JP2010037502A - Pressure-sensitive adhesive composition and pressure-sensitive adhesive film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pressure-sensitive adhesive composition capable of forming a pressure-sensitive adhesive optical film to be pasted on a glass member for a liquid crystal cell and having excellent releasing stability of a releasable sheet, a releasability from a glass member of a liquid crystal cell and durability in pasted state. <P>SOLUTION: The pressure-sensitive adhesive composition comprises (A) a copolymer produced by the copolymerization of an α,β-unsaturated compound, having at least one of carboxyl group and hydroxyl group and having a glass transition temperature of -80 to +10°C, (B) a silane compound having an amino group and an alkoxy group and having an amine value of 0.5-200 (mgKOH/g) and (C) a reactive compound reactive with at least one of the carboxyl group and the hydroxyl group in the copolymer (A). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a pressure-sensitive adhesive composition mainly comprising a copolymer obtained by polymerizing an α, β-unsaturated compound. Specifically, the pressure-sensitive adhesive composition is excellent in adhesion to an optical film, heat resistance, heat and humidity resistance and transparency, and can be suitably used as a pressure-sensitive adhesive composition for laminating an optical film on a liquid crystal cell member. About. Furthermore, this invention relates to the pressure sensitive adhesive film which uses a pressure sensitive adhesive composition.

Due to dramatic advances in electronics in recent years, various flat panel displays (FPD) such as liquid crystal displays (LCD), plasma displays (PDP), rear projection displays (RPJ), EL displays, light emitting diode displays, etc. As a device, it has come to be used in a wide range of fields. These FPDs are not only used fixed indoors, such as personal computer displays and liquid crystal televisions, but also mounted on vehicles such as car navigation displays and used in a moving state.
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 with a pressure-sensitive adhesive and used in a display device. Since the pressure-sensitive adhesive used in the display device is required to have excellent transparency, a pressure-sensitive adhesive mainly composed of an acrylic resin is generally used.

  By the way, among the various films described above, the polarizing film has a three-layer structure in which both surfaces of a polyvinyl alcohol-based polarizer are sandwiched between triacetyl cellulose-based or cycloolefin-based protective films. For this reason, in a polarizing film, the remarkable dimensional change by expansion / contraction accompanying the change of temperature or humidity arises according to the characteristic of the material which comprises each layer.

In addition, in the inspection process of a laminate with a polarizing film attached to the glass surface for a liquid crystal cell, the polarizing film etc. is peeled off and a new polarizing film etc. is attached to those that have air or dust trapped during lamination. Will be fixed. This re-pasting is also called “rework”.
However, since the laminated body is generally inspected after being stored at a high temperature for a certain period of time in order to improve adhesion, not only does the peel strength increase during that time, but it becomes difficult to peel off the polarizing film and the like. The glass member as the adherend is contaminated, such as adhesive residue and cloudiness, after re-peelability is reduced and peeled off.

  In addition, since the dimensional change due to the shrinkage of the polyvinyl alcohol film is severe under high temperature or high temperature and high humidity conditions, the laminate composed of the optical film / adhesive layer / adhered body is not subjected to high temperature or high temperature and high humidity conditions. When the dimensions of the polarizing film are changed, bubbles are generated at the interface between the adhesive layer and the adherend (foaming phenomenon), and the optical film is lifted from the adherend and peeled off (floating / peeling phenomenon). By adjusting the molecular weight of the main component of the pressure-sensitive adhesive composition and the degree of crosslinking of the pressure-sensitive adhesive composition, and increasing the adhesive strength, it resists the dimensional change of the polarizing film and foams even in harsh environments. Attempts have been made to prevent floating and peeling.

  However, simply trying to resist the dimensional change of the optical 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 becomes optical. It concentrates on the four corners and the peripheral edge of the film. As a result, in the display device using the polarizing film, there is a problem that light leaks from the peripheral end portion of the display device, that is, so-called white spots occur.

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

Conventionally, various pressure-sensitive adhesives have been proposed for such various requirements.
For example, a pressure-sensitive adhesive composition obtained by blending a propenoic acid-based pressure-sensitive adhesive containing a propenoic acid-based resin and a crosslinking agent with a polyether polyol is known (see Patent Document 1).

However, the pressure-sensitive adhesive optical film formed using the pressure-sensitive adhesive composition described in Patent Document 1, after being attached to an adherend, when exposed to high temperature or high temperature and high humidity conditions for a long time, Extremely small bubbles are generated in a streak-like state at the peripheral edge of the optical film. This phenomenon is called a “crack” because very small bubbles that appear as streaks look like a kind of crack.
In addition, about 10 bubbles of 10 μm or less, which cannot be confirmed unless using an electron microscope, are generated in the center part per 10 m ² .
Further, in a display device of 20 inches or more, the luminance of the light source must be set high from the viewpoint of easy viewing. In the pressure-sensitive adhesive optical film using the pressure-sensitive adhesive composition described in Patent Document 1, white spots were not regarded as a problem in a display device of less than 20 inches. However, there has also been a problem that white spots are conspicuous in a display device using a high-intensity light source used at 20 inches or more.

As pressure-sensitive adhesive compositions for forming pressure-sensitive adhesive optical films, propenoic acid-based pressure-sensitive adhesives containing a propenoic acid-based resin, a crosslinking agent, and various silane coupling agents are disclosed in various documents.
However, even if a relatively low molecular weight silane coupling agent such as 3-glycidoxypropyltrimethoxysilane or 3-aminopropyltrimethoxysilane is contained, the demand for rework becomes more severe, which is more severe. The request has become unsatisfactory. In addition, there has been a problem that cracks and foaming are likely to occur when exposed to an adherend for a long period of time under high temperature or high temperature and high humidity conditions.

  Further, for example, Patent Document 2 discloses that the propene copolymer contains a silane compound having a β-ketoester structure and an alkoxy group, and the silane compound is added to 100 parts by weight of the propenoic acid resin. A pressure-sensitive adhesive composition comprising an amount of 0.001 to 5 parts by weight has been proposed. However, the composition has a problem that durability with time is lowered due to liberation of the silane compound monomer (see Patent Document 2).

  Also, for example, Patent Document 3 discloses an propylene acid-based acrylic oligomer silane coupling agent obtained by copolymerizing a propylene copolymer with a silane compound having a polymerizable double bond site and a reactive acrylic monomer. A pressure-sensitive adhesive composition obtained by polymerizing the silane compound in an amount of 0.05 to 5 parts by weight with respect to 100 parts by weight of the resin has been proposed. Even if the pressure-sensitive adhesive film described in Patent Document 3 is attached to an adherend and exposed to a high temperature or a high temperature and high humidity for a long period of time, cracks in the vicinity of the peripheral edge portion or microscopic deformation in the central portion are required. Bubbles were not generated, and no white spots were observed on a display device of less than 20 inches (see Patent Document 3).

However, a pressure-sensitive adhesive optical film using a pressure-sensitive adhesive composition containing an acrylic oligomer type silane coupling agent obtained by copolymerizing a silane compound having a polymerizable double bond site and a reactive acrylic monomer, As described in detail below, there was a problem that the peelability from the peelable sheet was likely to be lowered.
The pressure-sensitive adhesive optical film is formed by applying a pressure-sensitive adhesive composition to the release-treated surface of a release-treated sheet-like substrate (hereinafter referred to as a peelable sheet), and drying the optical film. It can be obtained by laminating on the surface, or coating and drying the pressure-sensitive adhesive composition on the optical film, and laminating the release-treated surface of the peelable sheet on the surface of the pressure-sensitive adhesive layer. However, the pressure-sensitive adhesive optical film is not always attached to an adherend, that is, a liquid crystal cell member immediately after production. The obtained pressure-sensitive adhesive optical film is often used after being stored for a certain period. In such a case, when the peelable sheet was peeled off and the exposed pressure sensitive adhesive layer was to be attached to a liquid crystal cell member such as glass, there was a problem that the peelable sheet was difficult to peel off.

