JP2012201715A - Pressure-sensitive type adhesive resin composition, pressure-sensitive type adhesive and optical pressure-sensitive type adhesive film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new pressure-sensitive type adhesive resin composition formable of optical pressure-sensitive type adhesive films which are used for being adhered to optical members such as glass members for liquid crystal cells, are excellent in removability from the glass members for the liquid crystal cells and in adherend-staining resistance, and are excellent in durability (heat resistance, moist heat resistance) after adhered, and to provide a pressure-sensitive adhesive.SOLUTION: The pressure-sensitive type adhesive resin composition comprising a resin (A) prepared by polymerizing a monomer component consisting essentially of a hydroxy group-having ethylenic unsaturated monomer (a1) and a cyclic structure-having resin (B) is characterized in that the cyclic structure-having resin (B) has carboxy groups and does not have a hydroxy group.

Description

  The present invention relates to an optical pressure-sensitive adhesive film for adhering to an optical member such as a glass member for a liquid crystal cell, and has excellent removability and adherend contamination from the glass member for a liquid crystal cell. The present invention relates to a novel pressure-sensitive adhesive resin composition capable of forming an optical pressure-sensitive adhesive film excellent in durability (heat resistance and heat-and-moisture resistance) after wearing, and a pressure-sensitive adhesive.

  Due to dramatic advances in electronics in recent years, various flat panel displays (FPD) such as liquid crystal display (LCD), plasma display (PDP), rear projection display (RPJ), EL display, light emitting diode display, etc. It has come to be used as a display device in various fields. For example, these FPDs are not only used indoors, including personal computer displays and liquid crystal televisions, but are also used in vehicles such as car navigation displays.

For such display devices, various films such as an antireflection film for preventing reflection from an external light source and a protective film (protection film) for preventing scratches on the surface of the display device are usually used. For example, in a liquid crystal cell member constituting an LCD, a polarizing film or a retardation film is laminated.
Further, the FPD is not only used as a display device, but may be used as an input device by providing a touch panel function on the surface thereof. A protective film, an antireflection film, an ITO vapor deposition resin film, or the like is also used for the touch panel.
Such a film is attached to an adherend via a pressure-sensitive adhesive and used in a display device. Since the pressure-sensitive adhesive used in the display device is required to have excellent transparency, a pressure-sensitive adhesive mainly composed of an acrylic resin is generally used.

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

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

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

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

Further, 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.

  Further, for example, a propenoic acid resin composition obtained by copolymerizing a monomer containing an aromatic ring in order to improve heat resistance is disclosed (see Patent Document 4). It is disclosed that copolymerization is performed (see Patent Document 5), and a pressure-sensitive adhesive that does not cause appearance defects such as floating and peeling even in a high humidity and high temperature environment is disclosed by using the obtained copolymer. ing.

  However, the propenoic acid resin composition obtained by copolymerizing a monomer containing an aromatic ring or a heterocyclic ring as disclosed herein has an extremely high solution viscosity and creates a pressure-sensitive adhesive optical film. In this case, since it is difficult to create unless the non-volatile content is reduced as much as possible, there are many problems in industrially in terms of coating processability and price. Further, the obtained pressure-sensitive adhesive optical film 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, 100 ° C. However, in an environment of 85 ° C. and 90% relative humidity over time, the durability is not sufficient, and there is a problem that cracks and foaming are likely to 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 JP 2003-073646 A Japanese Patent No. 3989245 JP 2007-277510 A

  The present invention is an optical pressure-sensitive adhesive film for adhering to an optical member such as a glass member for a liquid crystal cell, and is excellent in removability from the glass member for a liquid crystal cell and adherend adherence. An object of the present invention is to provide a novel pressure-sensitive adhesive resin composition and a pressure-sensitive adhesive capable of forming an optical pressure-sensitive adhesive film having excellent durability (heat resistance and heat-and-moisture resistance).

The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems.
That is, the first invention comprises a resin (A) obtained by polymerizing a monomer component essentially comprising an ethylenically unsaturated monomer (a1) having a hydroxyl group, and a resin (B) having a cyclic structure. The resin composition for pressure-sensitive adhesives is a resin composition for pressure-sensitive adhesives, characterized in that the resin (B) having a cyclic structure has a carboxyl group and no hydroxyl group.

  The second invention is the pressure-sensitive adhesive resin composition according to the first invention, wherein the resin (B) having a cyclic structure has a weight average molecular weight of 5,000 to 100,000. About.

  The third invention is the pressure-sensitive adhesive resin according to the first or second invention, wherein the acid value of the resin (B) having a cyclic structure is 0.1 to 200 mgKOH / g. Relates to the composition.

  The fourth invention relates to the resin composition for pressure-sensitive adhesives according to any one of the first to third inventions, wherein the resin (A) does not have a carboxyl group.

  Moreover, 5th invention is resin (B) whose content of resin (A) is 50 to 99 weight% in total 100 weight% of resin (A) and resin (B) which has a cyclic structure, and (B) ) Is 1 to 50% by weight, and relates to the pressure-sensitive adhesive resin composition of any one of the first to fourth inventions.

  A sixth invention includes the pressure-sensitive adhesive resin composition of any one of the first to fifth inventions, and a reactive compound (C) capable of reacting with a hydroxyl group and a carboxyl group. And pressure sensitive adhesives.

  The seventh invention relates to the pressure-sensitive adhesive according to the sixth invention, wherein the reactive compound (C) is an isocyanate compound (c1).

  The eighth invention is characterized in that the reactive compound (C) is an ethyleneimine compound (c2), a glycidyl compound (c3), or an organometallic compound (c4). It relates to a pressure-sensitive adhesive.

  The ninth invention relates to a pressure-sensitive adhesive film in which a pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive according to any one of the sixth to eighth inventions is provided on at least one surface of a film-like substrate. .

  The tenth invention relates to an adhesive optical member in which a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive of any of the sixth to eighth inventions is provided on at least one surface of the optical member.

  Furthermore, an eleventh invention relates to an optical glass laminate in which an optical member, an adhesive layer made of the pressure-sensitive adhesive according to any of the sixth to eighth inventions, and glass are sequentially laminated.

  Furthermore, the twelfth aspect of the present invention is a monomer comprising an ethylenically unsaturated monomer (a1) having a hydroxyl group in the presence of a resin (B) having a cyclic structure and a carboxyl group and having no hydroxyl group. The present invention relates to a method for producing a pressure-sensitive adhesive resin composition, which comprises polymerizing a body component.

  By using the pressure-sensitive adhesive using the pressure-sensitive adhesive resin composition of the present invention, particularly in optical member applications that require heat resistance and heat-and-moisture resistance, the conditions are severer than conventional heat or wet heat conditions. However, it became a high-resistant pressure-sensitive adhesive film that does not cause foaming or peeling, and it became possible to provide an optical member that relieves stress concentration caused by expansion and contraction of the polarizing plate and does not cause thermal unevenness or whitening in the liquid crystal element. .

The matters necessary for carrying out the present invention are specifically described below.
The resin composition for pressure-sensitive adhesives of the present invention comprises a resin (A) obtained by polymerizing a monomer component essentially containing an ethylenically unsaturated monomer (a1) having a hydroxyl group, and a resin having a cyclic structure. And (B) a pressure-sensitive adhesive resin composition.

<Resin (A)>
The resin (A) obtained by polymerizing a monomer component essentially containing the ethylenically unsaturated monomer (a1) having a hydroxyl group used in the present invention is:
There is no particular limitation as long as it is a polymer of a compound having a radically polymerizable double bond in the molecule and is a polymer of an ethylenically unsaturated carboxylic acid ester or an alkenyl group-containing compound, but as a monomer used for polymerization It is essential to contain at least the ethylenically unsaturated monomer (a1) having a hydroxyl group.

Examples of the ethylenically unsaturated monomer (a1) having a hydroxyl group used in the present invention include a monomer containing a primary, secondary or tertiary hydroxyl group, and a reactive compound (C) described later. From the viewpoint of reactivity, an ethylenically unsaturated monomer containing a primary hydroxyl group is preferred.
As the monomer (a1), 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 (a1) having a hydroxyl group, and an ethylenically unsaturated monomer containing a primary hydroxyl group is particularly preferable.

As the other monomer copolymerizable with the monomer (a1), an ethylenically unsaturated carboxylic acid ester or an alkenyl group-containing compound can be used without particular limitation.
Examples of the ethylenically unsaturated carboxylic acid ester include 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;

  (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 2- (2-propenyloxy) ethyl, (2-methyl) propenoate 3,7-dimethylocta- Unsaturated groups such as 6-en-1-yl, (2-methyl) propenoic acid (E) -3,7-dimethylocta-2,6-dien-1-yl, ethenyl (2-methyl) propenoate Contains, no cyclic structure (2-methyl) propenoic acid esters;

  (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;

  Ether group-containing (2-methyl) propenoic esters such as 2-methoxyethyl (2-methyl) propenoate, 2-ethoxyethyl (2-methyl) propenoate, 2-phenoxyethyl (2-methyl) propenoate;

  (2-methyl) propenoic acid N-methylaminoethyl, (2-methyl) propenoic acid N-tributylaminoethyl, (2-methyl) propenoic acid N, N-dimethylaminoethyl, (2-methyl) propenoic acid N, (2-methyl) propenoic acid esters containing an amino group such as N-diethylaminoethyl and having no cyclic structure;

  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 that do not contain a hydroxyl group at the end, such as an oxirane adduct of (2-methyl) propenoic acid;

(2-methyl) propenoate sulfomethyl, (2-methyl) propenoate 2-sulfoethyl, (2-methyl) propenoate 2-sulfopropyl, (2-methyl) propenoate 3-sulfopropyl, (2-methyl) propene 2-sulfobutyl acid, 4-sulfobutyl (2-methyl) propenoate, 2-sulfobutyl (2-methyl) propenoate, 6-sulfohexyl (2-methyl) propenoate, sulfooctyl (2-methyl) propenoate, (2-methyl) propenoic acid alkyl esters containing sulfonyl groups such as 2-methyl) sulfenodecyl propenoate, sulfolauryl (2-methyl) propenoate, and sulfostearyl (2-methyl) propenoate;

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;

