer obtained by reacting at least one alcoholic hydroxyl group-containing compound selected from poly (ethene oxide) monoalkyl ethers is also the above-mentioned ethylene. Although it is contained in the unsaturated monomer, it is not particularly limited thereto. These may use only 1 type or may use multiple types together.

Next, the manufacturing method of the resin composition for pressure sensitive adhesives is demonstrated.
In the present invention, the resin composition for pressure-sensitive adhesives can be produced by the following two-stage process.
Step 1 of copolymerizing monomers to obtain resin (A), and
Production of a two-step process of Step 2 in which an active hydrogen group in the resin (A) and a compound (B) are reacted to form a urethane bond or a urea bond to obtain a resin composition for a pressure-sensitive adhesive. A process is mentioned.

The resin (A) in the present invention is a bulk polymerization, a solution polymerization, an emulsion polymerization, using 0.001 to 5 parts by weight of a polymerization initiator with respect to a total of 100 parts by weight of various monomers as described above. It is synthesized by a method such as suspension polymerization. Preferably, it is synthesized by solution polymerization.

  Examples of the polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane 1-carbonitrile) and 2 , 2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile) and dimethyl 2,2'-azobis (2-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, chain transfer agents such as α-methylethenylbenzene dimer and limonene may be used.

In the present invention, the functional group (b) of the compound (B) having the functional group (b) capable of reacting with an active hydrogen group to form a urethane bond or a urea bond is preferably an isocyanate group.
This isocyanate group is preferably a monofunctional group.

  Examples of the compound (B) include methyl isocyanate, ethyl isocyanate, propyl isocyanate, butyl isocyanate, octyl isocyanate, decyl isocyanate, octadecyl isocyanate, stearoyl isocyanate, cyclohexyl isocyanate, phenyl isocyanate, benzyl isocyanate, p-chlorophenyl isocyanate, and p-nitro. Phenyl isocyanate, 2-chloroethyl isocyanate, 2,4-dichlorophenyl isocyanate, 3-chloro-4-methylphenyl isocyanate, trichloroacetyl isocyanate, chlorosulfonyl isocyanate, (R)-(+)-α-methylbenzyl isocyanate, (S )-(−)-Α-methylbenzyl isocyanate, (R)-(−) — Examples thereof include 1- (1-naphthyl) ethyl isocyanate, (R)-(+)-1-phenylethyl isocyanate, (S)-(−)-1-phenylethyl isocyanate, p-toluenesulfonyl isocyanate, and the like.

In the present invention, the active hydrogen group of the resin (A) is preferably at least a hydroxyl group or an amino group in consideration of the reactivity with the compound (B). The amine value of the resin (A) is preferably from 0.1 to 100 mgKOH / g, more preferably from 0.5 to 50 mgKOH / g.
On the other hand, the hydroxyl value of the resin (A) is preferably from 0.1 to 100 mgKOH / g, more preferably from 0.5 to 50 mgKOH / g.

  If the amine value or hydroxyl value is lower than 0.1 mgKOH / g, the reactivity of the compound (B) with respect to the amino group or hydroxyl group is inferior, and the amount of urethane bonds or urea bonds pendant of the pressure-sensitive adhesive is reduced, resulting in heat resistance. May be reduced. On the other hand, when the amine value or the hydroxyl value is higher than 100 mgKOH / g, the reaction amount of the compound (B) increases and the pressure-sensitive adhesive layer becomes hard, which may cause a decrease in adhesive strength.

  In the present invention, a catalyst may be appropriately used in the reaction for forming a urethane bond or a urea bond. Catalysts include ammonia, amines, quaternary ammonium salts, quaternary phosphonium salts, alkali metal hydroxides, alkaline earth metal hydroxides, Lewis acids, tin, lead, titanium, iron, zinc, zirconium, Examples thereof include externally added catalysts such as organometallic compounds containing cobalt or the like, metal halides and the like.