From conventional propenoic acid-based pressure-sensitive adhesives using various silane coupling agents, release stability of peelable sheets, re-peelability from adherends called “reworkability”, and high durability after sticking It was not possible to obtain a pressure-sensitive adhesive optical film that satisfactorily balanced the properties.
JP-A-6-128539 Japanese Patent No. 3533446 JP 2008-101168 A

  The present invention is a pressure-sensitive adhesive optical film for adhering to a glass member for a liquid crystal cell, having excellent peel stability of the peelable sheet, excellent removability from the glass member for a liquid crystal cell, and after sticking An object of the present invention is to provide a pressure-sensitive adhesive composition capable of forming a pressure-sensitive adhesive optical film having excellent durability (heat resistance, heat and humidity 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 relates to a copolymer (A) having a glass transition temperature of −80 to 10 ° C. having at least one of a carboxyl group and a hydroxyl group, which is obtained by copolymerizing an α, β-unsaturated compound, an amine value, Is a reactive compound capable of reacting with at least one of a carboxyl group or a hydroxyl group in the silane compound (B) having an amino group and an alkoxy group of 0.5 to 200 (mgKOH / g) and the preceding copolymer (A) ( C), and a pressure-sensitive adhesive composition.

  In the second invention, the silane compound (B) has a silane compound (b1) having an amino group and an alkoxy group having an amine value greater than 200 (mgKOH / g), an alkoxy group, and an amino group. It is a reactive organism (B1) with the silane compound (b2) which does not carry out, It is related with the pressure sensitive adhesive composition as described in the said invention characterized by the above-mentioned.

  The third invention relates to 0.01 to 5 parts by weight of a silane compound (B) and a reactive compound with respect to 100 parts by weight of a copolymer of an α, β-unsaturated compound having a carboxyl group or a hydroxyl group in the side chain (A). (C) It is related with the pressure sensitive adhesive composition in any one of the said invention characterized by including 0.001-30 weight part.

  A fourth invention is characterized in that the α, β-unsaturated compound essentially comprises at least one compound selected from propenoic acid, 2-methylpropenoic acid, a propenoic acid derivative and a 2-methylpropenoic acid derivative. The pressure-sensitive adhesive composition according to any one of the above inventions.

  According to a fifth invention, a propenoic acid derivative in which the carboxyl group in the copolymer (A) is derived from at least one of propenoic acid and 2-methylpropenoic acid, and the hydroxyl group in the copolymer (A) has a hydroxyl group, It originates from at least one of 2-methylpropenoic acid derivatives having a hydroxyl group, and has propenoic acid, 2-methylpropenoic acid, a propenoic acid derivative having a hydroxyl group and a hydroxyl group in a total of 100% by weight of the α, β-unsaturated compound. The total of 2-methylpropenoic acid derivatives is 0.01 to 20% by weight, and relates to the pressure-sensitive adhesive composition according to the invention described above.

  According to a sixth aspect of the present invention, the reactive compound (C) has two or more functional groups capable of reacting with a carboxyl group or hydroxyl groups in one molecule. The present invention relates to a pressure-sensitive adhesive composition.

  A seventh invention is a pressure-sensitive adhesive optical film comprising an optical film and a pressure-sensitive adhesive layer located on at least one surface of the optical film, wherein the pressure-sensitive adhesive layer is any one of the above inventions. The present invention relates to a pressure-sensitive adhesive optical film formed from a pressure-sensitive adhesive composition.

  According to the present invention, a pressure-sensitive adhesive optical film for adhering to a glass member for a liquid crystal cell, excellent in peeling stability from the peelable sheet, excellent in removability from the glass member for liquid crystal cell, and sticking It has become possible to provide a pressure-sensitive adhesive composition that can form a pressure-sensitive adhesive optical film having excellent durability (heat resistance and heat and humidity resistance).

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

  The copolymer (A) used in the present invention is an α, β-unsaturated compound, that is, a copolymer obtained by copolymerizing a compound having a polymerizable α, β-unsaturated double bond in the molecule. And has a glass transition temperature of −80 to 10 ° C. and has at least one of a carboxyl group and a hydroxyl group. A carboxyl group or a hydroxyl group is located in a side chain position, and these functional groups react with a reactive compound (C) described later to form a pressure-sensitive adhesive layer.

  As the compound having an α, β-unsaturated double bond, at least one compound selected from propenoic acid, 2-methylpropenoic acid, a propenoic acid derivative and a 2-methylpropenoic acid derivative is used as an essential component. It is also preferable to use an alkenyl group-containing compound.

  Examples of the propenoic acid derivative or 2-methylpropenoic acid derivative include, for example, methyl (2-methyl) propenoate [combination of methyl propenoate and methyl 2-methylpropenoate is referred to as “methyl (2-methyl) propenoate”. To do. The same applies hereinafter. ], (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;

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

  For example, allyl (2-methyl) propenoate, 1-methylallyl (2-methyl) propenoate, 2-methylallyl (2-methyl) propenoate, 1-butenyl (2-methyl) propenoate, (2-methyl) propene 2-butenyl acid, 3-butenyl (2-methyl) propenoate, 1,3-methyl-3-butenyl (2-methyl) propenoate, 2-chloroallyl (2-methyl) propenoate, (2-methyl) propene Acid 3-chloroallyl, (2-methyl) propenoic acid-o-allylphenyl, (2-methyl) propenoic acid 2- (allyloxy) ethyl, (2-methyl) propenoic acid allyl lactyl, (2-methyl) propenoic acid citronellyl, Geranyl (2-methyl) propenoate, rosinyl (2-methyl) propenoate, cinnamyl (2-methyl) propenoate, (2-methyl) ) Containing more unsaturated groups vinyl propenoic acid (2-methyl) propenoic acid esters;

  For example, (2-methyl) propenoic acid perfluoromethyl, (2-methyl) propenoic acid perfluoroethyl, (2-methyl) propenoic acid perfluoropropyl, (2-methyl) propenoic acid perfluorobutyl, (2-methyl) ) Perfluorooctyl propenoate, trifluoromethyl methyl (2-methyl) propenoate, 2-trifluoromethyl ethyl (2-methyl) propenoate, diperfluoromethyl methyl (2-methyl) propenoate, (2-methyl) ) 2-perfluoroethylethyl acrylate, (2-methyl) propenoic acid 2-perfluoromethyl-2-perfluoroethylmethyl, (2-methyl) propenoic acid triperfluoromethylmethyl, (2-methyl) propenoic acid 2-perfluoroethyl-2-perfluorobutylethyl, (2-methyl) (2-methyl) propenoic acid perfluoroalkyl esters such as 2-perfluorohexylethyl lopenate, 2-perfluorodecylethyl (2-methyl) propenoate, 2-perfluorohexadecylethyl (2-methyl) propenoate Kind;

  For example, 2-hydroxyethyl (2-methyl) propenoate, 1-hydroxypropyl (2-methyl) propenoate, 2-hydroxypropyl (2-methyl) propenoate, 2-methoxyethyl (2-methyl) propenoate, Hydroxyl or alkoxysilyl group-containing (2-methyl) propenoic acid such as 2-ethoxyethyl (2-methyl) propenoate, 2-hydroxybutyl (2-methyl) propenoate, 4-hydroxybutyl (2-methyl) propenoate Esters;

  For example, N-methylaminoethyl (2-methyl) propenoate, N-tributylaminoethyl (2-methyl) propenoate, N, N-dimethylaminoethyl (2-methyl) propenoate, (2-methyl) propenoic acid Amino group-containing (2-methyl) propenoates such as N, N-diethylaminoethyl;

  For example, glycidyl (2-methyl) propenoate, (2-methyl) propenoate (3,4-epoxycyclohexyl) methyl, (2-methyl) propenoate (3-methyl-3-oxetanyl) methyl, (2-methyl) ) Heterocycle-containing (2-methyl) propenoates such as tetrahydrofurfuryl propenoate;

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

  For example, 2- (2′-hydroxy-5 ′-(2-methyl) propane-2-enoyloxyethylphenyl) -2H-benzotriazole, 2- (2′-hydroxy-5 ′-(2-methyl) Propane-2-enoyloxyethylphenyl) -5-chloro-2H-benzotriazole, 2- (2'-hydroxy-5 '-(2-methyl) propan-2-enoyloxypropylphenyl) -2H-benzo Triazole, 2- (2′-hydroxy-5 ′-(2-methyl) propane-2-enoyloxypropylphenyl) -5-chloro-2H-benzotriazole, 2- (2′-hydroxy-3′-tert) -Butyl-5 '-(2-methyl) propane-2-enoyloxyethylphenyl) -2H-benzotriazole, 2- (2'-hydroxy-3'-tert-butyl) Benzotriazole-based (2-methyl) propenoic acid derivatives such as ru-5 ′-(2-methyl) propane-2-enoyloxyethylphenyl) -5-chloro-2H-benzotriazole;

