JP2011190336A - Adhesive composition and adhesive sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an adhesive composition that has excellent transparency, adhesiveness and durability, has an easily adjustable refractive index and has a simple production method. <P>SOLUTION: The adhesive composition includes a polymerizable compound represented by formula (I) (wherein L is a direct bond or substituent represented by any of formulas (II)-(IV); X<SP>1</SP>, X<SP>2</SP>, X<SP>3</SP>, X<SP>4</SP>, X<SP>5</SP>, X<SP>6</SP>, X<SP>7</SP>and X<SP>8</SP>are each independently 1-10C alkyl which is substituted with a halogen atom or is not substituted, 6-20C aryl, 7-20C arylalkyl or a 2-20C heterocyclic group, hydrogen atom and halogen atom; and a methylene in the alkyl, aryl and arylalkyl may be interrupted by a unsaturated bond, -O-, -S-, -CO-, -COO- or -OCO-). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet. The pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet of the present invention are suitable for use in optical films for image display devices. The present invention also relates to a novel styrenic polymerizable compound useful as a raw material for pressure-sensitive adhesives.

  In recent years, images of liquid crystal display (LCD), plasma display panel (PDP), electroluminescence display (ELD), cathode ray tube display (CRT), fluorescent display tube, field emission display (FED), projection display, touch panel, etc. There is a growing demand for higher functionality such as improved brightness and visibility of optical films used in display devices.

As an optical film used for the image display device, for example, in LCD, an optical film such as a polarizing plate, a retardation film, an elliptically polarizing film, an optical isotropic film, a viewing angle widening film, a brightness enhancement film, and a light guide plate is used. It has been.
In the PDP, light that causes a deterioration in display quality such as 480 to 520 nm between blue and green, 550 to 600 nm between green and red, and light that causes malfunction of peripheral devices of 750 to 1100 nm. Optical films that selectively absorb light of unnecessary wavelength such as; optical films that absorb light of wavelengths of 480 to 500 nm and 540 to 560 nm to prevent reflection or reflection of external light such as fluorescent lamps; Optical film that absorbs ultraviolet rays to prevent the dye contained in the optical filter from being deteriorated by ultraviolet rays derived from sunlight, etc .; electromagnetic wave shielding film; color correction function, near infrared absorption function, ultraviolet absorption function, etc. Composite films that are integrated with each other are used.

  These optical films are used, for example, by adhering to the surface of the substrate of the image display device via an adhesive layer, and when using an adhesive layer, if the difference in the refractive index between the optical film and the adhesive layer is large, There was a problem that light was reflected at the interface between the optical film and the pressure-sensitive adhesive layer, and the transmittance of light from a backlight or the like was lowered. Also, if a refractive index adjuster is used to solve this, the compatibility with the adhesive is poor, the refractive index adjuster bleeds out or crystallizes in the adhesive layer, uneven reflection, reduced transmittance, There was a problem that a whitening phenomenon occurred.

From the viewpoint of reducing power consumption by effective use of light, it is required to prevent reflection in the backlight direction at the interface between the optical film and the pressure-sensitive adhesive layer.
The refractive index of materials generally used for optical films is 1.47 for triacetyl acetate (TAC), 1.49 to 1.53 for polyvinyl alcohol (PVA), 1.54 for polyethylene terephthalate (PET), polycarbonate (PC) has a wide range of 1.585 and glass 1.52, and the adhesive that bonds these materials has a ratio of total reflection as close as possible to these polymer materials and glass. It is necessary to reduce the transmittance and improve the transmittance.

  For example, Patent Document 1 discloses a pressure-sensitive adhesive composition that can reduce the total reflection of light at the interface between an optical film or an optical member and a pressure-sensitive adhesive layer by adjusting the refractive index of the pressure-sensitive adhesive, and An optical film having a pressure-sensitive adhesive layer formed of the pressure-sensitive adhesive composition is disclosed. Patent Document 2 discloses a pressure-sensitive adhesive having a high refractive index. Patent Document 3 discloses a liquid crystal display that is excellent in adhesion between the optical laminate and the glass substrate even under high temperature and high humidity conditions and that can suppress white spots caused by shrinkage of the optical film. An optical laminate with an adhesive layer for obtaining a plate is disclosed. Patent Document 4 discloses an optical pressure-sensitive adhesive composition in which the birefringence of the pressure-sensitive adhesive layer is brought close to zero and does not cause color unevenness and white spots in a liquid crystal element. However, these optical films are not satisfactory in terms of adhesiveness, durability, transparency and the like.

JP 2002-173656 A Special table 2003-535921 gazette JP 2006-330714 A JP 2007-169329 A

  An object of the present invention is to provide a pressure-sensitive adhesive composition which is excellent in transparency, adhesiveness and durability, can easily adjust the refractive index, and has a simple production method, and a pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive composition. It is to provide an adhesive sheet having excellent light transmittance.

  As a result of extensive studies, the present inventor can adjust the refractive index of the pressure-sensitive adhesive layer by preparing a pressure-sensitive adhesive composition using a styrenic novel polymerizable compound having a specific structure. The total refractive index is reduced by reducing the refractive index difference at the layer interface, and the birefringence of the pressure-sensitive adhesive composition is lowered. It was found that the light transmission efficiency can be improved as a result.

  This invention is made | formed based on the said knowledge, and provides the adhesive composition containing the polymeric compound represented by the following general formula (I).

（式中、Ｌは、直接結合又は下記一般式（II）〜（IV）のいずれかで表される置換基であり、Ｘ¹、Ｘ²、Ｘ³、Ｘ⁴、Ｘ⁵、Ｘ⁶、Ｘ⁷及びＸ⁸は、それぞれ独立して、ハロゲン原子で置換されているか無置換の炭素原子数１〜１０のアルキル基、炭素原子数６〜２０のアリール基、炭素原子数７〜２０のアリールアルキル基若しくは炭素原子数２〜２０の複素環基、水素原子、又はハロゲン原子を表し、該アルキル基、アリール基及びアリールアルキル基中のメチレン基は不飽和結合、−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−又は−ＯＣＯ−で中断されていてもよい。）

(In the formula, L is a direct bond or a substituent represented by any one of the following general formulas (II) to (IV), and X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ and X ⁸ are each independently a halogen atom-substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryl having 7 to 20 carbon atoms. Represents an alkyl group or a heterocyclic group having 2 to 20 carbon atoms, a hydrogen atom, or a halogen atom, and the methylene group in the alkyl group, aryl group and arylalkyl group is an unsaturated bond, -O-, -S-, (It may be interrupted by -CO-, -COO- or -OCO-).