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

  Examples of the quaternary ammonium salts include tetramethylammonium bromide, tetramethylammonium chloride, tetramethylammonium fluoride trihydrate, tetramethylammonium hexafluorophosphate, tetramethylammonium hydrogen phthalate, tetramethylammonium hydroxide pentahydrate. , Tetramethylammonium hydroxide, tetramethylammonium iodide, tetramethylammonium nitrate, tetramethylammonium perchlorate, tetramethylammonium tetrafluoroborate, tetramethylammonium tribromide, phenyltrimethylammonium bromide, tetraethylammonium bromide, tetraethylammonium chloride Tetraethylammonium fluoride trihydrate, tetraethylammonium hydroxide, tetraethylammonium iodide, tetraethylammonium perchlorate, tetraethylammonium tetrafluoroborate, tetraethylammonium-p-toluenesulfonate, tetrapropylammonium bromide, tetrapropylammonium chloride, 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 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 ethanoate, zirconium benzenecarboxylate, zirconium naphthenate, and the like.

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

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

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

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

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

  Further, the catalyst can be used as an internal addition catalyst by copolymerizing an ethylenically unsaturated monomer having a carboxyl group or an amide group as described above.

  The pressure sensitive adhesive of this invention is comprised by including the reactive compound (C) which can react with the above-mentioned resin composition for pressure sensitive adhesives and this resin composition.

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

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

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

  Examples of the aromatic polyisocyanate include 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6 -Tolylene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4 ', Examples thereof include 4 "-triphenylmethane triisocyanate.

  Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (also known as HMDI), pentamethylene diisocyanate, 1,2-propene diisocyanate, 2,3-butene diisocyanate, and 1,3-butene diisocyanate. , Dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate and the like.

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

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

  Further, 2-methyl-2- (hydroxymethyl) propane-1,3-diol adduct of the above polyisocyanate, trimer having an isocyanurate ring, and the like can also be used. 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.

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

  When a polyisocyanate compound is used as the reactive compound (C), a known catalyst can be used as necessary to accelerate the reaction. For example, a tertiary amine compound, an organometallic compound, and the like can be mentioned, and a single compound or a plurality of compounds can be used.

  Examples of the tertiary amine compound include triethylamine, triethenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, diazabicycloundecene (also known as DBU) and the like. 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.
Non-tin compounds include titanium compounds such as dibutyltitanium dichloride, tetrabutyltitanate, butoxytitanium trichloride, lead (Z) -octadeca-9-enoate, lead 2-ethylhexanoate, lead benzenecarboxylate, naphthenic acid Lead such as lead, iron such as iron 2-ethylhexanoate and iron acetylacetonate, cobalt such as cobalt benzenecarboxylate and cobalt 2-ethylhexate, zinc such as zinc naphthenate and zinc 2-ethylhexanoate System, zirconium naphthenate and the like.
Among the above catalysts, dibutyltin dilaurate (also known as DBTDL), tin 2-ethylhexanoate and the like are preferable in terms of reactivity and hygiene.

  Among reactive compounds (C), examples of oxirane compounds include 2,2-bis (hydroxyphenyl) propane, 2-chloromethyloxirane type oxirane resins and 2,2-bis (hydroxyphenyl) methane type, 2,2-bis (4-hydroxyphenyl) ethane type, 2,2-bis (4-hydroxyphenyl) butane type, 4,4′-sulfonyldiphenol type, 1,1-dichloro-2,2-bis ( 4-hydroxyphenyl) ethene 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, -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 These copolymerized oxirane resins, phenol novolac type, orthocresol novolak type, para tertiary butylphenol novolak type, paraoctylphenol novolak type, nonylphenol novolak type and their co-condensation type oxirane resins, ethene oxide diglycidyl ether, Polyethene oxide diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol diglycidyl ether, 2-methylpentane-2,4-diol triglycidyl ether Ter, diglycidylphenylamine, N, N, N ', N'-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N'-diglycidylaminomethyl) cyclohexane and the like.