  For example, 2-hydroxy-4- {2- (2-methyl) propane-2-enoyloxy} ethoxydiphenylmethanone, 2-hydroxy-4- {2-((2-methyl) propane-2-enoyloxy} butoxydiphenyl Methanone, 2,2′-dihydroxy-4- {2- (2-methyl) propane-2-enoyloxy} ethoxydiphenylmethanone, 2-hydroxy-4- {2- (2-methyl) propan-2-enoyloxy } Diphenylmethanone-based (2-methyl) propenoic acid derivatives such as ethoxy-4 ′-(2-hydroxyethoxy) diphenylmethanone;

  For example, 2,4-diphenyl-6- [2-hydroxy-4- (2- (2-methyl) propane-2-enoyloxyethoxy)]-S-triazine, 2,4-bis (2-methylphenyl) ) -6- [2-hydroxy-4- (2- (2-methyl) propane-2-enoyloxyethoxy)]-S-triazine, 2,4-bis (2-methoxyphenyl) -6- [ 2-hydroxy-4- (2- (2-methyl) propane-2-enoyloxyethoxy)]-S-triazine, 2,4-bis (2-ethylphenyl) -6- [2-hydroxy-4- (2- (2-Methyl) propane-2-enoyloxyethoxy)]-S-triazine, 2,4-bis (2-ethoxyphenyl) -6- [2-hydroxy-4- (2- (2- Methyl) propane-2-enoyloxyethoxy )]-S-triazine, 2,4-bis (2,4-dimethoxyphenyl) -6- [2-hydroxy-4- (2- (2-methyl) 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-based (2-methyl) ) Propenoic acid derivatives;

  For example, alkylene oxide-containing (2-methyl) propenoic acid derivatives such as ethylene oxide adduct of (2-methyl) propenoic acid;

  For example, ethylene glycol di (2-methyl) propenoate, triethylene glycol di (2-methyl) propenoate, tetraethylene glycol di (2-methyl) propenoate, trimethylolpropane tri (2-methyl) propenoate, tri (2-methyl) propenoic acid pentaerythritol, di (2-methyl) propenoic acid 1,1,1-trishydroxymethylethane, tri (2-methyl) propenoic acid 1,1,1-trishydroxymethylethane, tri ( And polyfunctional (2-methyl) propenoic acid esters such as 2-methyl) propenoic acid 1,1,1-trishydroxymethylpropane.

  Examples of the alkenyl group-containing compound include ethenylbenzene, α-isopropenylbenzene, β-isopropenylbenzene, 1-methylethenylbenzene, 2-methylethenylbenzene, 3-methylethenylbenzene, 1-butylethenyl. Aromatic vinyl monomers such as tenenylbenzene, 1-chloro-4-isopropenylbenzene, ethenylbenzenesulfonic acid and its sodium and potassium salts;

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

  For example, vinyl monomers containing trialkyloxysilyl groups such as vinyltrimethoxysilane and vinyltriethoxysilane;

  For example, cis-butenedioic acid diallyl, 2-methylidene succinate diallyl, (E) -but-2-enoic acid vinyl, (Z) -octadeca-9-enoic acid vinyl, (9Z, 12Z, 15Z) -octadeca-9 Vinyl ester monomers containing further unsaturated bonds such as vinyl 12,12,15-trienoate;

  For example, nitrile group-containing vinyl monomers such as 2-propenenitrile and 2-methyl-2-propenenitrile;

  For example, amide group-containing vinyl monomers such as propenamide and 2-methylpropenamide;

  For example, vinyl esters such as vinyl ethanoate, vinyl propanoate, vinyl pivalate, vinyl benzenecarboxylate, vinyl 3-phenyl-2-propenoate;

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

  For example, unsaturated carboxylic acid anhydrides such as 2,5-dihydrofuran-2,5-dione;

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

  Examples include chloroethylene, 1,1-dichloroethylene, allyl chloride, and allyl alcohol, but are not particularly limited thereto. These may use only 1 type or may use multiple types together.

  Moreover, in obtaining the copolymer (A) used for this invention, the compound which has (alpha), (beta) -unsaturated double bond other than these as needed can also be used, Examples include maleimide derivatives such as, for example, maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide;

  For example, alkenes such as ethene, propene, 1-butene, 2-butene, 2-methylpropene;

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

The copolymer (A) used in the present invention is appropriately selected from α, β-unsaturated compounds to be used for polymerization, so that a hydroxyl group, a carboxyl group, an amino group, an amide group, a maleimide group, a nitrile group are included in the structure. Various functional groups such as an epoxy group, an alkoxysilyl group, and an allyl group. In consideration of crosslinking reactivity with the reactive compound (C) described later, it is preferable to have at least one of a carboxyl group and a hydroxyl group.
The carboxyl group is preferably introduced into the copolymer (A) by using propenoic acid or 2-methylpropenoic acid during the copolymerization.
The hydroxyl group is preferably introduced into the copolymer (A) by using a propenoic acid derivative having a hydroxyl group or a 2-methylpropenoic acid derivative having a hydroxyl group during the copolymerization.

A compound having a carboxyl group or a hydroxyl group capable of reacting with the reactive compound (C) when the total of various α, β-unsaturated compounds used as raw materials for the copolymer (A) is 100% by weight. It is preferable that the total use amount of the compound to be included is 0.01 to 20% by weight. If it is less than 0.01% by weight, a sufficient cross-linked structure cannot be obtained, so the cohesive force of the pressure-sensitive adhesive layer is low, and the stability and durability during repeated use are inferior, which is not preferable.
On the other hand, if it exceeds 20% by weight, the cohesive force of the pressure-sensitive adhesive layer becomes too high, and as a result, the glass and the pressure-sensitive adhesive layer are easily peeled off, which is not preferable. In particular, when placed in an environment where the temperature and humidity vary, the glass and the pressure-sensitive adhesive layer are more easily peeled off.

The copolymer (A) forms a copolymer having a glass transition point (Tg) of −80 to 10 ° C. so as to exhibit well-balanced adhesive properties (particularly, compatibility between tack and cohesive force). It is preferable to select the α, β-unsaturated compound so that the glass transition point (Tg) is −60 to 0 ° C., and the α, β-unsaturated compound is selected. More preferably.
When the glass transition point of the copolymer is lower than −80 ° C., the cohesive force of the pressure-sensitive adhesive layer obtained by using the copolymer is lowered, and the peeling off tends to occur. On the other hand, when the glass transition point exceeds 0 ° C., a pressure-sensitive adhesive layer having sufficient tack cannot be obtained.

If the Tg of the homopolymer that can be formed from each monomer that is a constituent component of the copolymer (A) is known, the copolymer (A) can be formed based on the Tg of each homopolymer and the constituent ratio of each monomer. Tg can be obtained theoretically.
By the way, in the case of a pressure-sensitive adhesive composition, a small amount of the reactive compound (C) as a curing agent is generally blended with the copolymer (A) as a main component. Since the pressure-sensitive adhesive layer formed from such a pressure-sensitive adhesive composition has a loose cross-linked state (in other words, sparse), unlike a cured coating film that is densely cross-linked, the Tg of the pressure-sensitive adhesive layer Is approximately equal to Tg of the copolymer (A) before crosslinking. Accordingly, if the types and amounts of various α, β-unsaturated compounds are selected so that the Tg of the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition is 10 ° C. or lower, preferably 0 ° C. or lower. Good.

As the α, β-unsaturated compound, 2-ethylhexyl propenoate, n-butyl propenoate, n-octyl propenoate, isopropenoate which can form a homopolymer having a glass transition point (Tg) of −50 ° C. or less. -Octyl, iso-octyl propenoate, n-nonyl propenoate, iso-nonyl propenoate, n-decyl pepropenoate, lauryl propenoate, stearyl propenoate, decyl 2-methylpropenoate, lauryl 2-methylpropenoate, 2 -It is preferable to contain 20 to 80% by weight of a propenoic acid ester of alkyl side chain such as stearyl methylpropenoate or 2-methylpropenoic acid ester in a total of 100% by weight of the α, β-unsaturated compound.
Other compounds used for copolymerization with the above α, β-unsaturated compound include homopolymers having a glass transition point (Tg) in the range of −10 to 100 ° C. in order to control cohesion and improve heat resistance. An alkenyl group-containing compound or an α, β-unsaturated carboxylic acid ester, such as hydroxyl group, carboxyl group, amino group, amide group, maleimide group, nitrile group, epoxy group, alkoxysilyl group, allyl group, etc. Those having a functional group of Furthermore, a carboxyl group or a hydroxyl group is more preferable as the functional group in order to form a homogeneous cross-linked structure that does not clearly represent a dense distribution with the reactive compound (C). When the reactivity of the functional group in the copolymer (A) that reacts with the reactive compound (C) to form a crosslinked structure is slow, it takes a long time to complete the formation of the crosslinked structure. However, since it is not allowed for such a long time industrially, a uniform cross-linked state cannot be exhibited, and the pressure-sensitive adhesive layer has a sparse part and a dense part. The pressure-sensitive adhesive layer with such a coarse and dense distribution has a low cohesive force. Therefore, if the pressure-sensitive adhesive optical film is attached to an adherend and exposed to a harsh environment at high temperature or high humidity, it will be crosslinked. Since stress concentrates on the low density portion and foaming, floating and peeling are likely to occur, it is not preferable. Accordingly, the functional group in the copolymer (A) is preferably a carboxyl group or a hydroxyl group rich in reactivity.