（式中、Ｘ⁹、Ｘ¹⁰、Ｘ¹¹、Ｘ¹²、Ｘ¹³、Ｘ¹⁴、Ｘ¹⁵、Ｘ¹⁶、Ｘ¹⁷、Ｘ¹⁸、Ｘ¹⁹及びＸ²⁰は、それぞれ独立して、ハロゲン原子で置換されているか無置換の炭素原子数１〜１０のアルキル基、炭素原子数６〜２０のアリール基、炭素原子数７〜２０のアリールアルキル基若しくは炭素原子数２〜２０の複素環基、水素原子、又はハロゲン原子を表し、該アルキル基、アリール基及びアリールアルキル基中のメチレン基は不飽和結合、−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−又は−ＯＣＯ−で中断されていてもよく、Ｘ⁹、Ｘ¹⁰、Ｘ¹¹及びＸ¹²中、Ｘ¹³、Ｘ¹⁴、Ｘ¹⁵及びＸ¹⁶中並びにＸ¹⁷、Ｘ¹⁸、Ｘ¹⁹及びＸ²⁰中の隣接する置換基は互いに環を形成していてもよく、
Ｙは、ハロゲン原子で置換されているか無置換の炭素原子数１〜１０のアルキル基、炭素原子数６〜２０のアリール基、炭素原子数７〜２０のアリールアルキル基若しくは炭素原子数２〜２０の複素環基、又はハロゲン原子を表し、該アルキル基、アリール基及びアリールアルキル基中のメチレン基は不飽和結合、−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−又は−ＯＣＯ−で中断されていてもよく、
ｓは０〜８の数を表し、ｘは０〜４の数を表し、ｙは０〜４の数を表し、ｘとｙの数の合計は２〜４であり、
Ｒ¹及びＲ²は、ハロゲン原子で置換されているか無置換の炭素原子数１〜１０のアルキル基又は炭素原子数６〜２０のアリール基を表し、Ｒ¹及びＲ²は互いに環を形成していてもよい。）

(In the formula, X ⁹ , X ¹⁰ , X ¹¹ , X ¹² , X ¹³ , X ¹⁴ , X ¹⁵ , X ¹⁶ , X ¹⁷ , X ¹⁸ , X ¹⁹ and X ²⁰ are each independently substituted with a halogen atom. Or an unsubstituted alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms, a hydrogen atom Or a methylene group in the alkyl group, aryl group and arylalkyl group is interrupted by an unsaturated bond, -O-, -S-, -CO-, -COO- or -OCO-. In X ⁹ , X ¹⁰ , X ¹¹ and X ¹² , adjacent substituents in X ¹³ , X ¹⁴ , X ¹⁵ and X ^{16 and} in X ¹⁷ , X ¹⁸ , X ¹⁹ and X ²⁰ May be formed,
Y is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or 2 to 20 carbon atoms. A methylene group in the alkyl group, aryl group and arylalkyl group is an unsaturated bond, -O-, -S-, -CO-, -COO- or -OCO-. May be interrupted,
s represents the number of 0-8, x represents the number of 0-4, y represents the number of 0-4, the sum of the number of x and y is 2-4,
R ¹ and R ² represent a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R ¹ and R ² form a ring together. It may be. )

The present invention also provides a (co) polymer-containing pressure-sensitive adhesive composition obtained by (co) polymerizing the polymerizable compound represented by the general formula (I) contained in the pressure-sensitive adhesive composition. It is.
Moreover, this invention provides the adhesive sheet which has an adhesive layer formed from the said (co) polymer containing adhesive composition.
Moreover, this invention provides the polymeric compound represented by the said general formula (I).

The pressure-sensitive adhesive composition of the present invention is excellent in transparency, adhesiveness and durability, and has a simple production method.
Moreover, the pressure-sensitive adhesive composition of the present invention further contains an optional polymerizable compound other than the polymerizable compound represented by the above general formula (I), and copolymerizes it to give a refractive index of 1.45 to 1. .. can be arbitrarily adjusted within the range of 60. Therefore, if an adhesive layer is formed from the adhesive composition of the present invention and an optical film such as a polarizing film is attached to the substrate of the image display device, the reflectance at the interface between the adhesive layer and the optical film is minimized. The transmission efficiency of light from the backlight can be improved.
Furthermore, since the polymerizable compound represented by the general formula (I) contained in the pressure-sensitive adhesive composition of the present invention has a structure in which birefringence hardly occurs, the dimensional change in elongation / contraction with time In addition, it is possible to provide a pressure-sensitive adhesive layer in which birefringence due to orientation is reduced and white unevenness and white spots are suppressed.

Hereinafter, the pressure-sensitive adhesive composition of the present invention and the polymerizable compound of the present invention will be described in detail.
The pressure-sensitive adhesive composition of the present invention is a polymerizable composition comprising at least one polymerizable compound of the present invention represented by the general formula (I). In the polymerizable compound of the present invention, X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ and X ^{8 in} the above general formula (I), X ⁹ in the above general formula (II) , X ¹⁰ , X ¹¹ , X ¹² , X ¹³ , X ¹⁴ , X ¹⁵ and X ¹⁶ , X ¹⁷ , X ¹⁸ , X ¹⁹ and X ²⁰ and Y in the general formula (III), and the general formula (IV ) Of R ¹ and R ² , which are substituted or unsubstituted alkyl groups having 1 to 10 carbon atoms include, for example, methyl, ethyl, propyl, isopropyl, butyl, s-butyl, t -Butyl, isobutyl, amyl, isoamyl, t-amyl, hexyl, heptyl, isoheptyl, t-heptyl, n-octyl, isooctyl, t-octyl, 2-ethylhexyl, n-nonyl, n-decyl, trifluoromethyl, difluoro Methyl, monofluoromethyl, Interfluoroethyl, tetrafluoroethyl, trifluoroethyl, difluoroethyl, heptafluoropropyl, hexafluoropropyl, pentafluoropropyl, tetrafluoropropyl, trifluoropropyl, perfluorobutyl, methoxy, methoxyethoxy, methoxyethoxyethoxy, methylthio, Ethoxy, vinyloxy, propoxy, isopropoxy, butoxy, isobutoxy, t-butoxy, t-butoxycarbonylmethoxy, pentyloxy, isopentyloxy, t-pentyloxy, neopentyloxy, hexyloxy, cyclohexyloxy, isohexyloxy, heptyl Oxy, octyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy, cyclopropyl, cyclobutyl, cyclope Chill, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, straight chains such as cyclodecyl, for example, an alkyl group of branched and cyclic.