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 Hydroxy pivalate, Hydroxy pivalyl hydroxy di (2-methyl) propenoate Pivalate dicaprolactonate, di (2-methyl) propenoic acid 1,2-ethanediol, di (2-methyl) propenoic acid, 2,2'-oxyethane-1-ol, di (2-methyl) propenoic acid 3,6-dioxaoctane-1,8-diol, 1,6-hexanediol di (2-methyl) propenoate, 1,2-hexanediol di (2-methyl) propenoate, di (2-methyl) 1,5-hexanediol propenoate, 2,5-hexanediol di (2-methyl) propenoate, 1,7-heptanediol di (2-methyl) propenoate, 1,8 di (2-methyl) propenoate -Octanediol, di (2-methyl) propenoic acid 1,2-octanediol, di (2-methyl) propenoic acid 1,9-nonanediol di, di (2-methyl) propenoic acid 1,2- Decanediol, di (2-methyl) propenoic acid 1,10-decanediol, di (2-methyl) propenoic acid 1,2-decanediol, di (2-methyl) propenoic acid 1,12-dodecanediol, di ( 2-methyl) propenoic acid 1,2-dodecanediol, di (2-methyl) propenoic acid 1,14-tetradecanediol, di (2-methyl) propenoic acid 1,2-tetradecanediol, di (2-methyl) propene 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) propenoic acid 3-methyl-1,5-pentanediol, di (2-methyl) propenoate 2-methyl-2-propyl-1,3-propanediol, di (2-methyl) Cyl) propenoate 2,4-dimethyl-2,4-pentanediol, di (2-methyl) propenoate 2,2-diethyl-1,3-propanediol, di (2-methyl) propenoate 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, di (2-methyl) propenoate, 3-propanediol, di (2-methyl) propenoic acid 2,4-diethyl-1,5-pentanediol, di (2-methyl) propenoic acid 1,2-hexanediol, di (2-methyl) propene 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-octane Diol, 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-me L) 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) ) 3-methyl-1,5-pentanediol propenoate, 2-methyl-2-propyl-1,3-propanediol di (2-methyl) propenoate, 2,4-dimethyl di (2-methyl) propenoate -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-pentane Diol, di (2-methyl) propenoic acid dimethyloloctane, di (2-methyl) propenoic acid 2-ethyl-1,3-hexanediol, di (2-methyl) propenoic acid 2, -Dimethyl-2,5-hexanediol, 2-butyl-2-ethyl-1,3-propanediol di (2-methyl) propenoate, 2,4-diethyl-1,5 di (2-methyl) propenoate -Pentanediol, di (2-methyl) propenoic acid 3,6,9-trioxaundecane-1,11-diol, di (2-methyl) propenoic acid 3,6,9,12-tetraoxatetradecane-1, (2-methyl) propenoic acid bifunctional derivatives having no cyclic structure such as 14-diol and di (2-methyl) propenoic acid 1,1,1-trishydroxymethylethane;

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 2-ethyl-2- ( Hydroxymethyl) propane-1,3-diol, tri (2-methyl) propenoic acid 1,1,1-trishydroxymethylethane, tri (2 Methyl) propenoic acid 1,1,1-tris hydroxymethyl propane trifunctional such as (2-methyl) propenoic acid 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;

Examples of alkenyl group-containing compounds include:
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;
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- (oxetan-2-ylmethoxymethyl) (2-methyl) 2-propenamide, N, N-di (methoxymethyl) (2-methyl) 2- Aliphatic amide group-containing ethenyl monomers such as propenamide and N, N-di (ethoxymethyl) (2-methyl) 2-propenamide;

Ethenyl esters such as ethenyl ethanoate, ethenyl propanoate, ethenyl pivalate;
Metal salts and ammonium salts of alkenyl group-containing ethenyl sulfonates such as ammonium ethenyl sulfonate, sodium ethenyl sulfonate, potassium ethenyl sulfonate, alkenyl group-containing 2-propenyl sulfonate sodium, sodium ethenyl alkyl sulfosuccinate ;
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 sulfonic acids such as ethenylsulfonic acid, 2-propenylsulfonic acid, 2-methyl-2-propenylsulfonic acid;

Alkenyl such as (2-methyl) 2-propenamide sulfonic acid, tert-butyl- (2-methyl) 2-propenamide sulfonic acid, (2-methyl) 2-propenamide-2-methyl-1-propanesulfonic acid Group-containing amide sulfonic acids;

(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 Unsaturated phosphonic acids such as acid phosphooxyethene oxide (ethene oxide addition moles: 4 to 10) and (2-methyl) propenoic acid acid phosphooxypropene oxide (propene oxide addition moles: 4 to 10);

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

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.

  In addition, for example, a copolymerizable ethylenically unsaturated monomer obtained by reacting the above glycidyl group-containing ethenyl ester with a fatty acid is also included in the above-described ethylenically unsaturated monomer, In particular, it is not limited to these. These may use only 1 type or may use multiple types together.

  The pressure-sensitive adhesive of the present invention is obtained by reacting the hydroxyl group in the resin (A) and the carboxyl group in the resin (B) with the reactive compound (C) from the viewpoint of the durability of the pressure-sensitive adhesive. It is preferable that the chemical bonds to be generated have different characteristics. Therefore, it is preferable that the resin (A) does not have a carboxyl group as a functional group. Moreover, it is preferable that resin (A) does not have a cyclic structure from a viewpoint of the initial adhesiveness of a pressure sensitive adhesive. When a resin having a cyclic structure is used as the resin (A), initial adhesion may not be obtained, which is not preferable.

<Resin having a cyclic structure (B)>
The resin (B) having a cyclic structure in the present invention means an ethylenically unsaturated monomer (b1) having a heterocyclic ring, an aromatic ring or an alicyclic structure [hereinafter referred to as “ethylenically unsaturated monomer having a cyclic structure”. Also referred to as “mer (b1)”. And an ethylenically unsaturated monomer (b2) having a carboxyl group (however, an acid anhydride group also falls within the category),
Or it is resin which superpose | polymerizes the monomer component which has a heterocyclic ring, an aromatic ring, and an alicyclic structure, and has the ethylenically unsaturated monomer (b12) which has a carboxyl group.

Examples of the ethylenically unsaturated monomer (b1) having a heterocyclic ring, aromatic ring or alicyclic structure used in the present invention include:
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-o-2-propenylphenyl, (2-methyl) propenoic acid 2-propenyl lactyl, (2-methyl) propenoic acid (E) -3,7-dimethylocta-2,6- (2-methyl) propenoic acid esters having a cyclic structure such as dien-1-yl, rosinyl (2-methyl) propenoate, cinnamyl (2-methyl) propenoate, and further containing an unsaturated group;

(2-methyl) propenoic acid esters having a cyclic structure such as pentamethylpiperidinyl (2-methyl) propenoate and tetramethylpiperidinyl (2-methyl) propenoate and further containing an amino group;

(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;

(2-methyl) propenoic acid cyclic esters having a cyclic structure such as (2-methyl) propenoic acid sulfophenoxyethyl and (2-methyl) propenoic acid sulfocyclohexyl, and further containing a sulfonyl group;

  Furthermore, (2-methyl) propenoic acid sulfobenzylammonium, (2-methyl) propenoyloxyethyldimethylbenzylammonium-p-toluenesulfonate, (2-methyl) propenoyloxyethyltrimethylammonium-p-toluenesulfonate, (2 Metal salts and ammonium salts of (2-methyl) propenoic acid cyclic esters containing a sulfonyl group such as -methyl) propenoylaminopropyltrimethylammonium-p-toluenesulfonate;

Tetraethene oxide adduct of 2,2-bis (hydroxyphenyl) methane di (2-methyl) propenoate, tetraethene oxide adduct of di (2-methyl) propenoic acid-4,4′-sulfonyldiphenol, di Tetraethene oxide adduct of (2-methyl) propenoic acid-water-added 2,2-bis (hydroxyphenyl) propane, tetra (di (2-methyl) propenoic acid-water-added 2,2-bis (hydroxyphenyl) methane Ethene oxide adduct, di (2-methyl) propenoic acid-water-added 2,2-bis (hydroxyphenyl) propane, di (2-methyl) propenoic acid-water-added 2,2-bis (hydroxyphenyl) methane, di (2-Methyl) propenoic acid-2,2-bis (hydroxyphenyl) propane tetraethylene oxide adduct-dicaprolactonate , Di (2-methyl) propenoic acid-2,2-bis (hydroxyphenyl) methane tetraethene oxide adduct-dicaprolactonate and the like, bifunctional derivatives having a (2-methyl) propenoic acid-based cyclic structure ;

Ethenylbenzene, α-isopropenylbenzene, β-isopropenylbenzene, 1-methylethenylbenzene, 2-methylethenylbenzene, 3-methylethenylbenzene, 1-butylethenylbenzene, 1-chloro-4- Aromatic ethenyl monomers such as 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 type having a long chain alkyl group such as nylphenyl methyl octadecyl ether, isopropenyl phenyl methyl nonadecyl ether, isopropenyl phenyl methyl eicosyl ether, isopropenyl phenyl methyl henecosyl ether, isopropenyl phenyl methyl docosyl ether Monomer;

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 having no hydroxyl group at the terminal, 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 a polyalkene oxide moiety having no hydroxyl group to which end;

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)

Aliphatic amide group-containing ethenyl monomers having a cyclic structure such as N- (oxetane-3-ylmethoxymethyl) (2-methyl) 2-propenamide;

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

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;

Alkenyl group-containing aromatic sulfonic acids such as ethenylbenzenesulfonic acid, 2-propenyloxybenzenesulfonic acid, 2-methyl-2-propenyloxybenzenesulfonic acid;

Ammonium ethenylbenzenesulfonate, monomethylammonium ethenylbenzenesulfonate, dimethylammonium ethenylbenzenesulfonate, trimethylammonium ethenylbenzenesulfonate, tetramethylammonium ethenylbenzenesulfonate, ethylammonium ethenylbenzenesulfonate, Diethylammonium ethenylbenzenesulfonate, triethylammonium ethenylbenzenesulfonate, tetraethylammonium ethenylbenzenesulfonate, propylammonium ethenylbenzenesulfonate, dipropylammonium ethenylbenzenesulfonate, tripropylammonium ethenylbenzenesulfonate, Butenylammonium tenenylbenzenesulfonate, pentylbenzene ethenylbenzenesulfonate Ammonium salts of Moniumu or ethenyl benzenesulfonate alkenyl group-containing ethenylbenzene sulfonic acids such as 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 of alkenyl group-containing ethenyloxybenzene sulfonates such as ammonium ethenyloxybenzene sulfonate, sodium ethenyloxybenzene sulfonate, and potassium ethenyloxybenzene sulfonate;
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;

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

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

Examples include ethenyl esters having a cyclic structure such as ethenyl 3-phenyl-2-propenoate.