Of the reactive compounds (C), examples of amine compounds are preferably polyamines having two or more primary amino groups, and primary amino groups not directly bonded to an aromatic ring from the viewpoint of excellent reaction rate. An aliphatic polyamine (which may contain an aromatic ring in its skeleton), which is a polyamine having two or more of them, is preferred.
Aliphatic polyamines include 2,5-dimethyl-2,5-hexamethylenediamine, mensendiamine, 1,4-bis (2-amino-2-methylpropyl) piperazine, and propylene branched carbon at both ends of the molecule. Polypropene oxide (propene oxide diamine, propene skeleton triamine, etc.), ethenediamine, propenediamine, butenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethenehexamine, hexamethylenediamine Methylene group on amine nitrogen such as trimethylhexamethylenediamine, N-aminoethylpiperazine, 1,2-diaminopropane, iminobispropylamine, methyliminobispropylamine, ethene oxide skeleton diamine, etc. Bonded polyether skeleton diamine, 1,5-diamino-2-methylpentane, metaxylylenediamine (also known as MXDA), polyamidoamine, isophoronediamine, 1,3-bisaminomethylcyclohexane, 1-cyclohexylamino-3 -Aminopropane, 3-aminomethyl-3,3,5-trimethyl-cyclohexylamine, dimethyleneamine having a norbornane skeleton, and the like.
Among these, since the reaction rate is particularly high, 1,3-bisaminomethylcyclohexane, dimethyleneamine having a norbornane skeleton, metaxylylenediamine, H ₂ N (CH ₂ CH ₂ O) ₂ (CH ₂ ) ₂ NH ₂ (Ethene oxide skeleton diamine), propene oxide skeleton diamine, propene oxide skeleton triamine, and polyamidoamine are useful.

  In addition, ketimine which is a reaction product of these polyamines and ketones is also included in the amine compound. From the viewpoint of stability, adjustment of reactivity and overcoatability, 1-phenylethanone or 1-phenylethane-1-one Obtained from 1,3-bisaminomethylcyclohexane; 1-phenylethanone or 1-phenylethan-1-one and norbornane skeleton dimethyleneamine (NBDA); 1-phenylethanone or Obtained from 1-phenylethane-1-one and metaxylylenediamine; 1-phenylethanone or 1-phenylethane-1-one and Jeffamine EDR148, which is a diamine of an ethene oxide skeleton or a propene oxide skeleton, Jeffermin D230, Jeffermin D400, etc. Those obtained from JEFFAMINE T403 such that the triamine of pen oxide skeleton and the like can also be used.

  Among the reactive compounds (C), examples of the aziridine compound include N, N′-diphenylmethane-4,4′-bis (1-aziridinecarboxite), N, N′-toluene-2,4-bis ( 1-aziridinecarboxite), bisisophthaloyl-1- (2-methylaziridine), tri-1-aziridinylphosphine oxide, N, N′-hexamethylene-1,6-bis (1-aziridinecarboxite) ), 2-methylpentane-2,4-diol-tri-β-aziridinylpropionate, tetramethylolmethane-tri-β-aziridinylpropionate, tris-2,4,6- (1- Aziridinyl) -1,3,5-triazine, 2-methylpentane-2,4-diol tris [3- (1-aziridinyl) propionate], 2-methylpen Tan-2,4-diol tris [3- (1-aziridinyl) butyrate], 2-methylpentane-2,4-diol tris [3- (1- (2-methyl) aziridinyl) propionate], 2-methylpentane -2,4-diol tris [3- (1-aziridinyl) -2-methylpropionate], 2,2'-bishydroxymethylbutanol tris [3- (1-aziridinyl) propionate], pentaerythritol tetra [3 -(1-aziridinyl) propionate], diphenylmethane-4,4-bis-N, N'-ethyleneurea, 1,6-hexamethylenebis-N, N'-ethyleneurea, 2,4,6- (triethylene Imino) -Syn-triazine, bis [1- (2-ethyl) aziridinyl] benzene-1,3-carboxylic acid amide, etc. And the like.

  Of the reactive compounds (C), as the carbodiimide compound, a compound having two or more carbodiimide groups (—N═C═N—) in the molecule is preferably used, and a known polycarbodiimide can be used.

Moreover, as a carbodiimide compound, the high molecular weight polycarbodiimide produced | generated by carrying out the decarboxylation condensation reaction of diisocyanate in presence of a carbodiimidization catalyst can also be used.
Examples of such compounds include those obtained by subjecting the following diisocyanates to a decarboxylation condensation reaction.
As the diisocyanate, 4,4′-diphenylmethane diisocyanate, 3,3′-dimethoxy-4,4′-diphenylmethane diisocyanate, 3,3′-dimethyl-4,4′-diphenylmethane diisocyanate, 4,4′-diphenyl ether diisocyanate, 3,3′-dimethyl-4,4′-diphenyl ether diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1-methoxyphenyl-2,4-diisocyanate, isophorone diisocyanate, 4,4′- 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.