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

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

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

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

  The weight average molecular weight (Mw) of the copolymer (A) is preferably 50,000 to 2,000,000 in terms of adhesiveness, and more preferably in the range of 200,000 to 1,500,000. preferable. When the Mw exceeds 2,000,000, the fluidity of the copolymer becomes poor, so that the coating property of the pressure-sensitive adhesive composition deteriorates, and the pressure-sensitive adhesive layer itself is produced on the peelable sheet. It becomes difficult. On the other hand, when Mw is less than 50,000, the pressure-sensitive adhesive optical layer is liable to cohesive failure after the pressure-sensitive adhesive optical film is attached to a liquid crystal cell member such as glass, such being undesirable.

It is important that the pressure-sensitive adhesive composition of the present invention contains a silane compound (B) having an amino group and an alkoxy group with an amine value of 0.5 to 200 (mgKOH / g). It is preferable that it is 3-150 (mgKOH / g). When the silane compound moves to the adherend interface, the silanol site reacts with moisture at the adherend interface to form a silanol bond. At this time, the presence of the amino group increases the polarity of the silane compound, increases the intermolecular affinity with the copolymer (A), and consequently increases the affinity with the copolymer. As a result, the bonding force between the adherend and the copolymer is increased, and it is estimated that the removability and durability are improved by efficiently transferring the silane compound (B) to the contact interface. The Therefore, when the amine value is lower than 0.5 mgKOH / g, the polarity of the silane compound (B) is lowered, the durability is lowered due to insufficient adhesion, or the layered silane compound ( Since the peelability from a peeling film deteriorates by the remarkable improvement of adhesiveness of B) and a peeling film, it is not preferable.
On the other hand, if the amine value is larger than 200 (mgKOH / g), the amino group which is a hydrophilic group takes in moisture in the atmosphere excessively, and as a result, hydrolysis of the silane compound (B) is promoted by moisture in the atmosphere. , Since self-condensate is formed and the molecular weight is increased, interfacial migration is hindered, and therefore re-peelability is deteriorated.
Further, the number average molecular weight (Mn) of the silane compound (B) in the present invention is more preferably 1,000 or more. When the number average molecular weight (Mn) is 1,000 or less, the silane compound (B) is not preferable because it is easily released due to its low molecular weight and the removability is lowered.

  A silane compound (B) having an amino group having an amine value of 0.5 to 200 (mgKOH / g) and an alkoxy group is a silane compound having an amino group and an alkoxy group having an amine value larger than 200 (mgKOH / g). It can be obtained by reacting (condensation, hydrolysis, etc.) the compound (b1) and the silane compound (b2) having an alkoxy group and not having an amino group.

  Examples of the silane compound (b1) having an amino group and an alkoxy group having an amine value larger than 200 (mgKOH / g) include γ-aminopropylmethyldiethoxysilane and N-β (aminoethyl) γ-aminopropylmethyldimethoxy. Silane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, and the like. It is done.

  Examples of the silane compound (b2) having an alkoxy group and not having an amino group include tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, Methyltriacetoxysilane, methyltris (methoxyethoxy) silane, methyltris (methoxypropoxy) silane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltriisopropoxysilane , Butyltrimethoxysilane, butyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltrimethoxysilane, octyltri Toxisilane, Decyltrimethoxysilane, Decyltriethoxysilane, Cyclohexyltrimethoxysilane, Cyclohexyltriethoxysilane, Vinyltrimethoxysilane, Vinyltriethoxysilane, Vinyltriisopropoxysilane, Vinyltriacetoxysilane, Vinyltris (methoxyethoxy) silane, Vinyltris (methoxypropoxy) silane, allyltrimethoxysilane, allyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriisopropoxysilane, phenyltriacetoxysilane, tolyltrimethoxysilane, tolyltriethoxysilane, chloromethyl Trimethoxysilane, chloromethyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloro Propyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, cyanoethyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycid Xylpropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyl Triethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, dimethyldimethoxysilane, di Tildiethoxysilane, dimethyldiisopropoxysilane, dimethyldiacetoxysilane, dimethylbis (methoxyethoxy) silane, dimethylbis (methoxypropoxy) silane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldiisopropoxysilane, diethyldiacetoxy Silane, methylethyldimethoxysilane, methylethyldiethoxysilane, methylethyldiisopropoxysilane, methylethyldiacetoxysilane, methylpropyldimethoxysilane, methylpropyldiethoxysilane, methylpropyldiisopropoxysilane, methylpropyldiacetoxysilane, Divinyldimethoxysilane, divinyldiethoxysilane, divinyldiisopropoxysilane, divinyldiacetoxysilane, methylvinyldi Methoxysilane, methylvinyldiethoxysilane, methylvinyldiisopropoxysilane, methylvinyldiacetoxysilane, diallyldimethoxysilane, diallyldiethoxysilane, diallyldiisopropoxysilane, methylallyldimethoxysilane, methylallyldiethoxysilane, methylallyl Diisopropoxysilane, methylallyldiacetoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldiisopropoxysilane, diphenyldiacetoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, methylphenyldiisopropoxysilane, methyl Phenyldiacetoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, 3 , 3,3-trifluoropropylmethyldimethoxysilane, nonafluorohexylmethyldimethoxysilane, cyanoethylmethyldiethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethylmethyldiethoxy Silane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, and the like, and tetraalkoxylane is preferable. Ethoxysilane is preferred.

  The silane compound (B) is obtained by hydrolyzing and condensing a mixture of a silane compound (b1) having an amino group and a silane compound (b2) having no amino group, or by hydrolyzing the silane compound (b2) having no amino group. It can be obtained by condensing the decomposition product with the silane compound (b1) having an amino group, and is preferably obtained by hydrolyzing and condensing the mixture. Moreover, it is also possible to use a commercial product as this silane compound (B). Examples of commercially available products include “X-40-2651” manufactured by Shin-Etsu Chemical Co., Ltd.

  The pressure-sensitive adhesive composition of the present invention preferably contains 0.01 to 5 parts by weight of the silane compound (B) with respect to 100 parts by weight of the copolymer (A), and 0.1 to 3 parts by weight. It is more preferable to contain. If it is less than 0.01 part by weight, the effect of suppressing cracks and the effect of improving removability cannot be expected. On the other hand, if it exceeds 5 parts by weight, the cohesive force is insufficient, foaming is likely to occur in the durability test, and the optical properties are deteriorated, which is not preferable.

In this invention, silane compounds other than the silane compound (B) which has an amino group and an alkoxy group can further be used as needed.
For example, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyl Dimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyl Methoxysilane, N- (2-aminoethyl) 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane Tetramethoxysilane copolymer, 3-methacryloxypropyltrimethoxysilane-tetraethoxysilane copolymer, 3-methacryloxypropyltriethoxysilane-tetramethoxysilane copolymer, 3-methacryloxypropyltriethoxysilane-tetraethoxysilane copolymer, 3-methacrylate Roxypropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-methacryloxypropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-methacryloxypropylmethyldiethoxysilane-tetramethoxysilane copolymer, 3-methacryloxypropylmethyldiethoxysilane- Tetraethoxysilane copolymer, 3-acryloxypropyltrimethoxysilane-tetramethoxysilane copolymer -, 3-acryloxypropyltrimethoxysilane-tetraethoxysilane copolymer, 3-acryloxypropyltriethoxysilane-tetramethoxysilane copolymer, 3-acryloxypropyltriethoxysilane-tetraethoxysilane copolymer, 3-acryloxypropylmethyl Dimethoxysilane-tetramethoxysilane copolymer, 3-acryloxypropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-acryloxypropylmethyldiethoxysilane-tetramethoxysilane copolymer, 3-acryloxypropylmethyldiethoxysilane-tetraethoxysilane Copolymer, vinyltrimethoxysilane-tetramethoxysilane copolymer, vinyltrimethoxysilane-tetraethoxysilane copolymer Vinyltriethoxysilane-tetramethoxysilane copolymer, vinyltriethoxysilane-tetraethoxysilane copolymer, vinylmethyldimethoxysilane-tetramethoxysilane copolymer, vinylmethyldimethoxysilane-tetraethoxysilane copolymer, vinylmethyldiethoxysilane-tetramethoxysilane copolymer Vinylmethyldiethoxysilane-tetraethoxysilane copolymer, and the like.