Also, for example, the above-mentioned halogenated alkylethenylbenzene is reacted with at least one alcoholic hydroxyl group-containing compound selected from long-chain alcohols, poly (ethene oxide), and / or poly (ethene oxide) monoalkyl ethers. The copolymerizable ethylenically unsaturated monomer and the like obtained are also included in the ethylenically unsaturated monomer (b1) having the above-described cyclic structure, but are not particularly limited thereto. These may use only 1 type or may use multiple types together.

  Furthermore, these are ethenylbenzene, α-isopropenylbenzene, β-isopropenylbenzene, 1-methylethenylbenzene, 2-methylethenylbenzene, 3-methylethene from the viewpoint of copolymerization and heat resistance described later. The above aromatic ethenyl monomers such as tenenylbenzene and 1-butylethenylbenzene are preferred.

  As the ethylenically unsaturated monomer (b2) having a carboxyl group, conventionally known ones can be used. For example, propenoic acid, 2-methylpropenoic acid, (2-methyl) propenoic acid 2-carboxyethyl, ( 2-methyl) propenoic acid 5-carboxypentyl, 2-methylidenebutanedioic acid, cis-butenedioic acid, trans-butenedioic acid, penta-2-enedioic acid, 2-methyl (E) -2-butenedioic acid, etc. Of unsaturated carboxylic acids;

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 However, it is not limited to these. These may use only 1 type or may use multiple types together.

As the ethylenically unsaturated monomer (b12) having a carboxyl group and having a cyclic structure used in the present invention, for example,
2-phenyl (2-methyl) propenoic acid, 3-phenyl-2-propenoic acid, 2-methyl-3-phenyl-2-propenoic acid, (2-methyl) propenoic acid 2-[(benzyloxy) carbonylamino] Unsaturated carboxylic acids having a cyclic structure such as ethyl;

  Examples include alkenyl group-containing carboxylic acids such as ethenylbenzene carboxylic acid and isopropenylbenzene carboxylic acid, but are not particularly limited thereto. These may use only 1 type or may use multiple types together.

  Furthermore, these are propenoic acid, 2-methylpropenoic acid, (2-methyl) propenoic acid 2-carboxyethyl, (2-methyl) from the viewpoint of copolymerization and reactivity with the reactive compound (C) described later. Unsaturation such as 5-carboxypentyl propenoate, 2-methylidenebutanedioic acid, cis-butenedioic acid, trans-butenedioic acid, penta-2-enedioic acid, 2-methyl (E) -2-butenedioic acid Carboxylic acids or unsaturated groups such as 2,5-dihydrofuran-2,5-dione, 3-methylidenetetrahydrofuran-2,5-dione, 3-methyl-2,5-dihydrofuran-2,5-dione Carboxylic anhydrides are preferred.

  Examples of other monomers copolymerizable with the monomer (b1), (b2) or (b12) include ethylenically unsaturated carboxylic acid esters and alkenyl group-containing compounds, as described above, without particular limitation. Can be used.

Moreover, it is preferable that the resin (B) in this invention is a weight average molecular weights 5,000-100,000.
When the weight average molecular weight (hereinafter abbreviated as Mw) is less than 5,000, a pressure-sensitive adhesive film containing a reactive compound (C) described below is prepared in the coexistence with the resin (A). Adhesive residue and adherend contamination may occur during rework after being attached to an adherend such as a plate. On the other hand, when Mw is greater than 100,000, whitening tends to occur due to poor compatibility with the resin (A). The weight average molecular weight (Mw) is a value in terms of polyethenylbenzene measured by gel permeation chromatograph (GPC, solvent: tetrahydrofuran).

Moreover, it is important that the resin (B) having a cyclic structure in the present invention has a carboxyl group and no hydroxyl group.
When the resin (B) has a hydroxyl group, the hydroxyl group of the resin (B) is changed due to the reaction rate difference between the hydroxyl group of the resin (A) and the hydroxyl group of the resin (B) during the crosslinking reaction with the reactive compound (C) described later. It reacts preferentially with the reactive compound (C), the reaction between the hydroxyl group of the resin (A) and the reactive compound (C) is suppressed, and the cohesive force is produced when a pressure-sensitive adhesive film is prepared by the method described later. Decreases, heat resistance and moist heat resistance decrease, which is not preferable.

  Moreover, as an effect of the carboxyl group which resin (B) has, it is as follows. That is, since the chemical bonds generated by the reaction of the hydroxyl group in the resin (A) and the carboxyl group in the resin (B) with the reactive compound (C) have different characteristics, aggregation of the formed resin layer It is effective for maintaining power.

The configuration of the resin (B) includes the following configurations (1) to (5).
(1) monomer (b1) / monomer (b2) / other monomer (2) monomer (b12) / other monomer (3) monomer (b1) / monomer (B12) / other monomer (4) monomer (b2) / monomer (b12) / other monomer (5) monomer (b1) / monomer (b2) / single amount Body (b12) / Other monomers

In the case of the constitutions (1) to (4) above, the content of the monomer (b1) and the monomer (b2) constituting the resin (B), or the content of the monomer (b12) Any of them is preferably 30 to 50% by weight in 100% by weight of the resin (B). If it is less than 30% by weight, the heat resistance and heat-and-moisture resistance may be lowered, and the reactivity with the reactive compound (C) described later may be lowered, and the cohesive force of the pressure-sensitive adhesive film may be lowered. is there. On the other hand, when the amount is more than 50% by weight, the compatibility may be poor and the pressure-sensitive adhesive film may be whitened.
In the case of the configuration (5), either the content of the monomer (b1) and the monomer (b2) constituting the resin (B) or the content of the monomer (b12) Is preferably 30 to 40% by weight in 100% by weight of the resin (B). If it is less than 30% by weight, the heat resistance and heat-and-moisture resistance may be lowered, and the reactivity with the reactive compound (C) described later may be lowered, and the cohesive force of the pressure-sensitive adhesive film may be lowered. is there. On the other hand, when the amount is more than 50% by weight, the compatibility may be poor and the pressure-sensitive adhesive film may be whitened.

As the resin (B) having a cyclic structure used in the present invention,
For example, ethenylbenzene / propenoic acid copolymer, ethenylbenzene / 2-methylpropenoic acid copolymer, ethenylbenzene / cis-butenedioic acid copolymer, ethenylbenzene / 2,5-dihydrofuran-2 , 5-dione copolymers and the like, and even if a resin in which a part of the carboxyl group is esterified or amidated with monoalcohols or monoamines can be used without problems.
Although the esterification or amidation reaction proceeds even without a catalyst, it is preferable to use a tertiary amine compound described later as a catalyst because the reaction proceeds more effectively.

The acid value of the resin (B) having a cyclic structure in the present invention is preferably 0.1 to 200 mgKOH / g. More preferably, it is 5-100 mgKOH / g.
When the acid value is less than 0.1 mgKOH / g, the reactivity with the reactive compound (C) described later may be lowered, and the pressure-sensitive adhesive film cohesive force may be lowered.
On the other hand, when the acid value exceeds 200 mgKOH / g, the compatibility with the coexisting resin (A) becomes poor, and a whitening phenomenon may occur in the adhesive film.

<Resin composition for pressure-sensitive adhesive>
In the resin composition for pressure-sensitive adhesives in the present invention, the content of the resin (A) is 50 to 99% by weight, ie, cyclic, out of a total of 100% by weight of the resin (A) and the resin (B) having a cyclic structure. The content of the resin (B) having a structure is preferably 1 to 50% by weight. More preferable ranges are 60 to 90% by weight of the resin (A) and 10 to 40% by weight of the resin (B) having a cyclic structure.
When the content of the resin (A) is less than 50% by weight, that is, when the content of the resin (B) having a cyclic structure is more than 50% by weight, the compatibility between the resin (A) and the resin (B) decreases. Therefore, when the resin composition for pressure-sensitive adhesives is whitened, the energy elasticity is increased, and the pressure-sensitive adhesive film described later becomes rigid, so that floating and foaming are likely to occur under severe heat and wet heat conditions. There is.
On the other hand, when the content of the resin (A) is more than 99% by weight, that is, when the content of the resin (B) is less than 1% by weight, the cyclic structure contained in the resin (B) decreases, Since the rubber elasticity of the pressure-sensitive adhesive optical film described later becomes high and the resin composition for pressure-sensitive adhesive becomes rigid, it suppresses the shrinkage of the polarizing film when used as an optical glass laminate for a polarizing film. As a result, the heat resistance and the heat-and-moisture resistance may be lowered.

<Method for producing resin composition for pressure-sensitive adhesive>
The pressure-sensitive adhesive resin composition of the present invention is
Preparation of resin (A) and resin (B) separately in advance, and blending each of them in the above ratios to provide an admixable pressure-sensitive adhesive resin composition (Production Method 1) Is possible.
Further, the resin (A) prepared by swelling the resin (B) prepared in advance with the monomer component essentially comprising the monomer (a1), mixing them well until becoming transparent, and then performing a polymerization reaction. It is also possible to provide a composite resin composition for pressure-sensitive adhesives (Production Method 2) containing both the resin and the resin (B). At this time, a part of the resin (A) may be grafted and bonded to the resin (B) having a cyclic structure.

Thereafter, polymerization is performed in the presence of the resin composition (B) swollen by the monomer component having the monomer (a1) as an essential component, that is, the composite resin composition for pressure-sensitive adhesive provided by the production method 2. The resin subjected to the reaction (a composite type resin composition for pressure-sensitive adhesive) is referred to as a resin (A ′).
Here, the resin (A) is a resin having a hydroxyl group. In contrast, a resin having no hydroxyl group is referred to as a resin (X).
Here, the resin (B) is a resin having a cyclic structure and a carboxyl group and having no hydroxyl group. On the other hand, the following three resins (1) to (3) are denoted as resin (Y).
(1) Resin having no cyclic structure, carboxyl group and hydroxyl group (2) Resin having a cyclic structure and not having carboxyl group and hydroxyl group (3) Having a carboxyl group, cyclic structure and hydroxyl group Here, the resin (Y) may be contained in the resin (X).