  Among the reactive compounds (C), as the oxazoline compound, a compound having two or more oxazoline groups in the molecule is preferably used. Specifically, 2′-methylenebis (2-oxazoline), 2,2′- Ethene bis (2-oxazoline), 2,2'-ethene bis (4-methyl-2-oxazoline), 2,2'-propene bis (2-oxazoline), 2,2'-tetramethylene bis (2-oxazoline), 2 , 2'-hexamethylenebis (2-oxazoline), 2,2'-octamethylenebis (2-oxazoline), 2,2'-p-phenylenebis (2-oxazoline), 2,2'-p-phenylene Bis (4,4'-dimethyl-2-oxazoline), 2,2'-p-phenylenebis (4-methyl-2-oxazoline), 2,2'-p-phenylene (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 2,2'-bis (4-ethyl-2-oxazoline), 2,2'-bis (4-phenyl-2-oxazoline) and the like. Alternatively, ethenyl monomers such as 2-isopropenyl-2-oxazoline and 2-isopropenyl-4,4-dimethyl-2-oxazoline, and other monomers that can be copolymerized with these ethenyl monomers. It may be a copolymer with a monomer.

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

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

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

  Moreover, it is preferable to use 0.001-50 weight part of reactive compound (C) with respect to 100 weight part of resin compositions for pressure sensitive adhesives, and it is more preferable to use 0.01-30 weight part. When the usage-amount of a reactive compound (C) exceeds 50 weight part, there exists a possibility that the adhesiveness of a pressure sensitive adhesive film may fall. On the other hand, when the amount is less than 0.001 part by weight, the cohesive force of the adhesive layer is lowered, and the heat resistance and moist heat resistance may be lowered.

  The pressure-sensitive adhesive of the present invention preferably contains an organic solvent. In addition, as long as the effect of the present invention is not impaired, tackifier resins such as tackifiers, dyes, pigments, antioxidants, UV inhibitors, silane coupling agents, plasticizers, softeners, fillers, antistatic agents And anti-aging agent etc. may be blended.

  The pressure-sensitive adhesive film of the present invention is obtained by forming an adhesive layer made of the above-mentioned pressure-sensitive adhesive on a substrate. As a method for producing a pressure-sensitive adhesive film, for example, a pressure-sensitive adhesive is applied to a release-treated surface of a release film, dried, and a substrate is attached to the substrate, or a pressure-sensitive adhesive is applied to a substrate, A method of drying and bonding the release treatment surface of the release film to the surface of the adhesive layer is mentioned.

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

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

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

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

After applying a pressure-sensitive adhesive to a release liner or optical film by an appropriate method according to a conventional method, if the pressure-sensitive adhesive contains a liquid medium such as an organic solvent or water, the liquid is heated by a method such as heating. When the medium is removed or when the pressure-sensitive adhesive does not contain a liquid medium that should be volatilized, the molten resin layer is cooled and solidified to form an adhesive layer on the release liner or optical film can do.
The thickness of the adhesive layer is preferably 0.1 μm to 200 μm, 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.

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

Moreover, the adhesive optical member by which the adhesive bond layer was provided in the at least one surface of the optical member containing the said optical film can also be obtained.
Furthermore, an optical glass laminate in which an optical member, an adhesive layer, and glass are sequentially laminated can be obtained, and this can be suitably used for manufacturing a liquid crystal cell or the like.

  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, “part” and “%” represent “part by weight” and “% by weight”, respectively.

(Synthesis Example 1)
<Production of Resin (A) (Step 1)>
A polymerization tank, a stirrer, a thermometer, a reflux condenser, a dropping device, a polymerization tank and a dropping device of a polymerization reaction apparatus equipped with a nitrogen introduction pipe, the following, an ethylenically unsaturated monomer having an active hydrogen group (a), Other ethylenically unsaturated monomers, polymerization initiators, and solvents were charged in the following ratios.