X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ and X ^{8 in} the general formula (I), X ⁹ , X ¹⁰ , X ¹¹ , X in the general formula (II) ¹² , X ¹³ , X ¹⁴ , X ¹⁵ and X ¹⁶ , X ¹⁷ , X ¹⁸ , X ¹⁹ and X ²⁰ and Y in the general formula (III), and R ¹ and R ² in the general formula (IV) Examples of the substituted or unsubstituted aryl group having 6 to 20 carbon atoms represented by halogen atom include phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 1-phenanthryl, o-tolyl, m -Tolyl, p-tolyl, 3-fluorenyl, 9-fluorenyl, 1-tetrahydronaphthyl, 2-tetrahydronaphthyl, 1-acenaphthenyl, 1-indanyl, 2-indanyl, 4-vinylphenyl, 3-isopropylphenyl, 4-isopropyl Phenyl, 4-butylpheny 4-isobutylphenyl, 4-t-butylphenyl, 4-hexylphenyl, 4-cyclohexylphenyl, 4-octylphenyl, 4- (2-ethylhexyl) phenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2,4-di-t-butylphenyl, 2,5-di-t-butylphenyl 2,6-di-t-butylphenyl, 2,4-di-t-pentylphenyl, 2,5-di-t-amylphenyl, cyclohexylphenyl, biphenyl, 2,4,5-trimethylphenyl, 4- Chlorophenyl, 3,4-dichlorophenyl, 4-trichlorophenyl, 4-trifluorophenyl, perfluorophenyl, fluoro Noxy, 2-methylphenoxy, 3-methylphenoxy, 4-methylphenoxy, 2,3-dimethylphenoxy, 2,4-dimethylphenoxy, 2,5-dimethylphenoxy, 2,6-dimethylphenoxy, 3,4-dimethyl Phenoxy, 3,5-dimethylphenoxy, 2,3,4-trimethylphenoxy, 2,3,5-trimethylphenoxy, 2,3,6-trimethylphenoxy, 2,4,5-trimethylphenoxy, 2,4,6 -Trimethylphenoxy, 3,4,5-trimethylphenoxy, 2,3,4,5-tetramethylphenoxy, 2,3,4,6-tetramethylphenoxy group, 2,3,5,6-tetramethylphenoxy, Pentamethylphenoxy, ethylphenoxy, n-propylphenoxy, isopropylphenoxy, n-buty Ruphenoxy, sec-butylphenoxy, tert-butylphenoxy, n-hexylphenoxy, n-octylphenoxy, n-decylphenoxy, n-tetradecylphenoxy, 1-naphthoxy, 2-naphthoxy, 1-anthryloxy, 1- Phenanthryloxy, o-tolyloxy, m-tolyloxy, p-tolyloxy, 9-fluorenyloxy, 1-tetrahydronaphthoxy, 2-tetrahydronaphthoxy, 1-acenaphthenyloxy, 1-indanyloxy, 2 -Indanyloxy etc. are mentioned.

X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ and X ^{8 in} the general formula (I), X ⁹ , X ¹⁰ , X ¹¹ , X in the general formula (II) ¹² , X ¹³ , X ¹⁴ , X ¹⁵ and X ¹⁶ , X ¹⁷ , X ¹⁸ , X ¹⁹ and X ^{20 in} the above general formula (III) or substituted or unsubstituted carbon with a halogen atom represented by Y Examples of the arylalkyl group having 7 to 20 atoms include benzyl, phenethyl, 2-phenylpropyl, diphenylmethyl, triphenylmethyl, styryl, cinnamyl, 4-chlorophenylmethyl, benzyloxy group, 1-naphthylmethoxy group, and 2 -A naphthyl methoxy group, 1-anthryl methoxy, etc. are mentioned.

X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ and X ^{8 in} the general formula (I), X ⁹ , X ¹⁰ , X ¹¹ , X in the general formula (II) ¹² , X ¹³ , X ¹⁴ , X ¹⁵ and X ¹⁶ , X ¹⁷ , X ¹⁸ , X ¹⁹ and X ^{20 in} the above general formula (III) or substituted or unsubstituted carbon with a halogen atom represented by Y Examples of the heterocyclic group having 2 to 20 atoms include pyrrolyl, pyridyl, pyrimidyl, pyridazyl, piperazyl, piperidyl, pyranyl, pyrazolyl, triazyl, pyrrolidyl, quinolyl, isoquinolyl, imidazolyl, benzimidazolyl, triazolyl, furyl, furanyl, benzofuranyl, Thienyl, thiophenyl, benzothiophenyl, thiadiazolyl, thiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl, isothiazolyl, isoxazolyl Indolyl, yurolidyl, morpholinyl, thiomorpholinyl, 2-pyrrolidinon-1-yl, 2-piperidone-1-yl, 2,4-dioxyimidazolidin-3-yl, 2,4-dioxyoxazolidine-3- Ir etc. are mentioned.

X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ and X ^{8 in} the general formula (I), X ⁹ , X ¹⁰ , X ¹¹ , X in the general formula (II) ¹² , X ¹³ , X ¹⁴ , X ¹⁵ and X ¹⁶ , and the halogen atoms represented by X ¹⁷ , X ¹⁸ , X ¹⁹ and X ²⁰ and Y in the general formula (III) include fluorine, chlorine, bromine, Iodine is mentioned.

In X ⁹ , X ¹⁰ , X ¹¹ and X ¹² in the general formula (II) and adjacent substituents in X ¹³ , X ¹⁴ , X ¹⁵ and X ¹⁶ , X ¹⁷ and X in the general formula (III) ¹⁸ , X ¹⁹ and X ²⁰ adjacent to each other and the ring structure which may be formed by R ¹ and R ² in the general formula (IV) include cyclopentane ring, cyclohexane ring, cyclopentene ring, benzene Examples thereof include 5- to 7-membered rings such as a ring, piperidine ring, morpholine ring, lactone ring and lactam ring, and condensed rings such as a naphthalene ring, anthracene ring, fluorene ring, acenaphthene ring, indane ring and tetralin ring.

X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ and X ⁸ in the general formula (I) are a hydrogen atom, an unsubstituted alkyl group having 1 to 4 carbon atoms, or It is preferably an unsubstituted aryl group having 6 to 12 carbon atoms.

Among the polymerizable compounds represented by the above general formula (I), those in which L is the above general formula (II); those in which L is the above general formula (III); or R ¹ in the above general formula (IV) And R ² is an alkyl group having 1 to 10 carbon atoms (especially a cyclic alkyl group having 3 to 10 carbon atoms) or an aryl group having 6 to 20 carbon atoms [in particular, R ¹ is ¹ to ¹ carbon atoms] 10 alkyl groups (especially cyclic alkyl groups having 3 to 10 carbon atoms and R ² is an aryl group having 6 to 20 carbon atoms) are preferred because the refractive index of the resulting compound is increased.
Further, X ⁹ , X ¹⁰ , X ¹¹ , X ¹² , X ¹³ , X ¹⁴ , X ¹⁵ and X ^{16 in} the above general formula (II), X ¹⁷ , X ¹⁸ , X ^{19 in the} above general formula (III) X ²⁰ and Y are preferably a hydrogen atom, an unsubstituted alkyl group having 1 to 4 carbon atoms, or an unsubstituted aryl group having 6 to 12 carbon atoms.