Further, a resin subjected to a polymerization reaction in the presence of a resin (Y) swollen by a monomer component essentially comprising the monomer (a1) (a composite type resin composition for pressure-sensitive adhesives) Is denoted as resin (X1).
Further, a resin (composite type pressure-sensitive adhesive resin composition) subjected to a polymerization reaction in the presence of the resin (B) swollen by the monomer component not having the monomer (a1) It describes with resin (X2).
Also, a resin (composite type pressure-sensitive adhesive resin composition) subjected to a polymerization reaction in the presence of a resin (Y) swollen by a monomer component not having the monomer (a1) It describes with resin (X3).
Resin (X ′) including resins (X1), (X2), and (X3) other than resin (A ′), which is a composite resin composition for pressure-sensitive adhesive provided by production method 2 in the present invention ).

The composite-type pressure-sensitive adhesive resin composition (Production Method 2) is an admixture-type pressure-sensitive adhesive resin composition (Production Method 1), which is a mixture of the resin (A) and the resin (B). In contrast, the film layer formed from the pressure-sensitive adhesive and the general pressure-sensitive adhesive of the present invention is more transparent because both are intricately entangled and compatible with each other at the nanoscale, and sometimes bonded. Is preferable.
Moreover, since the hydroxyl groups of the resin (A ′) are uniformly distributed throughout the pressure-sensitive adhesive resin composition on a micro scale, the feeling using a pressure-sensitive adhesive containing a reactive compound (C) described later is used. When pressure adhesive optical film is used as an optical glass laminate, such pressure sensitive adhesives do not cause contamination such as adhesive residue or cloudiness on the glass when re-attaching to glass for liquid crystal cells (rework). Even if the polarizing film attached to the glass for a liquid crystal cell is exposed to more severe heat or wet heat conditions, volume contraction of the polarizing film can be suppressed.

The resin composition for pressure-sensitive adhesives of the present invention is a mixed resin of the resin (A) and the resin (B) in the production method 1 and the composite resin (A ′) in the production method 2. It is synthesized by a method such as polymerization, solution polymerization, emulsion polymerization, suspension polymerization or the like, preferably by solution polymerization.
Examples of the polymerization initiator used in the polymerization reaction include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane 1 -Carbonitrile), 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- And azo compounds such as imidazolin-2-yl) propane].

  Benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di (2-ethoxyethyl) peroxydicarbonate, t-butylperoxy Organics such as 2-ethylhexanoate, t-butylperoxyneodecanoate, t-butylperoxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, diacetyl peroxide A peroxide is mentioned.

  In the case of (Production Method 1), the amount of the polymerization initiator used for the polymerization reaction is preferably 0.001 to 5 parts by weight with respect to 100 parts by weight of the monomer composition (Production Method 2). In this case, 0.001 to 5 parts by weight is preferable with respect to 100 parts by weight in total of the resin (B) and the monomer composition.

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

  Further, the weight average molecular weight (Mw) of the resin (A) in (Production Method 1) and the composite resin (A ′) in (Production Method 2) is preferably 100,000 to 2,000,000. In this respect, the range of 200,000 to 1,500,000 is more preferable. If Mw exceeds 2,000,000, the fluidity of the pressure-sensitive adhesive resin composition becomes poor, making it difficult to produce a pressure-sensitive adhesive film. If the Mw is less than 100,000, the pressure-sensitive adhesive layer It is not preferable because cohesive failure easily occurs.

<Reactive compound (C)>
Next, the reactive compound (C) will be described.
In this invention, a pressure sensitive adhesive can be obtained by adding the reactive compound (C) which can react with a hydroxyl group and a carboxyl group to the resin composition for pressure sensitive adhesives.
As described above, the reactive compound (C) of the present invention is used to form a crosslinkable IPN structure in addition to the crosslink structure in order to form a crosslink structure with the pressure-sensitive adhesive resin composition. Is done. Here, the crosslinkable IPN structure is a resin (A) or a crosslinked product of the resin (A ′) and the reactive compound (C) and a crosslinked product of the resin (B) and the reactive compound (C). It is a structure that forms an interpenetrated polymer network (IPN) in which molecular chains are intertwined closely. The pressure-sensitive adhesive of the present invention is characterized by having this crosslinkable IPN structure, and obtained because it has a microphase separation structure in which a relatively soft viscoelastic structure is incorporated in an elastic structure having a cyclic structure. Although the pressure sensitive adhesive has a high non-volatile content, the solution viscosity is low and the coating processability is good, and the resulting pressure sensitive adhesive film has white spots while maintaining high heat resistance and moisture and heat resistance. It is possible to have suppression and reworkability.

The reactive compound (C) of the present invention includes a compound (Cf12) ((f1) having a functional group (f1) capable of reacting with a hydroxyl group and a functional group (f2) capable of reacting with a carboxyl group in the molecule. (F2) may be the same or different, so long as they are not limited.
In addition, a compound (Cf1) having two or more functional groups (f1) capable of reacting with a hydroxyl group in the molecule and hardly reacting with a carboxyl group, and a functional group capable of reacting with a carboxyl group in the molecule It may be a mixture with a compound (Cf2) that has two or more (f2) and hardly reacts with a hydroxyl group.

For the hydroxyl group in the pressure-sensitive adhesive resin composition of the present invention, an isocyanate group, an N-hydroxymethyl group or the like is preferably used as the functional group (f1) of the reactive compound (C). For the carboxyl group in the adhesive resin composition, the functional group (f2) of the reactive compound (C) is an oxirane group, amino group, aziridyl group, oxazoline group, metal chelate group, etc. Since it reacts preferentially in terms, it is preferably used.
However, as an exception, an isocyanate group may be used as the functional group (f2), and this is due to the catalytic action of the carboxyl group, in the moisture and outside air contained in the resin composition for pressure-sensitive adhesives. This is because the condensation reaction with moisture is promoted and polyurea is produced, so that physical polymer chain entanglement is formed between the pressure-sensitive adhesive resin composition and the cohesive force is apparently improved. .

In particular, in the present invention, in order to form an effective crosslinked IPN structure,
The isocyanate compound (c1) having an isocyanate group is preferably used for the hydroxyl group in the pressure-sensitive adhesive resin composition, and the glycidyl compound (c2) having an oxirane group and an aziridyl group are used for the carboxyl group. An ethyleneimine compound (c3) having an organic metal compound (c4) having a metal chelate group is preferably used.

  Examples of the isocyanate compound (c1) of the present invention include aromatic polyisocyanates, aliphatic polyisocyanates, araliphatic polyisocyanates, and alicyclic polyisocyanates.

  Aromatic polyisocyanates include 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-triisocyanate. Range isocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4 ', 4 " -Triphenylmethane triisocyanate etc. can be mentioned.

  Aliphatic polyisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene 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, , 4-tetramethylxylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate, and the like.

  Examples of alicyclic polyisocyanates include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl- Examples include 2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4′-methylene bis (cyclohexyl isocyanate), 1,4-bis (isocyanate methyl) cyclohexane and the like.

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

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

  When the isocyanate compound (c1) is used as the reactive compound (C), a known catalyst can be used as necessary for promoting 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 tertiary amine compounds include triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, 1,8-diazabicyclo [5,4,0] -7-undecene (DBU), and the like. Depending on the case, it can be used alone or in combination.

Examples of the glycidyl compound (c2) having an oxirane group include
2,2-bis (hydroxyphenyl) propane, 2-chloromethyloxirane type oxirane resins, 2,2-bis (hydroxyphenyl) methane type, 2,2-bis (4-hydroxyphenyl) ethane type, 2-bis (4-hydroxyphenyl) butane type, 4,4′-sulfonyldiphenol type, 1,1-dichloro-2,2-bis (4-hydroxyphenyl) ethene type, 1,3-bis [2- (4-hydroxyphenyl) -2-propyl] benzene type, 2,2-bis (4-hydroxy-3-methylphenyl) propane type, 2,2-bis (4-hydroxy-3-methylphenyl) methane type, 2,2-bis (4-hydroxy-3-methylphenyl) hexafluoropropane type, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane type, 2 , 2-bis (4-hydroxycyclohexyl) propane type, 2,2-bis (2-hydroxy-5-biphenylyl) propane type and copolymerized oxirane resins, phenol novolac type, orthocresol novolak type Paratertiary butylphenol novolak type, paraoctylphenol novolak type, nonylphenol novolak type and co-condensation type oxirane resins, ethene oxide diglycidyl ether, polyethene oxide diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1 , 6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, diglycidylaniline, N, N, N ′, N′-tetraglycidyl-m-xylile Diamine, 1,3-bis (N, N'-diglycidyl aminomethyl) cyclohexane.

Examples of the ethyleneimine compound (c3) having an aziridyl group include
N, N′-diphenylmethane-4,4′-bis (1-aziridinecarboxite), N, N′-toluene-2,4-bis (1-aziridinecarboxite), bisisophthaloyl-1- (2 -Methylaziridine), tri-1-aziridinylphosphine oxide, N, N′-hexamethylene-1,6-bis (1-aziridinecarboxite), 2-methylpentane-2,4-diol-tri-β -Aziridinylpropionate, 2,2-bis (hydroxymethyl) 1,3-propanediol-tri-β-aziridinylpropionate, tris-2,4,6- (1-aziridinyl) -1 3,5-triazine, 2-methylpentane-2,4-diol tris [3- (1-aziridinyl) propionate], 2-methylpentane-2,4-diol tris [3- (1-aziridinyl) butyrate], 2-methylpentane-2,4-diol tris [3- (1- (2-methyl) aziridinyl) propionate], 2-methylpentane-2,4-diol tris [ 3- (1-aziridinyl) -2-methylpropionate], 2,2-bis (hydroxymethyl) 1,3-propanedioltetra [3- (1-aziridinyl) propionate], diphenylmethane-4,4-bis -N, N'-ethyleneurea, 1,6-hexamethylenebis-N, N'-ethyleneurea, 2,4,6- (triethyleneimino) -Syn-triazine, bis [1- (2-ethyl) Aziridinyl] benzene-1,3-carboxylic acid amide and the like.