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

  After the air in the polymerization tank was replaced with nitrogen gas, the reaction was started at reflux temperature in a nitrogen atmosphere with stirring. When the polymerization conversion reached about 70%, the dropping of the mixture was started from the dropping device. After completion of the dropwise addition, the mixture was further aged with stirring for 8 hours, and then added with 167 parts of ethyl ethanoate and cooled to room temperature to obtain a resin (A) solution having a nonvolatile content of about 30%.

<Reaction of Compound (B) (Step 2)>
A polymerization reaction apparatus having a stirrer, a thermometer, a reflux condenser, a dropping apparatus, and a nitrogen introducing tube attached to the polymerization tank is prepared. Resin (A) solution, compound (B), catalyst and organic solvent are added to the polymerization tank and dropping apparatus. Were charged at the following ratios.

[Polymerization tank]
200 parts of resin (A) solution [Drip device]
Phenyl isocyanate (B) 15 parts tetrabutylammonium tetrahydroborate (catalyst) 0.1 part ethyl ethanoate 30 parts

After the air in the polymerization tank was replaced with nitrogen gas, the resin solution was stirred, and the temperature was raised to 120 ° C. over 1 hour while removing the solvent from the system. At this time, the amount of desorbed solvent was 30 parts.
Subsequently, the mixture containing the compound (B) was dropped at a constant rate over 1 hour from the dropping device. Furthermore, after reacting and aging for 12 hours with stirring, 35 parts of ethyl ethanoate was added and cooled to room temperature to complete the reaction, and the resin solution for pressure sensitive adhesive having a non-volatile content of about 30% having side chain urethane bonds. Got.

(Synthesis Example 2)
The composition of the monomer used in Step 1 of Synthesis Example 1 was changed, and charged into the polymerization tank and the dropping device at the following ratios, respectively.
[Polymerization tank]
N-butyl propenoate 24.6 parts methyl propenoate 10 parts propenoic acid 0.3 parts 2-methylpropenoic acid tetramethylpiperidinyl 15 parts 2-methylpropenoic acid 2-hydroxyethyl 0.1 parts ethyl ethanoate 30 parts 2,2'-Azobisisobutyronitrile 0.05 part [Drip device]
N-butyl propenoate 49.8 parts propenoic acid 0.2 parts ethyl ethanoate 36 parts 2,2'-azobisisobutyronitrile 0.05 part

  After the air in the polymerization tank was replaced with nitrogen gas, the mixture was heated to 90 ° C. while stirring and reacted for 8 hours to obtain a resin (A) solution having a nonvolatile content of about 30% in the same manner as in Synthesis Example 1. It was.

  Further, the compound (B) was reacted in the same manner as in Step 2 of Synthesis Example 1 to obtain a pressure-sensitive adhesive resin solution having a nonvolatile content of about 30%.

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

  After the air in the polymerization tank was replaced with nitrogen gas, the mixture was heated to 90 ° C. with stirring, and reacted for 8 hours. The resin (with a non-volatile content of about 30% was obtained in the same manner as in Step (1) of Synthesis Example 1. A) A solution was obtained.

  Further, the compound (B) was reacted in the same manner as in Step 2 of Synthesis Example 1 to obtain a pressure-sensitive adhesive resin solution having a nonvolatile content of about 30%.

(Synthesis Examples 4 to 6)
The phenyl isocyanate which is the compound (B) used in Step 2 of Synthesis Example 1 is 12 parts of cyclohexyl isocyanate (Synthesis Example 4), 8 parts of octadecyl isocyanate (Synthesis Example 5), and 8 parts of p-toluenesulfonyl isocyanate (Synthesis Example 6). Preparation was carried out in the same manner as in Step 2 of Synthesis Example 1 except that each was changed to a non-volatile content of about 30% with ethyl ethanoate to obtain a pressure-sensitive adhesive resin solution.

  The resin solutions for pressure-sensitive adhesives obtained in Synthesis Examples 1 to 6 have a solution appearance, nonvolatile content (NV), viscosity (Vis), weight average molecular weight (Mw), and glass transition temperature (Tg) as follows. evaluated. The results are shown in Table 1.