  Examples of the polymerizable compound represented by the general formula (I) include the following compounds A to Z.

Although the manufacturing method of the polymeric compound represented by the said general formula (I) is not specifically limited, For example, the polymeric compound whose L is a substituent represented by the said general formula (III) is bisphenol. It can be obtained by reacting the derivative (1) with halogenated methylstyrene in the presence of an alkali. The reaction formula is shown below. The following reaction can be performed according to a conventional method, for example, it may be performed at 40 to 90 ° C. for 30 minutes to 90 hours. In the following formula, X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ and X ⁸ , X ¹⁷ , X ¹⁸ , X ¹⁹ and X ²⁰ , Y, s, x and y are The same as in the general formula (I), and E represents a halogen atom. In addition, a polymerizable compound in which L is a substituent represented by the above general formula (II) or (IV) can be obtained in the same manner using a corresponding bisphenol derivative.

  Examples of the alkali used in the above reaction include sodium hydroxide, potassium hydroxide, calcium hydroxide, potassium carbonate and the like, and examples of the Lewis acid include an acid catalyst as exemplified above, tin tetrachloride, Examples thereof include boron trifluoride, titanium tetrachloride, activated clay, aluminum chloride, magnesium chloride, potassium permanganate, and potassium chromate. Examples of the phase transfer catalyst include tetramethylammonium chloride, tetrabutylammonium bromide, methyl Trioctylammonium chloride, methyltridecylammonium chloride, benzyltriethylammonium chloride, N, N-dimethylpyrrolidinium chloride, N-ethyl-N-methylpyrrolidinium iodide, N-butyl-N-methylpyrrolidinium bromide , N- N-methyl-pyrrolidinium chloride, N-ethyl-N-methylpyrrolidinium bromide, N-butyl-N-methylmorpholinium bromide, N-butyl-N-methylmorpholinium iodide, N-allyl -N-methylmorpholinium bromide, N-methyl-N-benzylpiperidinium chloride, N-methyl-N-benzylpiperidinium bromide, N, N-dimethylpiperidinium iodide, N-methyl-N- Examples include ethyl piperidinium acetate and N-methyl-N-ethyl piperidinium iodide. The alkali is preferably used in an amount of 0.1 to 2.0 mol, particularly 0.3 to 1.5 mol, per one hydroxyl group of the bisphenol compound (1).

  Moreover, a conventionally well-known solvent can be used for the said reaction, As this solvent, for example, ketones, such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone; Ether solvents such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, dipropylene glycol dimethyl ether; methyl acetate, ethyl acetate, acetic acid-n-propyl, isopropyl acetate, acetic acid-n -Ester solvents such as butyl; cellsolve solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether acetate; methanol, ethanol, iso- or n- Alcohol solvents such as propanol, iso- or n-butanol and amyl alcohol; BTX solvents such as benzene, toluene and xylene; Aliphatic hydrocarbon solvents such as hexane, heptane, octane and cyclohexane; turpentine oil, D-limonene Terpene hydrocarbon oil such as pinene; paraffinic solvents such as mineral spirit, swazol # 310 (Cosmo Matsuyama Oil Co., Ltd.), Solvesso # 100 (Exxon Chemical Co., Ltd.); carbon tetrachloride, chloroform, trichloroethylene, chloride Halogenated aliphatic hydrocarbon solvents such as methylene; Halogenated aromatic hydrocarbon solvents such as chlorobenzene; Carbitol solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N, N-dimethylformamide, N-methylpyrrolidone, etc. Among them, ketones or cellosolve solvent. These solvents can be used alone or in combination of two or more.

  The polymerizable compound of the present invention represented by the above general formula (I) is suitable as a raw material for the pressure-sensitive adhesive. Furthermore, a spacer layer of various optical recording media such as CD, DVD, MO, PD, VHS, DV, UMD, Blue-Ray Disk, HD DVD, etc .; a spacer of a multi-layer glass; a photocurable paint, a photocurable adhesive; In addition to various protective coating agents, various lenses, windows, etc., it can also be used in various applications such as analytical instrument applications, semiconductor device applications, astronomical observation applications, optical communication applications, and optical modeling applications.

  The pressure-sensitive adhesive composition of the present invention is a composition containing a polymerizable compound represented by the above general formula (I), and further a solvent and, if necessary, a polymerizable compound represented by the above general formula (I). And a monomer having an unsaturated bond and a thermal polymerization initiator. In the pressure-sensitive adhesive composition of the present invention, the content of the polymerizable compound represented by the general formula (I) is preferably 0.001 in a ratio to the total mass of the total solid content excluding the solvent from the pressure-sensitive adhesive composition. It is -50 mass%, More preferably, it is 0.1-30 mass%, Most preferably, it is 1-10 mass%.

  Examples of the monomer having an unsaturated bond include aromatic ring-containing acrylic monomers, styrene monomers, and aromatic ring-free ethylenically unsaturated monomers. In the pressure-sensitive adhesive composition of the present invention, the content of the monomer having an unsaturated bond is preferably 0.01 to 99% by mass, based on the total mass of the total solid content excluding the solvent from the pressure-sensitive adhesive composition. Preferably it is 50-95 mass%, Most preferably, it is 70-90 mass%. These monomers having an unsaturated bond can be used alone or in combination of two or more.

  Examples of the aromatic ring-containing acrylic monomer include an aromatic ring-containing acrylic monomer, 2-phenoxyethyl (meth) acrylate, and benzyl (described in JP-A Nos. 2002-173656 and 2003-13029). Examples include (meth) acrylic acid aryl esters such as (meth) acrylate, and at least one selected from these groups can be used.

  Examples of the styrene monomer include styrene, α-methyl styrene, p-methyl styrene, pt-butyl styrene, and the like.

The aromatic ring-free copolymerizable monomer is not particularly limited, and examples thereof include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, (meth ) Butyl acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, (meth) acrylic acid-n-octyl, isooctyl (meth) acrylate, (Meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid nonyl, (meth) acrylic acid isononyl, (meth) acrylic acid decyl, (meth) acrylic acid undecyl, (meth) acrylic acid dodecyl, (meth) acrylic acid tridecyl , Tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, (meta Hexadecyl acrylate, (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, stearyl (meth) methoxyethyl acrylate, (meth) cyclohexyl acrylate (meth) acrylic acid C _1-18 Alkyl ester; 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, tricyclodecandi (Meth) acrylic acid alkyl ester having two or more acrylic ester bonds such as methylol diacrylate; zinc (meth) acrylate.