Moreover, as an example of the organometallic compound (c4) having a metal chelate group,
Examples include compounds in which polyvalent metals such as aluminum, iron, copper, zinc, tin, titanium, titanium, nickel, antimony, magnesium, vanadium, chromium, and zirconium are coordinated to 2,4-pentanedione or ethyl acetoethanoate.

<Pressure sensitive adhesive>
The pressure-sensitive adhesive of the present invention includes a mixture of the resin (A) and the resin (B), or the reactive compound (C) added to the resin composition for pressure-sensitive adhesive containing the resin (A ′). Obtained in the state.
The pressure-sensitive adhesive of the present invention is suitable as a pressure-sensitive adhesive for optical members, and preferably contains an organic solvent. For example, adding organic solvents such as acetone, methyl ethanoate, ethyl ethanoate, cyclohexane, toluene, methyl ethyl ketone, isopropyl alcohol, other hydrocarbon solvents, and water to adjust the viscosity of the pressure sensitive adhesive. Or the pressure sensitive adhesive can be heated to reduce the viscosity. However, when adding an isocyanate compound (c1) as the reactive compound (C), the addition of water or alcohols is likely to deactivate the isocyanate group. Is required.

  In addition, a silane coupling agent, a softening agent, a dye, a pigment, an antioxidant, a tackifier, a plasticizer, a filler, an antiaging agent, and the like may be added as long as the effects of the present invention are not impaired. .

<Pressure-sensitive adhesive film>
Using the pressure-sensitive adhesive of the present invention, a laminated product composed of a pressure-sensitive adhesive layer and a film-like substrate (hereinafter referred to as “pressure-sensitive adhesive film”) can be obtained.
For example, a pressure-sensitive adhesive film can be obtained by applying a pressure-sensitive adhesive to various film-like substrates, drying and crosslinking and curing.
In coating, an appropriate liquid medium such as ethyl acetate, toluene, isopropyl alcohol, and other organic solvents and water can be added to adjust the viscosity, or the pressure sensitive adhesive can be heated. Thus, the viscosity can be lowered.

Examples of the film-like substrate include cellophane, various plastic films, rubber, cloth, rubber cloth, resin-impregnated cloth, glass plate, metal plate, wood and the like in a flat shape. Moreover, various base materials can also be used independently, and the thing in the multilayer state formed by laminating | stacking a several thing can also be used. Further, the surface can be peeled off.
Various plastic films include polyvinyl alcohol film, triacetyl cellulose film, polypropylene resin film such as polypropylene, polyethylene, polycycloolefin, ethylene-vinyl acetate copolymer, polyester resin such as polyethylene terephthalate and polybutylene terephthalate. Film, polycarbonate resin film, polynorbornene resin film, polyarylate resin film, acrylic resin film, polyphenylene sulfide resin film, polystyrene resin film, vinyl resin film, polyamide resin film And polyimide resin film, epoxy resin film, and the like.

After applying a pressure-sensitive adhesive to the film-like substrate 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 obtained by heating or the like. If the medium is removed or the pressure-sensitive adhesive does not contain a liquid medium to be volatilized, the pressure-sensitive adhesive layer in the molten state is cooled and solidified, and the pressure-sensitive adhesive is placed on the film-like substrate. An adhesive layer can be formed.
The thickness of the pressure-sensitive adhesive layer is preferably 0.1 μm to 200 μm, and more preferably 1 μm to 100 μm. If the thickness is 0.1 μm or less, sufficient adhesive strength may not be obtained, and even if the thickness exceeds 200 μm, characteristics such as adhesive strength are often not improved further.

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

<Adhesive optical member>
Next, the adhesive optical member of the present invention will be described.
The adhesive optical member of the present invention is a so-called sheet (also referred to as film as described above) optical member having various optical properties such as a polarizing film, a retardation film, an elliptically polarizing film, an antireflection film, and a brightness enhancement film. A pressure sensitive adhesive layer formed from the pressure sensitive adhesive of the present invention is laminated on at least one surface. The surface of the pressure-sensitive adhesive layer may be covered with a film-like substrate (hereinafter referred to as a release liner) that has been subjected to a release treatment.

The adhesive optical member of the present invention is, for example,
(A) A pressure-sensitive adhesive is applied to the release treated surface of the release liner, dried, and a film-like optical member is laminated on the surface of the adhesive layer.
(A) It can be obtained by directly applying a pressure-sensitive adhesive to a film-like optical member, drying it, and laminating the release treatment surface of the release liner on the surface of the adhesive layer.
The cross-linking reaction between the pressure-sensitive adhesive resin composition and the reactive compound (C) is performed when the pressure-sensitive adhesive is dried and when a film-like optical member or release liner is laminated on the pressure-sensitive adhesive layer surface. And proceed after lamination.

<Optical glass laminate>
Next, the optical glass laminate of the present invention will be described.
If necessary, remove the release liner covering the surface of the adhesive layer from the adhesive optical member of the present invention, and stick it to a film member or glass member to use as an optical laminate that can be used for optical applications. Can do.
In particular, by sticking to a glass member for a liquid crystal cell, an optical glass laminate having a configuration of film-like optical member / pressure-sensitive adhesive layer / liquid crystal cell glass member can be obtained.

  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.

<Manufacture of resin (A)>
(Synthesis Example 1)
In the reaction tank and dropping device of the polymerization reactor equipped with a reaction vessel, a stirrer, a thermometer, a reflux condenser, a dropping device, a nitrogen introducing tube, the following ethylenically unsaturated monomer (a1) having a hydroxyl group, other An ethylenically unsaturated monomer, an initiator, and an organic solvent were charged at the following ratios.

[Reaction tank]
N-butyl propenoate 40 parts 2-hydroxyethyl propenoate (a1) 1 part ethyl ethanoate (organic solvent) 50 parts 2,2′-azobisisobutyronitrile (initiator) 0.01 part [drip apparatus]
N-butyl propenoate 58 parts 2-hydroxyethyl propenoate (a1) 1 part ethyl ethanoate (organic solvent) 50 parts 2,2′-azobisisobutyronitrile (initiator) 0.01 part

  After replacing the air in the reaction tank with nitrogen gas, the temperature was raised to 80 ° C. in a nitrogen atmosphere while stirring. Next, a mixture of the ethylenically unsaturated monomer including (a1), the initiator, and the organic solvent was dropped from the dropping device over 1 hour. After completion of the dropwise addition, the reaction was continued for 6 hours with further stirring, and then 50 parts of ethyl ethanoate (hereinafter referred to as EAC) was added and cooled to room temperature to obtain a transparent solution having a concentration of about 40%.

(Synthesis Examples 2 and 3)
Synthesis Example except that the ethylenically unsaturated monomer (a1) having a hydroxyl group used in Synthesis Example 1 was changed to 4-hydroxybutyl propenoate (Synthesis Example 2) and N-hydroxyethylpropenamide (Synthesis Example 3) The reaction was carried out in the same manner as in Example 1, and the concentration was adjusted to about 40% with EAC to obtain a transparent solution.

(Synthesis Example 4)
In the reaction tank and dropping device of the polymerization reactor equipped with a reaction vessel, a stirrer, a thermometer, a reflux condenser, a dropping device, a nitrogen introducing tube, the following ethylenically unsaturated monomer (a1) having a hydroxyl group, other An ethylenically unsaturated monomer, an initiator, and an organic solvent were charged at the following ratios.

[Reaction tank]
N-butyl propenoate 30 parts benzyl 2-methylpropenoate 10 parts 2-hydroxyethyl propenoate (a1) 1 part ethyl ethanoate (organic solvent) 50 parts 2,2′-azobisisobutyronitrile (initiator) 0.01 part [Drip device]
N-butyl propenoate 58 parts 2-hydroxyethyl propenoate (a1) 1 part ethyl ethanoate (organic solvent) 50 parts 2,2′-azobisisobutyronitrile (initiator) 0.01 part

  After replacing the air in the reaction tank with nitrogen gas, the temperature was raised to 80 ° C. in a nitrogen atmosphere while stirring. Next, a mixture of the ethylenically unsaturated monomer including (a1), the initiator, and the organic solvent was dropped from the dropping device over 1 hour. After completion of the dropwise addition, the reaction was continued for 6 hours with further stirring, and then 50 parts of ethyl ethanoate was added and cooled to room temperature to obtain a transparent solution having a concentration of about 40%.

<Manufacture of resin (X)>
(Synthesis Example 5)
The reaction was conducted in the same manner as in Synthesis Example 1 except that the ethylenically unsaturated monomer (a1) having a hydroxyl group used in Synthesis Example 1 was changed to 2 parts of methyl propenoate. Adjusted to 40% to obtain a clear solution.

(Synthesis Example 6)
The reaction was conducted in the same manner as in Synthesis Example 1 except that the ethylenically unsaturated monomer (a1) having a hydroxyl group used in Synthesis Example 1 was changed to propenoic acid (b2), and the concentration was about 40 with ethyl ethanoate. % To obtain a clear solution.

<Manufacture of resin (B)>
(Synthesis Example 7)
The reaction vessel and the dropping device of the polymerization reactor equipped with a reaction vessel, a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube have the following ethylenically unsaturated monomer (b1) having a cyclic structure and a carboxyl group. The ethylenically unsaturated monomer (b2), the initiator, and the organic solvent were charged at the following ratios.

[Reaction tank]
Ethenylbenzene (b1) 65 parts (Z) -Butenedioic anhydride (b2) 35 parts Ethane ethanoate (organic solvent) 100 parts t-butylperoxy-2-ethylhexanoate (initiator) 0.1 Part

  After the air in the reaction vessel was replaced with nitrogen gas, the temperature was raised to 80 ° C. in a nitrogen atmosphere while stirring to initiate the reaction. Then, after further reacting for 8 hours with stirring, 50 parts of ethyl ethanoate was added and cooled to room temperature to obtain a light yellow transparent solution having a concentration of about 40%.