The symbols in Table 1 are as follows.
PAB: n-butyl propenoate, PAM: methyl propenoate, PAE: ethyl propenoate, PA: propenoic acid, MPAHE: 2-hydroxyethyl 2-methylpropenoate, MPAL: lauryl 2-methylpropenoate, PATMP: propenoic acid Tetramethylpiperidine, MPATA: 2,4-diamino-6-methylprop-2-enoyloxyethyl-1,3,5-triazine, EPR: etanylpyrrolidone, PhNCO: phenyl isocyanate, CHNCO: cyclohexyl isocyanate, ODNCO: octadecyl Isocyanate, PTSI: p-toluenesulfonyl isocyanate, EAc: ethyl ethanoate, AIBN: 2,2′-azobisisobutyronitrile, TBAB: tetrabutylammonium tetrahydroborate.

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

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

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

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

<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.
Apply and dry the resin solution for pressure sensitive adhesive on the peeled polyester film, scrape about 10 mg of the dried copolymer, put it in an aluminum pan as a sample, weigh it and set it in a differential scanning calorimeter, The aluminum pan of the same type without a sample was used as a reference, heated at a temperature of 100 ° C. for 5 minutes, and then rapidly cooled to −120 ° C. using liquid nitrogen. Thereafter, the temperature was increased at 10 ° C./min, and the glass transition temperature (Tg) (° C.) was determined from the DSC chart obtained during the temperature increase.

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

(Comparative Example 1)
Instead of the pressure-sensitive adhesive resin solution obtained in Step 2 of Synthesis Example 1 in the same manner as in Example 1, except that the resin (A) solution obtained in Step 1 of Synthesis Example 1 was used, An optical pressure-sensitive adhesive film was prepared. At this time, a marked increase in viscosity of the pressure-sensitive adhesive was observed, and a slight roughness was confirmed on the coated surface.

(Examples 2 and 3)
Example 1 except that the pressure-sensitive adhesive resin solution obtained in Step 2 of Synthesis Example 2 and 3 was used instead of the pressure-sensitive adhesive resin solution obtained in Step 2 of Synthesis Example 1, respectively. In the same manner as above, an optical pressure-sensitive adhesive film was produced.

(Comparative Examples 2 and 3)
Instead of the pressure-sensitive adhesive resin solution obtained in Synthesis Example 1, the resin (A) solution obtained in Step 1 of Synthesis Examples 2 and 3 was used, respectively, in the same manner as in Example 1. An optical pressure-sensitive adhesive film was prepared. At this time, a marked increase in viscosity was observed in both cases, and a slight roughness was confirmed on the coated surface.

(Examples 4 to 6)
Instead of the pressure-sensitive adhesive resin solution obtained in Step 2 of Synthesis Example 1, the pressure-sensitive adhesive resin solution obtained in Synthesis Examples 4 to 6 was used in the same manner as in Example 1. An optical pressure-sensitive adhesive film was prepared.

(Examples 7 to 10)
In Example 7, instead of 10 parts of TDI / MHPD as the reactive compound (C), the resin solution for pressure-sensitive adhesive used in Step 2 of Synthesis Example 1 was replaced with HBAP (2,2′-bishydroxymethylbutanol tris [ 3- (1-aziridinyl) propionate]) 0.1 part, in Example 8 TGMXDA (N, N, N ′, N′-tetraglycidyl-m-xylylenediamine) 5 parts, in Example 9 V-05 (Carbodilite V-05 which is a carbodiimide compound: manufactured by Nisshinbo Co., Ltd.) In Example 10, Example 1 except that 1 part of Al chelate (aluminum tris (acetylacetonate)) was added. In the same manner as above, an optical pressure-sensitive adhesive film was produced. In Example 10, the solvent was changed from ethyl ethanoate (EAc) to isopropyl alcohol (IPA).

(Examples 11 and 12)
In Example 11, instead of TDI / MHPD, the resin solution for pressure-sensitive adhesive obtained in Synthesis Example 1 was replaced with XDI / EHPD (2-methyl-2 of xylylene diisocyanate) as a reactive compound (C). -(Hydroxymethyl) propane-1,3-diol adduct) was added in part 1. In Example 12, 1 part of HMDI / burette (hexamethylene diisocyanate burette adduct) was added, and the dilution solvent was changed to IPA. Except for this, an optical pressure-sensitive adhesive film was produced in the same manner as in Example 1.