  The reactive compound (C) used in the present invention is a compound having in its molecule a functional group capable of reacting with a carboxyl group or a hydroxyl group in the copolymer (A). An isocyanate compound, an epoxy compound, an amine compound, an aziridine compound, a carbodiimide compound, an oxazoline compound, a melamine compound, a metal chelate, and the like can be mentioned. Among these, a carboxyl in the copolymer (A) is used to act as a crosslinking agent. A compound having two or more functional groups capable of reacting with a group or a hydroxyl group in the molecule is preferably used.

When the functional group in the copolymer (A) is a carboxyl group, examples of the functional group of the reactive compound (C) include an isocyanate group, an epoxy group, an amino group, an aziridyl group, and an oxazoline group. ) Is a hydroxyl group, examples of the functional group of the reactive compound (C) include an isocyanate group and an N-methylol group.
In particular, the polyisocyanate compound is preferably used because it is excellent in the adhesion of the resin composition after the crosslinking reaction and the adhesion to the coating layer.

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

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

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

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

  Examples of the tertiary amine compound include triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, diazabicycloundecene (DBU) and the like, and depending on the case, they can be used alone or in combination. .

Examples of organometallic compounds include tin compounds and non-tin compounds.
Examples of tin compounds include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (DBTDL), dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, tributyltin acetate , Triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate, tin 2-ethylhexanoate and the like.
Examples of non-tin compounds include titanium compounds such as dibutyltitanium dichloride, tetrabutyltitanate and butoxytitanium trichloride, lead compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate and lead naphthenate, 2- Examples thereof include iron-based compounds such as iron ethylhexanoate and iron acetylacetonate, cobalt-based compounds such as cobalt benzoate and cobalt 2-ethylhexate, zinc-based compounds such as zinc naphthenate and zinc 2-ethylhexanoate, and zirconium naphthenate. .
Among the above catalysts, dibutyltin dilaurate (DBTDL), tin 2-ethylhexanoate and the like are preferable in terms of reactivity and hygiene.

  Examples of the epoxy compound include bisphenol A-epichlorohydrin type epoxy resin, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol. Diglycidyl ether, trimethylolpropane triglycidyl ether, diglycidyl aniline, N, N, N ′, N′-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N′-diglycidylaminomethyl) And cyclohexane.

Examples of amine compounds are preferably polyamines having two or more primary amino groups, and a fatty acid which is a polyamine having two or more primary amino groups that are not directly bonded to an aromatic ring from the viewpoint of excellent curing speed. An aromatic polyamine (which may contain an aromatic ring in its skeleton) is preferred.
Aliphatic polyamines include 2,5-dimethyl-2,5-hexamethylenediamine, mensendiamine, 1,4-bis (2-amino-2-methylpropyl) piperazine, and propylene branched carbons at both ends of the molecule. Polypropylene glycol having an amino group bonded thereto (propylene skeleton diamine, such as “Jeffamine D230” and “Jeffamine D400” manufactured by Sun Techno Chemical Co., Ltd.), propylene skeleton triamine, such as “Jephamine T403”, ethylenediamine, Propylenediamine, butylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexamethylenediamine, trimethylhexamethylenediamine, N-aminoethylpiperazine, 1,2-dia Nopuropan, iminobispropylamine, methyl _{iminobispropylamine, H 2 N (CH 2 CH} 2 O) 2 (CH 2) 2 NH 2 [ Sun Techno Chemical Co., Ltd. "Jeffamine EDR148" (ethylene glycol skeleton diamine)] or the like Polyether skeleton diamine, 1,5-diamino-2-methylpentane (“MPMD” manufactured by DuPont Japan), metaxylylenediamine (MXDA), polyamidoamine (Sanwa Chemical) "X2000"), isophoronediamine, 1,3-bisaminomethylcyclohexane ("1,3BAC" manufactured by Mitsubishi Gas Chemical Company), 1-cyclohexylamino-3-aminopropane, 3-aminomethyl-3,3 5-Trimethyl-cyclohexylamine, dimethylene with norbornane skeleton Mention may be made of the Min (manufactured by Mitsui Chemicals, Inc. "NBDA"), and the like.
Among these, since the curing rate is particularly high, 1,3-bisaminomethylcyclohexane, dimethyleneamine having a norbornane skeleton, metaxylylenediamine, H ₂ N (CH ₂ CH ₂ O) ₂ (CH ₂ ) ₂ NH ₂ (ethylene glycol skeleton diamine), propylene skeleton diamine, propylene skeleton triamine, and polyamidoamine (trade name: X2000) are useful.

  Ketimine, which is a reaction product of these polyamines and ketones, is also included in the amino compound, and from the viewpoints of stability, reactivity adjustment and overcoatability, acetophenone or propiophenone and 1,3-bisaminomethylcyclohexane Obtained from acetophenone or propiophenone and dimethyleneamine (NBDA) having a norbornane skeleton; obtained from acetophenone or propiophenone and metaxylylenediamine; acetophenone or propiophenone; Also obtained from Jeffamine EDR148, Jeffamine D230, Jeffamine D400, etc., which are diamines having an ethylene glycol skeleton or propylene skeleton, or Jeffamine T403, which is a triamine having a propylene skeleton, etc. It is possible to use.

  Examples of aziridine compounds include N, N′-diphenylmethane-4,4′-bis (1-aziridinecarboxite), N, N′-toluene-2,4-bis (1-aziridinecarboxite), bisiso Phthaloyl-1- (2-methylaziridine), tri-1-aziridinylphosphine oxide, N, N′-hexamethylene-1,6-bis (1-aziridinecarboxite), trimethylolpropane-tri-β -Aziridinylpropionate, tetramethylolmethane-tri-β-aziridinylpropionate, tris-2,4,6- (1-aziridinyl) -1,3,5-triazine, trimethylolpropane tris [ 3- (1-aziridinyl) propionate], trimethylolpropane tris [3- (1-aziridinyl) butyrate], Trimethylolpropane tris [3- (1- (2-methyl) aziridinyl) propionate], trimethylolpropane tris [3- (1-aziridinyl) -2-methylpropionate], pentaerythritol tetra [3- (1- Aziridinyl) propionate], diphenylmethane-4,4-bis-N, N'-ethyleneurea, 1,6-hexamethylenebis-N, N'-ethyleneurea, 2,4,6- (triethyleneimino) -Syn -Triazine, bis [1- (2-ethyl) aziridinyl] benzene-1,3-carboxylic acid amide and the like.

  As the carbodiimide compound, a compound having two or more carbodiimide groups (—N═C═N—) in the molecule is preferably used, and known polycarbodiimides can be used.

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

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

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

  As the oxazoline compound, a compound having two or more oxazoline groups in the molecule is preferably used. Specifically, 2'-methylenebis (2-oxazoline), 2,2'-ethylenebis (2-oxazoline), 2 2,2'-ethylenebis (4-methyl-2-oxazoline), 2,2'-propylenebis (2-oxazoline), 2,2'-tetramethylenebis (2-oxazoline), 2,2'-hexamethylene Bis (2-oxazoline), 2,2'-octamethylenebis (2-oxazoline), 2,2'-p-phenylenebis (2-oxazoline), 2,2'-p-phenylenebis (4,4 ' -Dimethyl-2-oxazoline), 2,2'-p-phenylenebis (4-methyl-2-oxazoline), 2,2'-p-phenylenebis (4-phenyl- -Oxazoline), 2,2'-m-phenylenebis (2-oxazoline), 2,2'-m-phenylenebis (4-methyl-2-oxazoline), 2,2'-m-phenylenebis (4 4'-dimethyl-2-oxazoline), 2,2'-m-phenylenebis (4-phenylenebis-2-oxazoline), 2,2'-o-phenylenebis (2-oxazoline), 2,2'- o-phenylenebis (4-methyl-2-oxazoline), 2,2'-bis (2-oxazoline), 2,2'-bis (4-methyl-2-oxazoline), 2,2'-bis (4 -Ethyl-2-oxazoline), 2,2'-bis (4-phenyl-2-oxazoline) and the like. Alternatively, vinyl monomers such as 2-isopropenyl-2-oxazoline and 2-isopropenyl-4,4-dimethyl-2-oxazoline and other monomers that can be copolymerized with these vinyl monomers It may be a copolymer with the body.