  In addition, various monomers known as monomers for modifying acrylic pressure-sensitive adhesives can also be used as the monomer having an unsaturated bond. Examples of the monomer include hydroxyl group-containing copolymerization such as 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 6-hydroxyhexyl (meth) acrylate. Monomers; carboxyl group-containing copolymerizable monomers such as (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid and fumaric acid; vinyl esters such as vinyl acetate; (meth) acrylonitrile; (meth) acrylamide Amide group-containing copolymerizable monomers such as glycidyl (meth) acrylate and other epoxy group-containing copolymerizable monomers; N, N-dimethylaminoethyl (meth) acrylic acid alkyl ester and other amino group-containing copolymers And other monomers.

  In the pressure-sensitive adhesive composition of the present invention, the aromatic ring-containing acrylic monomer is 30 to 60% by mass, and the aromatic ring-free copolymerizable monomer is a proportion of the total mass of the monomer having an unsaturated bond. It is preferable to use 30 to 60 mass% of the monomer and 0.01 to 10 mass% of the modifying monomer. When each monomer is used in such a ratio, it becomes easier to adjust the refractive index between 1.45 and 1.60.

  As said solvent, what was illustrated as a solvent used in manufacturing the polymeric compound represented by the said general formula (I) is mentioned. The content of the solvent in the pressure-sensitive adhesive composition of the present invention is particularly limited as long as each component can be uniformly dissolved and dispersed and the pressure-sensitive adhesive composition of the present invention can be applied or formed into a film. Although it is not a thing, the range from which the total solid content except the solvent in the adhesive composition of this invention becomes 30-70 mass%, especially 40-60 mass% is suitable.

  The said thermal-polymerization initiator points out the compound which generate | occur | produces a radical by heating, for example, an organic peroxide, an azo compound, a redox initiator, etc. are mentioned.

  Examples of the organic peroxide include benzoyl peroxide, cumene hydroperoxide, di-t-butyl peroxide, t-butyl hydroperoxide and dicumyl peroxide, acetyl peroxide, lauroyl peroxide, cyclohexanone peroxide, dibenzoyl Peroxides, peroxides such as tert-butyl permaleate; peroxycarbonates such as 1,6bis (t-butylperoxycarbonyloxy) hexane; peroxyketals; potassium persulfate, sodium persulfate, ammonium persulfate, etc. Examples include persulfates.

  Examples of the azo compound include 2,2′-azobispropane, 2,2′-dichloro-2,2′-azobispropane, 1,1′-azo (methylethyl) diacetate, and 2,2′-azo. Bisisobutane, 2,2′-azobisisobutyramide, 2,2′-azobisisobutyronitrile (AIBN), methyl 2,2′-azobis-2-methylpropionate, 2,2′-dichloro-2 2,2′-azobisbutane, 2,2′-azobis-2-methylbutyronitrile, dimethyl 2,2′-azobisisobutyrate, 3,5-dihydroxymethylphenylazo-2-methylmalonodinitrile, 2,2′- Examples thereof include azobis-2-methylvaleronitrile, dimethyl 4,4′-azobis-4-cyanovalerate, 2,2′-azobis-2,4-dimethylvaleronitrile and the like.

  Examples of the redox initiator include a combination of hydrogen peroxide-iron (II) salt, organic oxide-dimethylaniline, cerium (IV) salt-alcohol, and the like.

  Although the usage-amount of the said thermal-polymerization initiator is not specifically limited, Usually, the range for 0.01-10 mass% is preferable in the ratio occupied to the total mass of the total solid except a solvent from an adhesive composition.

  The pressure-sensitive adhesive composition of the present invention is obtained by (co) polymerizing the polymerizable compound represented by the general formula (I) with a monomer having the unsaturated bond, which is contained as necessary. It is used as a (co) polymer-containing pressure-sensitive adhesive composition of the present invention containing a (co) polymer having a polymerizable compound represented by formula (I) as a constituent monomer. The pressure-sensitive adhesive composition of the present invention containing the polymerizable compound represented by the general formula (I) can potentially become a pressure-sensitive adhesive, and the polymerizable compound represented by the general formula (I) is By being a (co) polymer, the function as an adhesive is exhibited. Polymerization methods include solution polymerization methods using the above thermal polymerization initiators, emulsion polymerization methods and bulk polymerization methods, radical polymerization performed by irradiating light and radiation using a photopolymerization initiator described later, anionic polymerization, and cation. Various polymerization methods such as polymerization, coordination polymerization, and living polymerization can be employed. In addition, also about the (co) polymer containing adhesive composition of this invention, the description about the adhesive composition of this invention containing the polymeric compound represented by the said general formula (I) is applied suitably. it can.

From the viewpoint of ensuring the tackiness of the pressure-sensitive adhesive composition, the (co) polymer preferably has a weight average molecular weight Mw in the range of 1 × 10 ^{5 to} 5 × 10 ⁶ .

  The solution polymerization method, emulsion polymerization method and bulk polymerization method performed using the thermal polymerization initiator can be performed according to a conventional method. For example, these polymerization reactions are preferably performed at 50 to 120 ° C. for 5 to 20 hours.

Preferred types of the light are ultraviolet rays, visible rays, infrared rays and the like. You may use electromagnetic waves, such as an electron beam and an X-ray. Usually, ultraviolet rays or visible rays are preferable. A preferable wavelength range is 150 to 500 nm. A more preferable range is 250 to 450 nm, and a most preferable range is 300 to 400 nm. The light source is a low-pressure mercury lamp (sterilization lamp, fluorescent chemical lamp, black light), high-pressure discharge lamp (high-pressure mercury lamp, metal halide lamp), or short arc discharge lamp (super-high pressure mercury lamp, xenon lamp, mercury xenon lamp). Among them, an ultrahigh pressure mercury lamp can be preferably used. Light from the light source may be directly applied to the adhesive composition, or the adhesive composition may be irradiated with a specific wavelength (or a specific wavelength region) selected by a filter. Preferred irradiation energy density is 2~5000mJ / cm ^2, more preferably ranges are 10~3000mJ / cm ^2, particularly preferred range is 100 to 2000 mJ / cm ^2. A preferable illuminance is 0.1 to 5000 mW / cm ² , and a more preferable illuminance is 1 to 2000 mW / cm ² .