(Synthesis Examples 8 and 9)
The same procedure as in Synthesis Example 7 except that the ethylenically unsaturated monomer (b2) having a carboxyl group used in Synthesis Example 7 was changed to propenoic acid (Synthesis Example 8) and 2-methylpropenoic acid (Synthesis Example 9). The reaction was carried out and the concentration was adjusted to about 40% with ethyl ethanoate to obtain a clear solution.

(Synthesis Example 10)
The reaction vessel and the dropping device of the polymerization reactor equipped with a reaction vessel, a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube have the following ethylenically unsaturated monomer (b1) having a cyclic structure and a carboxyl group. The ethylenically unsaturated monomer (b2), the initiator, and the organic solvent were charged at the following ratios.

[Reaction tank]
2-methylpropenoic acid benzyl (b1) 40 parts n-butyl propenoate 20 parts propenoic acid (b2) 1 part methyl ethyl ketone (organic solvent) 50 parts 2,2'-azobisisobutyronitrile (initiator) 0.01 Part [Drip device]
N-butyl propenoate 38 parts propenoic acid (b2) 1 part methyl ethyl ketone (organic solvent) 50 parts 2,2'-azobisisobutyronitrile (initiator) 0.01 part

  After replacing the air in the reaction tank with nitrogen gas, the temperature was raised to 80 ° C. in a nitrogen atmosphere with stirring, and the reaction was performed for 8 hours. After completion of the reaction, methyl ethyl ketone (hereinafter referred to as MEK): 50 parts In addition, the mixture was cooled to room temperature to obtain a transparent solution having a concentration of about 40%.

(Synthesis Examples 11-13)
The ethylenically unsaturated monomer (b1) having a cyclic structure used in Synthesis Example 10 was converted to phenoxyethyl propenoate (Synthesis Example 11), cyclohexyl propenoate (Synthesis Example 12), N-ethenyl-2-pyrrolidone (Synthesis Example) The reaction was carried out in the same manner as in Synthesis Example 9 except that it was changed to 13), and the concentration was adjusted to about 40% with MEK to obtain a transparent solution.

(Synthesis Example 14)
Resin (B) having a cyclic structure obtained in Synthesis Example 7, monoalcohol, organic solvent in a reaction tank and a dropping apparatus of a polymerization reaction apparatus equipped with a reaction tank, a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction pipe And the catalyst were charged at the following ratios.

[Reaction tank]
Resin (B) solution obtained in Synthesis Example 7 100 parts dodecyl alcohol (monoalcohol) 26 parts ethyl ethanoate (organic solvent) 6 parts 1,8-diazabicyclo [5,4,0] -7-undecene (catalyst) 0.01 parts

  After replacing the air in the reaction tank with nitrogen gas, the temperature was raised to 80 ° C. in a nitrogen atmosphere with stirring, and the reaction was performed for 8 hours. After completion of the reaction, 33 parts of ethyl ethanoate was added and cooled to room temperature. As a result, a pale yellow transparent solution having a concentration of about 40% was obtained.

(Synthesis Example 15)
Monoalcohol used in Synthesis Example 14: The reaction was performed in the same manner as in Synthesis Example 15 except that dodecyl alcohol was changed to dodecylamine (monoamine) and no catalyst was used, and the concentration was adjusted to about 40% with ethyl ethanoate. As a result, a pale yellow transparent solution was obtained.

(Synthesis Example 16)
The following reaction was carried out in the same manner as in Synthesis Example 10 except that the ethylenically unsaturated monomer (b12) having a cyclic structure and a carboxyl group, an initiator and an organic solvent were charged in the following ratios, respectively. Was adjusted to about 40% to obtain a clear solution.

[Reaction tank]
Ethenyl benzene carboxylic acid (b12) 41 parts n-butyl propenoate 20 parts methyl ethyl ketone (organic solvent) 50 parts 2,2'-azobisisobutyronitrile (initiator) 0.01 part [Drip device]
N-butyl propenoate 38 parts ethenylbenzenecarboxylic acid (b12) 1 part methyl ethyl ketone (organic solvent) 50 parts 2,2'-azobisisobutyronitrile (initiator) 0.01 part

<Manufacture of resin (Y)>
(Synthesis Example 17)
In the reaction vessel of the polymerization reactor equipped with a reaction vessel, a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube, the following ethylenically unsaturated monomer (b2) having a carboxyl group, other monomers, start The agent and the organic solvent were charged at the following ratios.

[Reaction tank]
N-butyl propenoate 99 parts propenoic acid (b2) 1 part toluene (organic solvent) 100 parts 2,2′-azobisisobutyronitrile (initiator) 0.5 part

  After replacing the air in the reaction tank with nitrogen gas, the temperature was raised to 80 ° C. in a nitrogen atmosphere with stirring, the reaction was performed for 8 hours, and after completion of the reaction, 50 parts of toluene was added and cooled to room temperature. A clear solution with a concentration of about 40% was obtained.

(Synthesis Example 18)
The reaction was conducted in the same manner as in Synthesis Example 17 except that the ethylenically unsaturated monomer (b2) having a carboxyl group used in Synthesis Example 17 was changed to hydroxyethyl propenoate, and the concentration was adjusted to about 40% with toluene. Adjusted to obtain a clear solution.

(Synthesis Example 19)
The ethylenically unsaturated monomer (b2) having a carboxyl group in 99 parts of ethenylbenzene, which is an ethylenically unsaturated monomer (b1) having a cyclic structure, is substituted with n-butyl propenoate used in Synthesis Example 17. ) Was changed to 2-hydroxyethyl propenoate: 1 part, the initiator was changed to 0.01 part of t-butylperoxy-2-ethylhexanoate, and the organic solvent was changed to 100 parts of ethyl ethanoate. The reaction was carried out in the same manner as in Synthesis Example 16, and the concentration was adjusted to about 40% with ethyl ethanoate to obtain a transparent solution.

<Production Method of Resin (A ′) (Production Method 2)>
(Synthesis Example 20)
Polymerization tank, stirrer, thermometer, reflux condenser, dropping device, polymerization tank and dropping device of a polymerization reaction apparatus equipped with a nitrogen introduction tube, resin (B) prepared in Synthesis Example 7 and the following ethylenically unsaturated monomer Each body was charged at the following ratio.

[Polymerization tank]
Resin (B) solution prepared in Synthesis Example 7 50 parts n-butyl propenoate 30 parts methyl propenoate 10 parts 2-hydroxyethyl propenoate (a1) 0.5 part ethyl ethanoate (organic solvent) 15 parts 2,2 '-Azobisbutyronitrile 0.05 parts [Drip device]
N-butyl propenoate 39 parts 2-hydroxyethyl propenoate (a1) 0.5 part ethyl ethanoate (organic solvent) 22 parts 2,2′-azobisbutyronitrile 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 rate reaches about 70%, the above-mentioned ethylenically unsaturated monomer (a1) having a hydroxyl group, other ethylenically unsaturated monomers, a polymerization initiator, and a mixture of an organic solvent from a dropping device. The dripping was started. After completion of dropping, the mixture was further aged with stirring for 8 hours, and then added with ethyl ethanoate: 83 parts, cooled to room temperature, and a resin (resin (B)) that is a composite pressure-sensitive adhesive resin composition. A clear solution of A ′) was obtained.

(Synthesis Examples 21-29)
The reaction was conducted in the same manner as in Synthesis Example 20 except that the resin (B) solution used in Synthesis Example 20 was changed to the resin (B) solution obtained in Synthesis Examples 8 to 16, and the concentration was adjusted with ethyl ethanoate. Adjust to about 40% to obtain a clear solution.

<Manufacture of resin (X ')>
(Synthesis Examples 30 to 32)
The reaction was conducted in the same manner as in Synthesis Example 20 except that the resin (B) solution used in Synthesis Example 20 was changed to the resin (Y) solution obtained in Synthesis Examples 17 to 19, and the concentration was reduced to about ethyl ethanoate. Adjusted to 40% to obtain a clear solution.

(Synthesis Example 33)
Polymerization tank, stirrer, thermometer, reflux condenser, dropping device, polymerization tank and dropping device of a polymerization reaction apparatus equipped with a nitrogen introduction tube, resin (B) prepared in Synthesis Example 7 and the following ethylenically unsaturated monomer Each body was charged at the following ratio.

[Polymerization tank]
Resin (B) solution prepared in Synthesis Example 7 50 parts n-butyl propenoate 40 parts propenoic acid 0.5 parts ethyl ethanoate (organic solvent) 15 parts 2,2′-azobisbutyronitrile 0.05 part [ Dripping device]
N-butyl propenoate 39 parts propenoic acid 0.5 parts ethyl ethanoate (organic solvent) 22 parts 2,2'-azobisbutyronitrile 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 rate reached about 70%, the dropping of the mixture of the ethylenically unsaturated monomer, the polymerization initiator, and the organic solvent was started from the dropping device. After completion of dropping, the mixture was further aged with stirring for 8 hours, and then added with 83 parts of ethyl ethanoate and cooled to room temperature. Resin (X ') A clear solution was obtained.

(Synthesis Example 34)
The reaction was conducted in the same manner as in Synthesis Example 33 except that the resin (B) solution used in Synthesis Example 33 was changed to the resin (Y) solution obtained in Synthesis Example 19, and the concentration was about 40% with ethyl ethanoate. To obtain a clear solution.

  Resin (A ') which is resin (A), resin (B), resin (X), resin (Y), and resin composition resin for composite pressure-sensitive adhesives obtained in Synthesis Examples 1 to 34 And solution of resin (X ′), raw material composition, solution appearance, nonvolatile content concentration (%), solution viscosity, weight average molecular weight (Mw), acid value (AV), hydroxyl value (OHV), and glass transition temperature (Tg) ) Was determined according to the following method, and the results are shown in Table 1.

<< Solution appearance >>
The appearance of the resin (A), the resin (B), and the resin (A ′) and resin (X ′), which are composite resin compositions for pressure-sensitive adhesives, were visually evaluated.

<Measurement of nonvolatile content concentration (NV)>
About 1 g of resin (A), resin (B), and resin (A ′) or resin (X ′), which is a composite resin composition for pressure-sensitive adhesive, are weighed in a metal container, and 150 It was dried in an oven at 20 ° C. for 20 minutes, and the residue was weighed and the remaining rate was calculated to obtain the nonvolatile content concentration (%).