  The melamine compound is a compound having a triazine ring in the molecule, and examples thereof include melamine, benzoguanamine, cyclohexanecarboguanamine, methylguanamine, vinylguanamine, hexamethoxymethylmelamine, tetramethoxymethylbenzoguanamine and the like. These low-condensates, alkyl etherified formaldehyde resins and aminoplast resins may also be used.

  Examples of metal chelate compounds 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 acetylacetone and ethyl acetoacetate. Can be mentioned.

  The pressure-sensitive adhesive composition of the present invention preferably contains 0.001 to 30 parts by weight of the reactive compound (C) with respect to 100 parts by weight of the copolymer (A), and 0.01 to 20 parts by weight. It is more preferable to contain part. If the amount of the reactive compound (C) used exceeds 30 parts by weight, the adhesiveness of the resulting pressure-sensitive adhesive layer tends to decrease, and if it is less than 0.001 parts by weight, the cohesive force decreases, and heat resistance and moisture resistance Thermal properties tend to decrease.

The pressure-sensitive adhesive composition of the present invention preferably contains an organic solvent, and other silane coupling agents, softeners, dyes, pigments, antioxidants as long as the effects of the present invention are not impaired. , Tackifier, plasticizer, filler, anti-aging agent and the like may be blended.
For example, the organic solvent such as acetone, methyl acetate, ethyl acetate, cyclohexane, toluene, methyl ethyl ketone, isopropyl alcohol, and other hydrocarbon solvents and water are further added to adjust the viscosity of the pressure sensitive adhesive composition. Alternatively, the pressure-sensitive adhesive composition can be heated to lower the viscosity.

The pressure-sensitive adhesive composition of the present invention is suitable as a pressure-sensitive adhesive composition for optical films. That is, it is preferably used for forming a pressure-sensitive adhesive optical film comprising an optical film and a pressure-sensitive adhesive layer located on at least one surface of the optical film.
The pressure-sensitive adhesive optical film of the present invention can be obtained as follows.
Apply and dry the pressure-sensitive adhesive composition on the release-treated surface of the release sheet, laminate the optical film on the surface of the pressure-sensitive adhesive layer, or apply and dry the pressure-sensitive adhesive composition on the optical film. Then, a pressure-sensitive adhesive optical film can be obtained by laminating the release-treated surface of the peelable sheet on the surface of the pressure-sensitive adhesive layer.
The reaction between the copolymer (A) and the silane compound (B) and the cross-linking reaction between the copolymer (A) and the reactive compound (C) are caused when the pressure-sensitive adhesive composition is dried and the formed sensitivity. When laminating a sheet-like optical film or peelable sheet on the surface of the pressure-sensitive adhesive layer, the process proceeds after the lamination.

  Examples of the peelable sheet include those obtained by subjecting the surface of a sheet-like substrate such as cellophane, various plastic sheets, and paper to a release treatment. Various sheet base materials can be used alone or in a multilayered state in which a plurality of base materials are laminated.

  Various plastic sheets are also referred to as various plastic films, such as polyvinyl alcohol films, triacetyl cellulose films, films of polyolefin resins such as polypropylene, polyethylene, polycycloolefin, and ethylene-vinyl acetate copolymer, polyethylene terephthalate and polybutylene terephthalate. Polyester resin 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, polyimide resin film, epoxy resin film and the like.

  Examples of the optical film used in the present invention include a polarizing film, a retardation film, an elliptically polarizing film, an antireflection film, and a brightness enhancement film.

  The polarizing film, also called a polarizing plate, is sandwiched between two triacetylcellulose protective films (hereinafter referred to as “TAC film”) and two cycloolefin films on both sides of a polyvinyl alcohol (PVA) polarizer. It is a multilayer structure film.

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

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

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

<Production of copolymer (A)>
(Synthesis Example 1)
The following α and β-unsaturated compounds were charged in the polymerization tank, the stirrer, the thermometer, the reflux condenser, the dropping device, and the polymerization tank and the dropping device of the polymerization reaction apparatus equipped with the nitrogen introduction tube at the following ratios, respectively.

[Polymerization tank]
N-butyl propenoate 29 parts methyl propenoate 20 parts propenoic acid 0.5 parts 4-hydroxybutyl propenoate 0.5 parts ethyl acetate 30 parts 2,2'-azobisisobutyronitrile 0.05 part [drip apparatus ]
N-butyl propenoate 49 parts propenoic acid 0.5 part propenoate 4-hydroxybutyl 0.5 part ethyl acetate 36 parts 2,2'-azobisisobutyronitrile 0.05 part

  After the air in the polymerization tank was replaced with nitrogen gas, the reaction was started at a reflux temperature in a nitrogen atmosphere while stirring. When the polymerization rate reached about 70%, the dropping of the mixture of the α, β-unsaturated compound, the polymerization initiator and the organic solvent was started from the dropping device. After completion of the dropwise addition, the mixture was further aged with stirring for 8 hours, and then 197 parts of toluene was added and cooled to room temperature. A transparent solution having a nonvolatile content of 30.1% containing a copolymer of α, β-unsaturated compound was obtained. Obtained. The Tg of the copolymer determined from DSC was −33 ° C.

(Synthesis Example 2)
The composition of the α, β-unsaturated compound used in Synthesis Example 1 was changed, and charged in the polymerization tank and the dropping device at the following ratios respectively. Otherwise, polymerization was performed in the same manner as in Synthesis Example 1, and α, β- A clear solution containing a copolymer of unsaturated compounds was obtained.
[Polymerization tank]
2-ethylhexyl propenoate 30 parts n-butyl propenoate 19 parts methyl 2-methylpropenoate 10 parts propenoic acid 1 part ethyl acetate 30 parts 2,2′-azobisisobutyronitrile 0.05 part [drip apparatus]
2-ethylhexyl propenoate 35 parts n-butyl propenoate 4 parts propenoic acid 1 part ethyl acetate 36 parts 2,2'-azobisisobutyronitrile 0.05 part

(Synthesis Example 3)
The composition of the α, β-unsaturated compound used in Synthesis Example 1 was changed, and charged in the polymerization tank and the dropping device at the following ratios respectively. Otherwise, polymerization was performed in the same manner as in Synthesis Example 1, and α, β- A clear solution containing a copolymer of unsaturated compounds was obtained.
[Polymerization tank]
Lauryl 2-methylpropenoate 30 parts Ethyl propenoate 9 parts Vinyl ethanoate 10 parts 2-Hydroxyethyl propenoate 1 part Ethyl acetate 30 parts 2,2'-Azobisisobutyronitrile 0.05 part [Drip device]
Lauryl 2-methylpropenoate 45 parts Ethyl propenoate 4 parts 2-Hydroxyethyl propenoate 1 part Ethyl acetate 36 parts 2,2'-Azobisisobutyronitrile 0.05 part

(Synthesis Example 4)
In addition to the α, β-unsaturated compound, an ultraviolet absorber is further added, and charged in the polymerization tank and the dropping device at the following ratios, respectively. Otherwise, polymerization is performed in the same manner as in Synthesis Example 1, and α, β-unsaturated. A transparent liquid containing a copolymer of the compound was obtained.
[Polymerization tank]
N-butyl propenoate 29 parts methyl 2-methylpropenoate 10 parts methyl propenoate 10 parts 4-hydroxybutyl propenoate 0.5 parts ethyl acetate 30 parts 2,2′-azobisisobutyronitrile 0.05 part [ Dripping device]
N-butyl propenoate 50 parts 4-hydroxybutyl propenoate 0.5 parts ethyl acetate 36 parts 2,2'-azobisisobutyronitrile 0.05 part

(Synthesis Example 5)
The composition of the α, β-unsaturated compound used in Synthesis Example 1 was changed, and charged in the polymerization tank and the dropping device at the following ratios respectively. Otherwise, polymerization was performed in the same manner as in Synthesis Example 1, and α, β- A clear solution containing a copolymer of unsaturated compounds was obtained.
[Polymerization tank]
2-ethylhexyl propenoate 20 parts methyl propenoate 30 parts propenoic acid 1 part ethyl acetate 30 parts 2,2′-azobisisobutyronitrile 0.05 part [drip apparatus]
2-ethylhexyl propenoate 47 parts propenoic acid 2 parts ethyl acetate 36 parts 2,2'-azobisisobutyronitrile 0.05 part

(Synthesis Example 6)
The composition of the α, β-unsaturated compound used in Synthesis Example 1 was changed, and charged in the polymerization tank and the dropping device at the following ratios respectively. Otherwise, polymerization was performed in the same manner as in Synthesis Example 1, and α, β- A clear solution containing a copolymer of unsaturated compounds was obtained.
[Polymerization tank]
N-Butyl propenoate 30 parts Benzyl propenoate 20 parts 2-Methylpropenoate 2-hydroxyethyl 1 part Ethyl acetate 30 parts 2,2'-azobisisobutyronitrile 0.05 part [Drip device]
N-Butyl propenoate 48 parts 2-Methylpropenoate 2-hydroxyethyl 1 part Ethyl acetate 36 parts 2,2'-Azobisisobutyronitrile 0.05 part

  For the α, β-unsaturated compound copolymer (A) obtained in Synthesis Examples 1 to 6, the solution appearance, nonvolatile content concentration (%), solution viscosity, weight average molecular weight (Mw), and Tg were determined as follows. The results are shown in Table 1.