  As the photopolymerization initiator, conventionally known compounds can be used. For example, benzoyl peroxide, 2,2′-azobisisobutyronitrile, benzophenone, phenylbiphenyl ketone, 1-hydroxy-1- Benzoylcyclohexane, benzyl, benzyldimethyl ketal, 1-benzyl-1-dimethylamino-1- (4′-morpholinobenzoyl) propane, 2-morpholy-2- (4′-methylmercapto) benzoylpropane, thioxanthone, 1-chloro -4-propoxythioxanthone, isopropylthioxanthone, diethylthioxanthone, ethyl anthraquinone, 4-benzoyl-4'-methyldiphenyl sulfide, benzoin butyl ether, 2-hydroxy-2-benzoylpropane, 2-hydroxy-2- ( '-Isopropyl) benzoylpropane, 4-butylbenzoyltrichloromethane, 4-phenoxybenzoyldichloromethane, methyl benzoylformate, 1,7-bis (9'-acridinyl) heptane, 9-n-butyl-3,6-bis (2 '-Morpholinoisobutyroyl) carbazole, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, p-methoxyphenyl-2,4-bis (trichloromethyl) -s- Triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2-naphthyl-4,6-bis (trichloromethyl) ) -S-triazine, 2- (p-butoxystyryl) -s-triazine, 2- (p-butoxystyryl) ) -5-trichloromethyl-1,3,4-oxadiazole, 9-phenylacridine, 9,10-dimethylbenzphenazine, benzophenone / Michler's ketone, hexaarylbiimidazole / mercaptobenzimidazole, thioxanthone / amine, bis ( 2,4,6-trimethylbenzoyl) -phenylphosphine oxide, as well as JP 2000-80068, JP 2001-233842, JP 2005-97141, JP 2006-516246, JP 3860170. No. 3, Patent No. 3798008, WO 2006/018933, compounds represented by the following general formula (a) or (c), and the like.

（式中、Ｒ³、Ｒ⁴及びＲ⁵は、各々独立に、Ｒ、ＯＲ、ＣＯＲ、ＳＲ、ＣＯＮＲＲ’又はＣＮを表し、Ｒ及びＲ’は、アルキル基、アリール基、アリールアルキル基又は複素環基を表し、これらはハロゲン原子及び／又は複素環基で置換されていてもよく、これらのうちアルキル基及びアリールアルキル基のアルキレン部分は、不飽和結合、エーテル結合、チオエーテル結合、エステル結合により中断されていてもよく、また、Ｒ及びＲ’は一緒になって環を形成していてもよく、Ｒ⁶は、ハロゲン原子又はアルキル基を表し、Ｒ⁷は、水素原子、ハロゲン原子、アルキル基又は下記一般式（ｂ）で表される置換基を表し、ａは０〜４の整数であり、ａが２以上の時、複数のＲ⁴は異なる基でもよい。）

(Wherein R ³ , R ⁴ and R ⁵ each independently represents R, OR, COR, SR, CONRR ′ or CN, and R and R ′ represent an alkyl group, an aryl group, an arylalkyl group or a complex Represents a cyclic group, which may be substituted with a halogen atom and / or a heterocyclic group, and among these, the alkylene part of the alkyl group and the arylalkyl group is formed by an unsaturated bond, an ether bond, a thioether bond, or an ester bond. R 6 and R ′ may be combined to form a ring, R ⁶ represents a halogen atom or an alkyl group, and R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group. A group or a substituent represented by the following general formula (b), a is an integer of 0 to 4, and when a is 2 or more, a plurality of R ⁴ may be different groups.

（式中、環Ｍはシクロアルカン環、芳香環又は複素環を表し、Ｒ⁸はハロゲン原子又はアルキル基を表し、Ｚ¹は酸素原子、硫黄原子又はセレン原子を表し、Ｚ²は炭素原子数１〜５のアルキレン基を表し、ｂは０〜４の整数であり、ｂが２以上の時、複数のＲ⁸は異なる基でもよい。）

(In the formula, ring M represents a cycloalkane ring, an aromatic ring or a heterocyclic ring, R ⁸ represents a halogen atom or an alkyl group, Z ¹ represents an oxygen atom, a sulfur atom or a selenium atom, and Z ² represents the number of carbon atoms. 1 to 5 represents an alkylene group, b is an integer of 0 to 4, and when b is 2 or more, a plurality of R ⁸ may be different groups.

（式中、Ｒ¹¹及びＲ¹²は、それぞれ独立に、Ｒ¹⁵、ＯＲ¹⁵、ＣＯＲ¹⁵、ＳＲ¹⁵、ＣＯＮＲ¹⁶Ｒ¹⁷又はＣＮを表し、Ｒ¹⁵、Ｒ¹⁶及びＲ¹⁷は、それぞれ独立に、水素原子、炭素原子数１〜２０のアルキル基、炭素原子数６〜３０のアリール基、炭素原子数７〜３０のアリールアルキル基又は炭素原子数２〜２０の複素環基を表し、アルキル基、アリール基、アリールアルキル基及び複素環基の水素原子は更にＯＲ¹⁸、ＣＯＲ¹⁸、ＳＲ¹⁸、ＮＲ¹⁹Ｒ²⁰、ＣＯＮＲ¹⁹Ｒ²⁰、−ＮＲ¹⁹−ＯＲ²⁰、−ＮＣＯＲ¹⁹−ＯＣＯＲ²⁰、−Ｃ（＝Ｎ−ＯＲ¹⁸）−Ｒ¹⁹、−Ｃ（＝Ｎ−ＯＣＯＲ¹⁸）−Ｒ¹⁹、ＣＮ、ハロゲン原子、−ＣＲ¹⁸＝ＣＲ¹⁹Ｒ²⁰、−ＣＯ−ＣＲ¹⁸＝ＣＲ¹⁹Ｒ²⁰、カルボキシル基、エポキシ基で置換されていてもよく、Ｒ¹⁸、Ｒ¹⁹及びＲ²⁰は、それぞれ独立に、水素原子、炭素原子数１〜２０のアルキル基、炭素原子数６〜３０のアリール基、炭素原子数７〜３０のアリールアルキル基又は炭素原子数２〜２０の複素環基を表し、上記Ｒ¹⁵、Ｒ¹⁶、Ｒ¹⁷、Ｒ¹⁸、Ｒ¹⁹及びＲ²⁰で表される置換基のアルキレン部分のメチレン基は、不飽和結合、エーテル結合、チオエーテル結合、エステル結合、チオエステル結合、アミド結合又はウレタン結合により１〜５回中断されていてもよく、上記置換基のアルキル部分は分岐側鎖があってもよく、環状アルキルであってもよく、上記置換基のアルキル末端は不飽和結合であってもよく、また、Ｒ¹⁶とＲ¹⁷及びＲ¹⁹とＲ²⁰はそれぞれ一緒になって環を形成していてもよい。Ｒ¹³及びＲ¹⁴は、それぞれ独立に、Ｒ¹⁵、ＯＲ¹⁵、ＳＲ¹⁵、ＣＯＲ¹⁵、ＣＯＮＲ¹⁶Ｒ¹⁷、ＮＲ¹⁶ＣＯＲ¹⁷、ＯＣＯＲ¹⁵、ＣＯＯＲ¹⁵、ＳＣＯＲ¹⁵、ＯＣＳＲ¹⁵、ＣＯＳＲ¹⁵、ＣＳＯＲ¹⁵、ＣＮ、ハロゲン原子又は水酸基を表す。Ｚ³は、直接結合又はＣＯを表し、Ｚ⁴は、酸素原子、硫黄原子、セレン原子、ＣＲ²¹Ｒ²²、ＣＯ、ＮＲ²³又はＰＲ²⁴を表し、Ｒ²¹、Ｒ²²、Ｒ²³及びＲ²⁴は、それぞれ独立に、Ｒ¹⁵、ＯＲ¹⁵、ＣＯＲ¹⁵、ＳＲ¹⁵、ＣＯＮＲ¹⁶Ｒ¹⁷又はＣＮを表し、Ｒ¹³は、−Ｚ²−を介して隣接するベンゼン環の炭素原子の１つと結合して環構造を形成していてもよく、あるいはＲ¹³とＲ¹⁴が一緒になって環を形成していてもよく、Ｒ²²、Ｒ²³及びＲ²⁴は、それぞれ独立に、隣接するどちらかのベンゼン環と一緒になって環を形成していてもよい。）