<< Measurement of solution viscosity (Vis) >>
Resin (A), resin (B), and resin type resin composition for composite pressure-sensitive adhesives Resin (A ′) and resin (X ′) in a B-type viscometer in an atmosphere of 23 ° C. (Manufactured by Tokyo Keiki Co., Ltd.) Using a # 3 rotor, measurement was performed under the conditions of 12 rpm and 1 minute rotation, and the solution viscosity (mPa · s) was obtained.

<< Measurement of weight average molecular weight (Mw) >>
The weight average molecular weight (Mw) of the resin (A ′) and the resin (X ′), which are the resin (A), the resin (B), and the composite resin composition for pressure-sensitive adhesives, is measured by Showa Denko KK GPC (Gel Permeation Chromatography) “Shodex GPC System-21” was used. GPC is liquid chromatography that separates and quantifies substances dissolved in a solvent based on the difference in molecular size, and the weight average molecular weight (Mw) is determined in terms of ethenylbenzene.

<Measurement of acid value (AV)>
Resin (B) and the resin (A ′) and resin (X ′), which are composite resin compositions for pressure-sensitive adhesives, are each precision with about 2.5 g of sample in a stoppered Erlenmeyer flask. Then, 100 ml of a toluene / ethanol (2/1 by volume) mixture was added and dissolved. To this was added a phenolphthalein test solution as an indicator, which was held for 30 seconds, and then titrated with a 0.1N alcoholic potassium hydroxide solution until the solution turned light red.
The acid value (mgKOH / g) was determined by the following equation as the value of the resin in the dry state.
Acid value (mgKOH / g) = {(5.611 × a × F) / S} / (Nonvolatile content concentration / 100)
Where S: Amount of sample collected (g)
a: Consumption of 0.1N alcoholic potassium hydroxide solution (ml)
F: Potency of 0.1N alcoholic potassium hydroxide solution

<< Measurement of hydroxyl value (OHV) >>
Resin (A) and the resin (A ′) and resin (X ′), which are composite resin compositions for pressure-sensitive adhesives, are each precision with about 2.5 g of sample in a stoppered Erlenmeyer flask. And 100 ml of a toluene / ethanol (volume ratio: toluene / ethanol = 2/1) mixed solution is added and dissolved. Further, 5 ml of an acetylating agent (a solution in which 25 g of ethane acid anhydride was dissolved in pyridine to make a volume of 100 ml) was added and stirred for about 1 hour. To this, phenolphthalein reagent is added as an indicator and lasts for 30 seconds. Thereafter, the solution is titrated with a 0.1N alcoholic potassium hydroxide solution until the solution becomes light red.
The hydroxyl value was determined by the following formula. The hydroxyl value was a numerical value in the dry state of the resin (unit: mgKOH / g).
Hydroxyl value (mgKOH / g) = [{(ba) × F × 28.25} / S] / (Non-volatile content concentration / 100) + D
Where S: Amount of sample collected (g)
a: Consumption of 0.1N alcoholic potassium hydroxide solution (ml)
b: Consumption of 0.1N alcoholic potassium hydroxide solution in the empty experiment (ml)
F: Potency of 0.1N alcoholic potassium hydroxide solution
D: Acid value (mgKOH / g)

<< Measurement of glass transition temperature (Tg) >>
An “SSC5200 disk station” (manufactured by Seiko Instruments Inc.) was connected to a robot DSC (differential scanning calorimeter, “RDC220” manufactured by Seiko Instruments Inc.) and used for measurement.

  A resin (A), a resin (B) obtained in each synthesis example, and a resin (A ′) or resin (X ′) solution, which is a composite resin composition for pressure-sensitive adhesives, is stripped. About 10 mg of the dried polyester film (hereinafter referred to as polyester release liner), dried, scraped about 10 mg of the dried resin, 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 was used as a reference, heated at a temperature of 100 ° C. for 5 minutes, and then rapidly cooled to −120 ° C. using liquid nitrogen. Thereafter, the temperature was raised at 10 ° C./min, and the glass transition temperature (Tg, unit: ° C.) was determined from the DSC chart obtained during the temperature elevation.

The symbols shown in Table 1 are as follows.
PAB: n-butyl propenoate, PAM: methyl propenoate, PA: propenoic acid, PAPhE: phenoxyethyl propenoate, PACH: cyclohexyl propenoate, MPA: 2-methylpropenoic acid, PPABz: benzyl 2-methylpropenoate, PAHE : 2-hydroxyethyl propenoate, PAHB: 4-hydroxybutyl 2-methylpropenoate, HEAA: N-hydroxyethylpropenamide, EB: ethenylbenzene, EBA: ethenylbenzene carboxylic acid, EP: N-ethenyl-2 -Pyrrolidone, B2Anh: (Z) -butenedioic anhydride, DA: dodecyl alcohol, DAm: dodecylamine, AIBN: 2,2'-azobisisobutyronitrile, PBOEH: t-butylperoxy-2-ethyl Hexanoate, DBU: 1,8- Azabicyclo [5,4,0] -7-undecene, EAC: ethyl ethanoic acid, MEK: methyl ethyl ketone, TOL: Toluene.

The parentheses shown in Table 1 are as follows.
Resin (A), Resin (X), Resin (B), and Resin (Y) are expressed in parentheses by the ethylenic unsaturation of the composite pressure-sensitive adhesive resin composition provided by Production Method 2, respectively. Represents the monomer composition.

Example 1
For 100 parts of the resin (A) solution obtained in Synthesis Example 1, 25 parts of the resin (B) solution prepared in Synthesis Example 7 was used as a reactive compound (C). 2 parts of 5 parts of 2-methylpentane-2,4-diol adduct of sinate and 0.2 part of HBAP (2,2′-bishydroxymethylbutanol tris [3- (1-aziridinyl) propionate]) Then, ethyl ethanoate was added and stirred well so that the coating viscosity was 2000 to 3000 mPa · s to obtain a pressure-sensitive adhesive.
This was coated on a polyester release liner so that the thickness after drying was 20 μm, and dried at 100 ° C. for 2 minutes to form a pressure-sensitive adhesive layer.
After drying, one side of a polarizing film having a multilayer structure in which both sides of a polyhydroxyethene (PHE) polarizer are sandwiched between triacetyl cellulose protective films (hereinafter referred to as “TAC film”) is bonded to the resin layer. A laminate having a configuration of “release liner / pressure-sensitive adhesive layer / TAC film / PHE / TAC film” was obtained.
Next, the obtained laminate was aged (dark reaction) for 1 week under the condition of a temperature of 23 ° C. and a relative humidity of 50%, and the reaction of the pressure-sensitive adhesive layer was advanced to obtain an adhesive optical member.

(Comparative Examples 1 and 2)
Instead of the resin (A) solution obtained in Synthesis Example 1, the resin (X) solution prepared in Synthesis Example 5 (Comparative Example 1) and the resin (X) solution prepared in Synthesis Example 6 (Comparative Example 2) A pressure-sensitive adhesive film for optics was obtained in the same manner as in Example 1 except that each was used.

(Comparative Example 3)
The resin (B) used in Example 1 and the reactive compound (C) HBAP (2,2′-bishydroxymethylbutanol tris [3- (1-aziridinyl) propionate]) 0.2 part are not used. Except for the above, an optical pressure-sensitive adhesive film was obtained in the same manner as in Example 1.

(Comparative Examples 4-6)
In Example 1, instead of the resin (B) solution used, the resin (B) solution prepared in Synthesis Example 17 (Comparative Example 4) and the resin (B) solution prepared in Synthesis Example 18 (Comparative Example 5) ), An optical pressure-sensitive adhesive film was obtained in the same manner as in Example 1 except that the resin (B) solution (Comparative Example 6) prepared in Synthesis Example 19 was used.
Among these, in Comparative Example 6, in order to increase the viscosity, ethyl ethanoate was added in excess (3 times the amount of Example 1) to reduce the coating viscosity, and an optical pressure-sensitive adhesive film was obtained.

(Examples 2 to 4)
Instead of the resin (A) solution obtained in Synthesis Example 1, the resin (A) obtained in Synthesis Example 2 (Example 2), Synthesis Example 3 (Example 3), and Synthesis Example 4 (Example 4) An optical pressure-sensitive adhesive film was produced in the same manner as in Example 1 except that the solution was used.
Among these, since Example 4 had high viscosity, ethyl ethanoate was added in excess (twice the amount of Example 1) to reduce the coating viscosity, and an optical pressure-sensitive adhesive film was obtained.

(Examples 5 to 13)
In Example 1, instead of using the resin (B) solution obtained in Synthesis Example 7 used, the resin (B) solution obtained in Synthesis Examples 8 to 16 (Examples 5 to 13) was used. Obtained an optical pressure-sensitive adhesive film in the same manner as in Example 1.

(Examples 14 and 15)
In place of 5 parts of TDI / MHPD (2-methylpentane-2,4-diol adduct of tolylene diisocyanate) as the reactive compound (C) in the resin solution used in Example 1, Example 14 5 parts of XDI / EHPD (2-methyl-2- (hydroxymethyl) propane-1,3-diol adduct of xylylene diisocyanate), Example 15 is HMDI / burette (burette adduct of hexamethylene diisocyanate) An optical pressure-sensitive adhesive film was prepared in the same manner as in Example 1 except that 1 part of 5 parts was added.

(Examples 16 and 17)
The resin solution used in Example 1 was replaced with 0.2 part of HBAP (2,2′-bishydroxymethylbutanol tris [3- (1-aziridinyl) propionate]) as the reactive compound (C). In Example 16, 2 parts of TGMXDA (N, N, N ′, N′-tetraglycidyl-m-xylylenediamine) was used, and in Example 17, 0.5 part of Al chelate (aluminum tris (2,4-pentadionate)) was used. Was added in the same manner as in Example 1 except that 1 part of each was added.