<< Solution appearance >>
The appearance of the copolymer (A) solution was visually evaluated.

<Measurement of non-volatile content>
About 1 g of each solution of copolymer (A) is weighed in a metal container, dried in an oven at 150 ° C. for 20 minutes, the residue is weighed, and the remaining rate is calculated. did.

<< Measurement of solution viscosity >>
Each solution of the copolymer (A) was measured at 23 ° C. with a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd.) using a # 3 rotor at 12 rpm for 1 minute, and the solution viscosity (mPa S)

<< Measurement of weight average molecular weight (Mw) >>
The weight average molecular weight (Mw) of the copolymer (A) was measured using Showa Denko GPC (gel permeation chromatography) “Shodex GPC System-21”. GPC is liquid chromatography that separates and quantifies substances dissolved in a solvent based on the difference in molecular size, and the weight average molecular weight (Mw) is determined in terms of polystyrene.

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

Example 1
To 100 parts by weight of the copolymer solution obtained in Synthesis Example 1, 15 parts by weight of toluene was added, and as a silane alkoxy oligomer (B) having an amino group and an alkoxy group, “X-40-2651” ( 1.0 parts by weight of Shin-Etsu Chemical Co., Ltd.) and 1.5 parts by weight of TDI / TMP (tolylene diisocyanate trimethylopropanepropane adduct) may be added as the reactive compound (C). Stirring to obtain a pressure sensitive adhesive composition.
This was coated on a release-treated polyester film (hereinafter referred to as “release film”) so that the thickness after drying was 25 μm, and dried at 100 ° C. for 2 minutes to form a pressure-sensitive adhesive layer. .
After drying, one side of a polarizing film having a multilayer structure in which both sides of a polyvinyl alcohol (PVA) polarizer are sandwiched between triacetyl cellulose-based protective films (hereinafter referred to as “TAC film”) is bonded to the resin layer. A laminate having a structure of “/ pressure-sensitive adhesive layer / TAC film / PVA / 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 a pressure-sensitive adhesive optical film.

(Comparative Example 1)
Example 1 except that the silane alkoxy oligomer (B) “X-40-2651” (manufactured by Shin-Etsu Chemical Co., Ltd.) having an amino group and an alkoxy group is not added to the copolymer solution obtained in Synthesis Example 1. In the same manner as described above, a pressure-sensitive adhesive optical film was obtained.

(Comparative Example 2)
In place of the silane alkoxy oligomer “X-40-2651” (manufactured by Shin-Etsu Chemical Co., Ltd.) having an amino group and an alkoxy group, the mercapto group-containing silane alkoxy oligomer is added to the copolymer solution obtained in Synthesis Example 1. A pressure-sensitive adhesive optical film was prepared in the same manner as in Example 1 except that 1.0 part by weight of X-41-1805 ”(manufactured by Shin-Etsu Chemical Co., Ltd.) was added.

(Comparative Examples 3-5)
Instead of the silane alkoxy oligomer “X-40-2651” (manufactured by Shin-Etsu Chemical Co., Ltd.) having an amino group and an alkoxy group, the copolymer solution obtained in Synthesis Example 1 (manufactured by Shin-Etsu Chemical Co., Ltd.) “KBE-603” = N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, “KBM-573” = N-phenyl-3-aminopropyltrimethoxysilane, “KBM-403” = 3- A pressure-sensitive adhesive optical film was produced in the same manner as in Example 1 except that 1.0 part by weight of glycidoxypropyltrimethoxysilane was added.

(Examples 2 to 4)
In Example 2, instead of TDI / TMP, the copolymer solution obtained in Synthesis Example 1 was replaced with HBAP (2,2′-bishydroxymethylbutanol tris [3- (1- Aziridinyl) propionate]), TGMXDA (N, N, N ′, N′-tetraglycidyl-m-xylylenediamine) in Example 3, V-05 (“carbodilite V-05” which is a carbodiimide compound) in Example 4. : Nisshinbo Co., Ltd.) was added in the same manner as in Example 1 except that 0.15 parts of each was added.

(Example 5)
15 parts of isopropyl alcohol (IPA) is added to the copolymer solution obtained in Synthesis Example 1, and 0.15 parts by weight of Al chelate (aluminum tris (acetylacetonate)) is added as a reactive reaction product (C). And well stirred to obtain a pressure-sensitive adhesive composition of the present invention. Using this, a pressure-sensitive adhesive optical film was produced in the same manner as in Example 1.

(Examples 6 and 7)
A pressure-sensitive adhesive optical film was prepared in the same manner as in Example 1 except that the copolymer solutions obtained in Synthesis Examples 2 and 5 were used instead of the copolymer solution obtained in Synthesis Example 1, respectively. Produced.

(Examples 8 to 10)
The pressure-sensitive adhesive optics were the same as in Example 1 except that the copolymer solutions obtained in Synthesis Examples 3, 4, and 6 were used instead of the copolymer solution obtained in Synthesis Example 1, respectively. A film was prepared.

(Examples 11 to 16)
In contrast to the copolymer solutions obtained in Synthesis Examples 3, 4 and 6 used in Examples 8 to 10, in Examples 11 to 13, XDI / TMP (xylylene diisocyanate) was used as the reactive compound (C). The trimethylolpropane adduct body of Example 14 to 16 was carried out except that 1.5 parts of HMDI / burette (hexamethylene diisocyanate burette adduct body) was added as the reactive compound (C). In the same manner as in Examples 8 to 10, pressure-sensitive adhesive optical films were produced.

  About the silane compound (B) and various silane coupling agents used in each Example and each Comparative Example, the amine value (mgKOH / g) and the number average molecular weight were determined according to the following methods, and the results are shown in Table 2. In addition, the molecular weight of the silane compound used in Comparative Examples 3 to 5 is a calculated value.

<< Measurement of amine value (mgKOH / g) >>
About 1 g of a sample is accurately weighed in a 200 ml conical beaker and dissolved by adding 50 ml of a toluene / isopropyl alcohol (weight ratio 1: 1) mixture. Further, add 30 ml of methanol and dissolve sufficiently. This is titrated with 0.1N hydrochloric acid solution. The titration end point was judged from potentiometric titration (automatic potentiometric titrator GT-100 manufactured by Mitsubishi Chemical Corporation), and the amine value was calculated from the obtained end point.
The amine value was determined by the following formula. The amine value was a numerical value of the dry state of the resin (unit: mgKOH / g).
Amine value (mgKOH / g) = a × 0.1 × 56.1 × F / (sample weight (g) × solid content (%))
Where S: Amount of sample collected (g)
a: Consumption of 0.1N hydrochloric acid solution (ml)
F: Potency of 0.1N hydrochloric acid solution

<< Measurement of Number Average Molecular Weight (Mn) >>
The number average molecular weight (Mn) of the silane compound (B) was measured using GPC (gel permeation chromatography) “HPC-8020” manufactured by Tosoh Corporation.
GPC is liquid chromatography in which a substance dissolved in a solvent (THF; tetrahydrofuran) is separated and quantified by the difference in molecular size, and the number average molecular weight (Mn) is determined in terms of polystyrene.

  Various performances of the pressure-sensitive adhesive compositions and the pressure-sensitive adhesive optical films obtained in the examples and comparative examples were evaluated by the following methods. The results are shown in Table 3.