(Wherein R ¹¹ and R ¹² each independently represent R ¹⁵ , OR ¹⁵ , COR ¹⁵ , SR ¹⁵ , CONR ¹⁶ R ¹⁷ or CN, and R ¹⁵ , R ¹⁶ and R ¹⁷ are each independently Represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms, an alkyl group, aryl group, further oR ¹⁸ is a hydrogen atom of the arylalkyl group and heterocyclic ^{group, COR 18, SR 18, NR} 19 R 20, CONR 19 R 20, -NR 19 -OR 20, -NCOR 19 -OCOR 20, -C ^{(= N-OR 18) -R} 19, -C (= N-OCOR 18) -R 19, CN, halogen ^{atom, -CR 18 = CR 19 R 20} , -CO-CR 18 = CR 19 R 20, carboxyl Group, which may be substituted with an epoxy group, R ¹⁸ , R ¹⁹ and R ²⁰ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or 2 to 20 carbon atoms. The methylene group of the alkylene part of the substituent represented by R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ is an unsaturated bond, an ether bond, a thioether bond, an ester It may be interrupted 1 to 5 times by a bond, a thioester bond, an amide bond or a urethane bond, and the alkyl part of the substituent may have a branched side chain, may be a cyclic alkyl, The alkyl terminal may be an unsaturated bond, and R ¹⁶ and R ¹⁷ and R ¹⁹ and R ²⁰ may be combined to form a ring, and R ¹³ and R ¹⁴ are each independently , R ^15, OR ^15, S ^{15, COR 15, CONR 16 R} 17, NR 16 COR 17, OCOR 15, COOR 15, SCOR 15, OCSR 15, COSR 15, CSOR 15, CN, .Z 3 represents a halogen atom or a hydroxyl group, a direct bond or CO Z ⁴ represents an oxygen atom, a sulfur atom, a selenium atom, CR ²¹ R ²² , CO, NR ²³ or PR ²⁴ , and R ²¹ , R ²² , R ²³ and R ²⁴ are each independently R ¹⁵ OR ¹⁵ , COR ¹⁵ , SR ¹⁵ , CONR ¹⁶ R ¹⁷ or CN, and R ¹³ is bonded to one of the carbon atoms of the adjacent benzene ring via —Z ² — to form a ring structure. Alternatively, R ¹³ and R ¹⁴ may be combined to form a ring, and R ²² , R ²³ and R ²⁴ are each independently a ring together with one of the adjacent benzene rings. May be formed. )

  The pressure-sensitive adhesive composition of the present invention is obtained as a pressure-sensitive adhesive by obtaining the above (co) polymer by a polymerization reaction and then adding a crosslinking agent as necessary to form a crosslink in the (co) polymer. The cohesive force of can be further increased. For crosslinking the (co) polymer, a conventional heat crosslinking method is preferably used. For example, what is necessary is just to heat at 50-130 degreeC for 1 minute-100 hours.

  As the crosslinking agent, conventionally known compounds can be used, for example, polyfunctional melamine compounds, polyisocyanate compounds, glycidyl compounds, aziridine compounds, oxazoline compounds, epoxy resins, melamine resins, amide resins, urea resins. , Dialdehydes, methylol polymers, aziridine compounds, metal chelate compounds, metal alkoxides, metal salts, butylated melamine compounds, and the like. When the crosslinking agent is used, the amount of the crosslinking agent used is 100 parts by mass with respect to the total amount of the polymerizable compound represented by the general formula (I) and the monomer having the unsaturated bond other than the polymerizable compound. The range of 0.001 to 10 parts by mass is preferable.

  Examples of the polyfunctional melamine compound include methylated trimethylol melamine and butylated hexamethylol melamine.

  Examples of the polyisocyanate compound include aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate and xylylene diisocyanate, aliphatic polyisocyanates such as hexamethylene diisocyanate, alicyclic polyisocyanates such as isophorone diisocyanate and hydrogenated diphenylmethane diisocyanate, and the like. , And biurets, isocyanurates, and adducts that are a reaction product with low molecular active hydrogen-containing compounds such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylol propane, castor oil, etc. it can.

  Examples of the glycidyl compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerin diglycidyl ether, neopentyl glycol diglycidyl ether, and 1,6-hexanediol diester. Glycidyl ether, diglycidyl aniline, N, N, N ′, N′-tetraglycidyl m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, trimethylolpropane polyglycidyl ether, diglycerol Polyfunctional glycidyl compounds such as polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether .

  Specific examples of the aziridine compound include 1,1 ′-(methylene-di-p-phenylene) bis-3,3-aziridylurea and 1,1 ′-(hexamethylene) bis-3,3-aziridyl. Urea, ethylenebis- (2-aziridinylpropionate), tris (1-aziridinyl) phosphine oxide, 2,4,6-triaziridinyl-1,3,5-triazine, trimethylolpropane-tris- (2- Aziridinyl propionate) and the like.

  The pressure-sensitive adhesive composition of the present invention can contain a silane coupling agent as necessary to further enhance the adhesion. When the silane coupling agent is used, the amount of the silane coupling agent used is the total amount of the polymerizable compound represented by the general formula (I) and the monomer having the unsaturated bond other than the polymerizable compound 100. The range of 0.001-10 mass parts is preferable with respect to mass parts.

  Examples of the silane coupling agent include polymerizable unsaturated group-containing silicon compounds such as vinyltrimethoxysilane, vinyltriethoxysilane, and 3-methacryloxypropyltrimethoxysilane; 3-glycidoxypropyltrimethoxysilane, 2- Silicon compounds having an epoxy structure such as (3,4-epoxycyclohexyl) ethyltrimethoxysilane; 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2 -Aminoethyl) -3-aminopropylmethyldimethoxysilane and other amino group-containing silicon compounds; 3-chloropropyltrimethoxysilane; γ-mercaptopropyltrimethoxysilane and other mercapto group-containing silicon compounds. These may be used individually by 1 type and may be used in combination of 2 or more type.