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

<Evaluation method of pot life>
About the obtained pressure-sensitive adhesive, the viscosity at 25 ° C. was measured every 12 hours until 10 hours later using a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd.) under the conditions of 12 rpm and 1 minute rotation. (Pot life) was evaluated in three stages.
○: “Viscosity increase rate up to 8 hours is less than 2 times. Very good.”
Δ: “Viscosity increase rate up to 5 hours is less than 2 times, but viscosity increase rate up to 8 hours is 2 times or more. Good.”
X: “Gelation in less than 5 hours.

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

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

<Evaluation method of removability (reworkability)>
The obtained pressure-sensitive adhesive film for optical use is cut into a size of 25 mm × 150 mm, the release film is peeled off, and is attached to a float glass plate with a thickness of 1.1 mm using a laminator, and the condition is 5 ° C. at 50 ° C. It was held in an autoclave for 20 minutes to obtain a laminate of an optical pressure-sensitive adhesive film and a glass plate. The laminate was allowed to stand at 23 ° C. and 50% relative humidity 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 cloudiness and good appearance. No problem”
Δ: “Slight cloudiness is observed, but there is no practical problem”
X: “Transfer of the adhesive layer is recognized over the entire surface, which is not practical”.

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

From the results of Table 2, Comparative Examples 1 to 3 have poor pot life and coatability, and when left under severe high temperature or high temperature and high humidity for a long period of time, foaming, floating and the like occur. And it turns out that it is inferior to durability.
On the other hand, the pressure-sensitive adhesive and the optical pressure-sensitive adhesive film using the pressure-sensitive adhesive resin composition of the present invention have coating processability, heat resistance, moist heat resistance, optical characteristics, and optical film rework. It turns out that it is excellent in property.

  The pressure-sensitive adhesive resin composition of the present invention is suitable for use as an optical member, and in addition to general labels and seals, paints, elastic wall materials, waterproof coating materials, floor materials, tackifiers, adhesives Adhesives for laminated structures, sealing agents, molding materials, coating agents for surface modification, binders (magnetic recording media, ink binders, casting binders, fired brick binders, graft materials, microcapsules, glass fiber sizing, etc.), Urethane foam (hard, semi-rigid, soft), urethane RIM, UV / EB curable resin, high solid paint, thermosetting elastomer, microcellular, fiber processing agent, plasticizer, sound absorbing material, vibration damping material, surfactant, Gel coating agent, resin for artificial marble, impact resistance agent for artificial marble, resin for ink, film (laminate adhesive, protective agent) Film), laminated glass resin, reactive diluent, various molding materials, elastic fiber, artificial leather, as a raw material for synthetic leather, can also very effectively used as various resin additives and a raw material thereof or the like.

Claims (9)

  The active hydrogen group of the resin (A) having an active hydrogen group is modified with a compound (B) having a functional group (b) capable of forming a urethane bond or a urea bond by reacting with the active hydrogen group. And a pressure-sensitive adhesive resin composition.   The resin (A) having an active hydrogen group is a resin obtained by polymerizing a monomer component essentially comprising an ethylenically unsaturated monomer (a) having an active hydrogen group. 1. The pressure-sensitive adhesive resin composition according to 1.   The resin composition for pressure-sensitive adhesives according to claim 1 or 2, wherein the active hydrogen group of the resin (A) having an active hydrogen group is a hydroxyl group or an amino group.   The resin group for pressure-sensitive adhesives according to any one of claims 1 to 3, wherein the functional group (b) is an isocyanate group.   A pressure-sensitive adhesive comprising the pressure-sensitive adhesive resin composition according to claim 1 and a reactive compound (C) capable of reacting with the resin composition.   An optical pressure-sensitive adhesive film comprising a pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive according to claim 5 on at least one surface of a film-like substrate.   An adhesive optical member comprising a pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive according to claim 5 provided on at least one surface of the optical member.   An optical glass laminate in which an optical member, an adhesive layer made of the pressure-sensitive adhesive according to claim 5, and glass are sequentially laminated.   Modifying the active hydrogen group of the resin (A) having an active hydrogen group with a compound (B) having a functional group (b) capable of reacting with the active hydrogen group to form a urethane bond or a urea bond. A method for producing a resin composition for a pressure-sensitive adhesive.