(Example 18)
As a reactive compound (C), 100 parts by weight of a composite pressure-sensitive adhesive resin composition containing both the resin (A) and the resin (B) obtained in Synthesis Example 20 was used as a reactive compound (C). 4 parts MHPD (2-methylpentane-2,4-diol adduct of tolylene diisocyanate) and HBAP (2,2′-bishydroxymethylbutanol tris [3- (1-aziridinyl) propionate]) Ethane ethanoate was added and stirred well so that two types of 16 parts and a coating viscosity of 2000 to 3000 mPa · s were obtained, and a pressure-sensitive adhesive was obtained in the same manner as in Example 1.

(Comparative Examples 7 to 11)
An optical pressure-sensitive optical system in the same manner as in Example 18 except that the resin solution obtained in Synthesis Examples 31 to 35 was used instead of the resin (A) solution obtained in Synthesis Example 20 used in Example 18. An adhesive film was prepared.
Among these, since Comparative Examples 10 and 11 have high viscosities, ethyl ethanoate was added in excess (3 times the amount of Example 18) to reduce the coating viscosity, and a pressure-sensitive adhesive film for optical use was obtained. It was.

(Examples 19 to 27)
An optical pressure-sensitive adhesive film for optical use in the same manner as in Example 18 except that the resin solutions prepared in Synthesis Examples 21 to 29 were used instead of the resin solution obtained in Synthesis Example 20 used in Example 18. Got.

(Examples 28 and 29)
Of the reactive compound (C) of Example 17, 4 parts of TDI / MHPD (2-methylpentane-2,4-diol adduct of tolylene diisocyanate) were used. In Example 28, XDI / EHPD (xylylene diene) was used. 4 parts of 2-methyl-2- (hydroxymethyl) propane-1,3-diol adduct body of isocyanate), except that in Example 29, HMDI / burette (hexamethylene diisocyanate burette adduct body) was changed to 4 parts. Produced an optical pressure-sensitive adhesive film in the same manner as in Example 17.

(Examples 30 and 31)
Of the reactive compound (C) of Example 18, 0.16 part of HBAP (2,2′-bishydroxymethylbutanol tris [3- (1-aziridinyl) propionate]) was used. In Example 30, TGMXDA (N, N, N ′, N′-tetraglycidyl-m-xylylenediamine) 1.6 parts, except that in Example 31, Al chelate (aluminum tris (2,4-pentadionate)) was changed to 0.4 parts. Produced an optical pressure-sensitive adhesive film in the same manner as in Example 18.

  The pot life and coating processability of the pressure-sensitive adhesives obtained in each Example and each Comparative Example were evaluated by the following methods. Moreover, about the obtained adhesive optical member, various performance was evaluated with the following method. The results are shown in Table 2.

<Evaluation method of pot life>
About the obtained pressure sensitive adhesive resin composition, after adding a reactive compound (C), using a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd.) with a viscosity at 25 ° C. every 10 hours until 12 hours, Measurement was performed under the condition of rotation for 1 minute, and the pot life was evaluated in three stages.
○: “Viscosity increase rate up to 8 hours is less than twice. No problem at all”
Δ: “Slight increase in viscosity is observed, but the rate of increase in viscosity up to 5 hours is less than 2 times. Practical use is possible.”
X: “A sudden increase in viscosity was observed and gelled in less than 5 hours.

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

<< Evaluation method of optical characteristics >>
The pressure sensitive adhesive obtained in each Example and Comparative Example was applied to a peelable film with a comma coater at a speed of 2 m / min, dried in a 100 ° C. oven, and a pressure sensitive adhesive layer having a thickness of 25 μm was formed. Then, a peelable film was bonded to the surface of the adhesive layer to produce a pressure-sensitive adhesive film sandwiched between the peelable films.
After aging this for one week at a temperature of 23 ° C. and a relative humidity of 50%, both release learners were removed, and the appearance of the pressure-sensitive adhesive layer alone was judged visually, and HAZE was “NDH-300A” [Japan Made by Denshoku Industries Co., Ltd.].
○: No problem in practical use and very good. HAZE: less than 1.
(Triangle | delta): Cloudiness etc. are not recognized, but HAZE: 1 or more and less than 3 can be used without a problem practically.
X: Some cloudiness is recognized or HAZE: 3 or more. There are practical problems.

<Evaluation method of removability (reworkability)>
The adhesive optical member obtained in each example and comparative example was cut into a size of 25 mm × 150 mm, the release liner was peeled off, and was attached to a float glass plate with a thickness of 1.1 mm using a laminator at 50 ° C. It was held in an autoclave at 5 atm for 20 minutes to obtain an optical glass laminate of a polarizing film and a glass plate.
This optical glass laminate was left 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 °, and the glass surface after peeling was visually observed in three stages. evaluated.
○: No fogging, no problem in practical use, very good.
Δ: Some fogging is observed, but no problem in practical use and good.
X: Transfer of the adhesive layer was observed over the entire surface, which is impractical.

<Method for evaluating heat resistance and heat and humidity resistance>
The adhesive optical members obtained in each Example and Comparative Example were cut into a size of 150 mm × 80 mm, the release liner was peeled off, and the absorption axis of each polarizing film was placed on both sides of a 1.1 mm thick float glass plate. Were attached using a laminator so as to be orthogonal to each other. Subsequently, the glass plate on which the polarizing film was attached was held in an autoclave at 50 ° C. and 5 atm for 20 minutes to obtain an optical glass laminate of the polarizing film and the glass plate.
As evaluation of heat resistance, floating peeling and deviation after leaving the optical glass laminate at 95 ° C. for 1000 hours, and light leakage (white spots) when light was transmitted through the laminate were visually observed.
In addition, as an evaluation of the heat and moisture resistance, floating peeling and deviation after leaving the optical glass laminate for 1000 hours at 80 ° C. and 90% relative humidity, and light leakage when light is transmitted through the optical glass laminate. (White spots) were visually observed.
The heat resistance and moist heat resistance were evaluated based on the following four-stage evaluation criteria.
A: No floating peeling, misalignment, foaming, or whitening is observed, and there is no practical problem at all and it is very good.
○: No floating peeling, whitening, or foaming was observed, and the deviation was less than 0.2 mm.
Δ: Slightly floating peeling, foaming, and whitening are observed, but the deviation is less than 02 to 0.5 mm, and there is no problem in practical use. ×: There are floating peeling, foaming, whitening, and practical use. It is impossible.

The new symbols shown in Table 2 are as follows.
TDI / MHPD: 2-methylpentane-2,4-diol adduct of tolylene diisocyanate, HBAP: 2,2′-bishydroxymethylbutanol tris [3- (1-aziridinyl) propionate], TGMXDA: N, N, N ′, N′-tetraglycidyl-m-xylylenediamine, Al chelate: aluminum tris (2,4-pentadionate), XDI / EHPD: 2-methyl-2- (hydroxy) of xylylene diisocyanate Methyl) propane-1,3-diol adduct, HMDI / burette: burette adduct of hexamethylene diisocyanate, EAC: ethyl ethanoate.

As described above, it can be seen that the pressure-sensitive adhesive of the present invention is excellent in heat resistance, heat and humidity resistance, optical properties, peelability of the peelable film, and reworkability. In particular, the composite type in which the resin (A ′) is produced by interposing the resin (B) of Examples 18 to 32 rather than the mixed type of the resin (A) and the resin (B) of Examples 1 to 17 is used. It can be seen that both heat resistance and moisture heat resistance are superior.
In contrast, Comparative Examples 1 and 2 using the resin (X), Comparative Examples 4 to 6 using the resin (Y), and the resin (X ′) containing no hydroxyl group even if the resin (B) is interposed. About the comparative example 10 used, or the comparative examples 7-9 and 11 which used resin (X ') created by interposing resin (Y), after sticking to a glass plate, under high temperature or under high temperature and high humidity When it is left for a long period of time, foaming, floating and the like are generated, and it is recognized that the durability is inferior.
The pressure-sensitive adhesive of the present invention is suitable for optical glass laminate applications, as well as paints, elastic wall materials, coating waterproofing materials, flooring materials, tackifiers, adhesives, adhesives for laminated structures, sealing agents, Molding materials, surface modification coating agents, binders (magnetic recording media, ink binders, casting binders, fired brick binders, graft materials, microcapsules, glass fiber sizing, etc.), urethane foams (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 coat agent, resin for artificial marble, resistance for artificial marble Impact imparting agent, ink resin, film (laminate adhesive, protective film, etc.), laminated glass resin, Sex 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 (12)

  Resin composition for pressure-sensitive adhesives comprising a resin (A) obtained by polymerizing a monomer component essentially comprising an ethylenically unsaturated monomer having a hydroxyl group (a1) and a resin (B) having a cyclic structure A resin composition for pressure-sensitive adhesives, wherein the resin (B) having a cyclic structure has a carboxyl group and does not have a hydroxyl group.   The resin composition for pressure-sensitive adhesives according to claim 1, wherein the resin (B) having a cyclic structure has a weight average molecular weight of 5,000 to 100,000.   The resin composition for pressure-sensitive adhesives according to claim 1 or 2, wherein the acid value of the resin (B) having a cyclic structure is 0.1 to 200 mgKOH / g.   The resin composition for pressure-sensitive adhesives according to claim 1, wherein the resin (A) does not have a carboxyl group.   In a total of 100% by weight of the resin (A) and the resin (B) having a cyclic structure, the content of the resin (A) is 50 to 99% by weight, and the content of the resin (B) having a cyclic structure is 1 to 50 The pressure-sensitive adhesive resin composition according to any one of claims 1 to 4, wherein the resin composition is in wt%.   A pressure-sensitive adhesive comprising the pressure-sensitive adhesive resin composition according to claim 1 and a reactive compound (C) capable of reacting with a hydroxyl group and a carboxyl group.   The pressure-sensitive adhesive according to claim 6, wherein the reactive compound (C) is an isocyanate compound (c1).   The pressure-sensitive adhesive according to claim 6, wherein the reactive compound (C) is an ethyleneimine compound (c2), a glycidyl compound (c3), or an organometallic compound (c4).   A pressure-sensitive adhesive film comprising a pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive according to claim 6 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 6 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 any one of claims 6 to 8, and glass are sequentially laminated.   It is characterized by polymerizing a monomer component essentially comprising an ethylenically unsaturated monomer (a1) having a hydroxyl group in the presence of a resin (B) having a cyclic structure and a carboxyl group and not having a hydroxyl group. A method for producing a pressure-sensitive adhesive resin composition.