<Evaluation method of pot life>
About the pressure sensitive adhesive composition obtained in each Example and Comparative Example, after addition of the reactive compound (C), at 25 ° C. every 1 hour up to 10 hours with a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd.) The viscosity was measured under the conditions of 12 rpm and 1 minute rotation, and the pot life was evaluated in three stages.
○: No problem at all. Viscosity increase rate up to 12 hours is less than 2 times.
Δ: A slight increase in viscosity is observed, and the rate of increase in viscosity up to 12 hours is less than twice.
X: A sudden increase in viscosity was observed and gelled in less than 12 hours. There are practical problems.

<Evaluation method of coating processability>
The pressure-sensitive adhesive composition obtained in each Example and Comparative Example was applied to a release-treated polyester film with a comma coater at a speed of 2 m / min, dried in a 100 ° C. oven, and a thickness of 25 μm. A pressure-sensitive adhesive layer was formed, and a 50 μm thick polyester film was bonded to the surface of the pressure-sensitive adhesive layer to produce a pressure-sensitive adhesive sheet. The state of the coated surface was visually observed and evaluated in three stages.
○: No problem at all.
Δ: Slight repellency and foaming are observed at the end of the coated surface, but there is no practical problem.
X: Repelling, foaming and streaking are recognized on the coated surface, and there are practical problems.

<< Evaluation method of optical characteristics >>
The pressure-sensitive adhesive compositions obtained in each Example and Comparative Example were applied to the release-treated polyester film and dried in the same manner as described above to form a pressure-sensitive adhesive layer having a thickness of 25 μm. A pressure-sensitive adhesive sheet in which a release-treated polyester film was bonded to the surface of the pressure-sensitive adhesive layer was obtained. The pressure-sensitive adhesive sheet sandwiched between the release-treated polyester films was aged for one week under conditions of a temperature of 23 ° C. and a relative humidity of 50%. Then, both release-treated polyester films were removed, and the pressure-sensitive adhesive layer alone was removed. While visually judging the appearance, HAZE was measured by “NDH-300A” [manufactured by Nippon Denshoku Industries Co., Ltd.].
○: No problem in practical use. HAZE: less than 1.
(Triangle | delta): Cloudiness etc. are not recognized and it is 1 or more and less than 3.
X: Some cloudiness is recognized or HAZE: 3 or more. There are practical problems.

<Peelability of release sheet>
Using the pressure-sensitive adhesive compositions obtained in each Example and Comparative Example, a laminate having a configuration of “release film / pressure-sensitive adhesive layer / TAC film / PVA / TAC film” was obtained.
Next, the obtained laminate was aged at a temperature of 23 ° C. and a relative humidity of 50% for 1 week, and then the release film covering one surface of the pressure-sensitive adhesive layer was peeled off, and the peelability at that time (JIS K6301). In accordance with the peel strength and transferability of the adhesive to the release film).
Separately, the obtained laminate was aged for 3 weeks at a temperature of 23 ° C. and a relative humidity of 50%, and then the release film was peeled off in the same manner, and the peelability at that time was evaluated.
○: “The peel strength after 3 weeks is less than 1.2 times that after aging for 1 week, and there is no transfer of the adhesive to the release film, and there is no problem in practical use.”
Δ: “The peel strength after 3 weeks is 1.2 times or more and less than 1.5 times after aging for 1 week, there is no transfer of the adhesive to the release film, and there is no practical problem.”
X: “The peel strength after 3 weeks is 1.5 times or more after aging for 1 week, or the transfer of the adhesive to the release film is observed.

<Evaluation method of removability (reworkability)>
The pressure-sensitive adhesive optical film obtained in each Example and Comparative Example was cut into a size of 25 mm × 150 mm, the release film was peeled off, and was attached to a float glass plate with a thickness of 1.1 mm using a laminator, 50 ° C. And kept in an autoclave at 5 atm for 20 minutes to obtain a laminate of a polarizing plate and a glass plate.
The laminate was allowed to stand at 23 ° C. and 50% relative humidity for 1 week, and then peeled off at a speed of 300 mm / min in the direction of 180 °. The haze on the glass surface after peeling was visually observed and evaluated in three stages.
○: No cloudiness and no problem in practical use.
Δ: Some cloudiness is observed, but there is no practical problem.
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 pressure-sensitive adhesive optical film obtained in each example and comparative example was cut into a size of 150 mm × 80 mm, the release film was peeled off, and the absorption of each polarizing plate on both surfaces of a 1.1 mm thick float glass plate The laminator was used to stick the axes so that they were orthogonal. Subsequently, the glass plate on which the polarizing plate was attached was held in an autoclave at 50 ° C. and 5 atm for 20 minutes to obtain a laminate of the polarizing plate and the glass plate.
As evaluation of heat resistance, floating peeling after leaving the laminate at 95 ° C. for 1000 hours, and light leakage (white spots) when light was transmitted through the laminate were visually observed.
In addition, as an evaluation of moisture and heat resistance, the laminate was left to stand for 1000 hours at 80 ° C. and a relative humidity of 90%, and light leakage (white spots) when light was transmitted through the laminate was visually observed. did.
The heat resistance and moist heat resistance were evaluated based on the following four-stage evaluation criteria.
A: No floating peeling, foaming or whitening is observed, and there is no problem in practical use.
○: No floating peeling or whitening was observed, the deviation was less than 0.2 mm, and there was no problem in practical use.
Δ: Slightly floating peeling, foaming, and whitening are observed, but the displacement is less than 02 to 0.5 mm, and there is no practical problem. X: There are floating peeling, foaming, and whitening, which is not practical.

As described above, it can be seen that the pressure-sensitive adhesive composition of the present invention is excellent in coating processability, heat resistance, moisture and heat resistance, optical properties, peelability of the release film, and rework.
On the other hand, in the case of the comparative example 1 which does not contain a silane compound (B) and the comparative example 3 which has an amino group but has a too large amine value, it turns out that rework property is unsatisfactory. Moreover, in the comparative example 2 which uses the silane compound "X-41-1805" which does not have an amino group in a molecule | numerator, the peelability of a peeling film becomes inferior. Furthermore, Comparative Example 4 using a silane compound having an amino group but a low amine value, and Comparative Example 5 using a silane compound having no amino group and a low molecular weight have poor reworkability, and When it is left on a glass plate for a long period of time under high temperature or high temperature and high humidity, foaming or peeling off occurs, and it is recognized that the durability is poor.

Claims (7)

Copolymer (A) having a glass transition temperature of −80 to 10 ° C. and having an amine value of 0.5 to 200 (mgKOH) having at least one of a carboxyl group or a hydroxyl group, which is obtained by copolymerizing an α, β-unsaturated compound / G) a silane compound (B) having an amino group and an alkoxy group, and a reactive compound (C) capable of reacting with at least one of a carboxyl group and a hydroxyl group in the copolymer (A). A pressure-sensitive adhesive composition.   The silane compound (B) is a silane compound (b1) having an amino group and an alkoxy group having an amine value greater than 200 (mgKOH / g), and a silane compound (b2) having an alkoxy group and no amino group. The pressure-sensitive adhesive composition according to claim 1, wherein the pressure-sensitive adhesive composition is a reaction product (B1). Copolymerization of α, β-unsaturated compound having carboxyl group or hydroxyl group in side chain (A) 100 parts by weight of silane compound (B) 0.01-5 parts by weight and reactive compound (C) 0. The pressure-sensitive adhesive composition according to claim 1 or 2, comprising 001 to 30 parts by weight. The α, β-unsaturated compound essentially comprises at least one compound selected from propenoic acid, 2-methylpropenoic acid, a propenoic acid derivative and a 2-methylpropenoic acid derivative. Any one of the pressure-sensitive-type adhesive compositions. The carboxyl group in the copolymer (A) is derived from at least one of propenoic acid or 2-methylpropenoic acid, and the hydroxyl group in the copolymer (A) is a propenoic acid derivative having a hydroxyl group or 2-methyl having a hydroxyl group. Propenoic acid, 2-methylpropenoic acid, propenoic acid derivative having a hydroxyl group and 2-methylpropenoic acid derivative having a hydroxyl group in a total of 100% by weight of the α, β-unsaturated compound derived from at least one of the propenoic acid derivatives The pressure-sensitive adhesive composition according to claim 4, wherein the total is 0.01 to 20% by weight. The pressure-sensitive type according to any one of claims 1 to 5, wherein the reactive compound (C) has two or more functional groups capable of reacting with a carboxyl group or hydroxyl groups per molecule. Adhesive composition. A pressure-sensitive adhesive optical film comprising an optical film and a pressure-sensitive adhesive layer located on at least one surface of the optical film, wherein the pressure-sensitive adhesive layer is a pressure-sensitive adhesive according to any one of claims 1 to 6. A pressure-sensitive adhesive optical film formed from a composition.