  The pressure-sensitive adhesive composition of the present invention can further contain a chain transfer agent, a surfactant and the like.

  Examples of the chain transfer agent include thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N- (2-mercaptopropionyl) glycine, 2-mercaptonicotinic acid, 3- [N- (2-mercaptoethyl) carbamoyl] propionic acid, 3- [N- (2-mercaptoethyl) amino] propionic acid, N- (3-mercaptopropionyl) alanine, 2-mercaptoethanesulfonic acid, 3 -Mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, dodecyl (4-methylthio) phenyl ether, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-propanol, 3-mercapto- 2-butanol, mercapto Enol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercapto-3-pyridinol, 2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopro Mercapto compounds such as pionate), disulfide compounds obtained by oxidizing the mercapto compound, iodinated alkyls such as iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid, etc. Compounds and the like. These may be used alone or in combination of two or more.

  Examples of the surfactant include fluorine surfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates, anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates, and alkyl sulfates, and higher amines. Cationic surfactants such as halogenates and quaternary ammonium salts, nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters and fatty acid monoglycerides, amphoteric surfactants, silicone surfactants Surfactants such as agents can be used, and these can be used alone or in combination of two or more.

  In the pressure-sensitive adhesive composition of the present invention, the properties of the cured product can be improved by using a thermoplastic organic polymer. Examples of the thermoplastic organic polymer include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly (meth) acrylic acid, styrene- (meth) acrylic acid copolymer, (meth) acrylic acid- Examples include methyl methacrylate copolymer, polyvinyl butyral, cellulose ester, polyacrylamide, and saturated polyester. These may be used alone or in combination of two or more.

  When the pressure-sensitive adhesive composition of the present invention is used for an optical film for an image display device, the pressure-sensitive adhesive composition of the present invention includes a light absorber that absorbs light having a wavelength of 550 to 620 nm and a color tone adjusting function. A pressure-sensitive adhesive layer can be formed by containing a light absorber corresponding to 480 to 500 nm or a near-infrared absorber corresponding to 750 to 1100 nm, which has light reflection and reflection prevention.

  Examples of the light absorber having a color tone adjusting function include trimethine indolium compounds, trimethine benzoxazolium compounds, trimethine benzothiazolium compounds, and the like used for the removal of orange light of 550 to 620 nm. Trimethine cyanine compounds; pentamethine cyanine compounds such as pentamethine oxazolium compounds and pentamethine thiazolium compounds; squarylium dyes; azomethine dyes; xanthene dyes; azo dyes; pyromethene dyes; azo metal complexes: rhodamine dyes; A porphyrin compound; a dipyrromethene metal chelate compound;

  In addition, as the above-mentioned light absorber for 480 to 500 nm having a function of preventing reflection of external light, monomethine cyanine derivatives; trimethine indolium compounds, trimethine oxazolium compounds, trimethine thiazolium compounds, indolidene trimes Trimethine cyanine compounds such as tinthiazonium compounds; merocyanine compounds; phthalocyanine compounds; naphthalocyanine compounds; porphyrin compounds; dipyrromethene metal chelate compounds.

  Further, as a near infrared absorber for infrared light remote control malfunction prevention function for 750 to 1100 nm, pentamethine cyanine such as pentamethine benzoindolium compound, pentamethine benzoxazolium compound, pentamethine benzothiazolium compound, etc. Compound: Heptamethine cyanine compounds such as heptamethine indolium compound, heptamethine benzoindolium compound, heptamethine oxazolium compound, heptamethine benzoxazolium compound, heptamethine thiazolium compound, heptamethine benzothiazolium compound Diimonium compounds; aminium compounds; squarylium compounds; bis (stilbenedithiolato) compounds, bis (benzenedithiolato) nickel compounds, bis (camphagethiolato) nickel compounds, etc. Kell complex; squarylium compound; azo dyes; phthalocyanine compounds; porphyrin compound; dipyrromethene metal chelate compounds, and the like.

  In addition, the pressure-sensitive adhesive composition of the present invention includes, as necessary, thermal polymerization inhibitors such as anisole, hydroquinone, pyrocatechol, t-butylcatechol, phenothiazine; curing catalyst; monoglycidyl ethers, dioctyl phthalate, dibutyl phthalate. Reactive or non-reactive diluents (plasticizers) such as benzyl alcohol and coal tar; glass fiber, carbon fiber, cellulose, silica sand, cement, kaolin, clay, aluminum hydroxide, bentonite, talc, silica, fine Fillers or pigments such as powdered silica, titanium dioxide, carbon black, graphite, iron oxide, bituminous substances; dyes; candelilla wax, carnauba wax, wood wax, ibota wax, beeswax, lanolin, whale wax, montan wax, petroleum wax , Fatty acid wax, fatty acid Lubricants such as stealth, fatty acid ethers, aromatic esters, aromatic ethers; tackifiers such as rosin resins, terpene resins, petroleum resins, coumarone / indene resins, styrene resins; thickeners; thixotropic agents; Antioxidant; Light stabilizer; Ultraviolet absorber; Flame retardant; Antifoaming agent; Adhesion promoter; Fluidity improver; Adhesion improver; Softener; Dispersant; Leveling agent; Conventional additives such as emulsifiers; antibacterial agents; cross-linking aids; antiblocking agents; colloidal silica and colloidal alumina may be included. In the pressure-sensitive adhesive composition of the present invention, these optional additives may be used alone or in combination of two or more.

  In the pressure-sensitive adhesive composition of the present invention, any additive (a polymerizable compound represented by the general formula (I), a monomer having an unsaturated bond other than the polymerizable compound, a thermal polymerization initiator, a crosslinking agent, In the case of containing an additive other than a silane coupling agent and a solvent, the content thereof is 100 parts by mass in total of the polymerizable compound represented by the general formula (I) and the monomer having an unsaturated bond. The range of 100 parts by mass or less is preferable.

  The pressure-sensitive adhesive composition of the present invention can be suitably used mainly as a pressure-sensitive adhesive used for an optical filter for an image display device. In addition, a pressure-sensitive adhesive tape for protecting a semiconductor wafer surface, a protective film for automobiles, a thermal adhesive film label It can also be used for applications such as sealing (adhesion of paper).

  When the pressure-sensitive adhesive used for the optical filter for an image display device is used, the pressure-sensitive adhesive composition of the present invention is used for fixing or bonding optical films such as a viewing angle widening film, a retardation film, and a polarizing plate. The (co) polymer-containing pressure-sensitive adhesive composition may be used as it is after being applied onto a support substrate of an image display device or an optical film. Further, as described later, an adhesive layer (adhesive film) formed from the (co) polymer-containing adhesive composition of the present invention is formed on a release liner, and the adhesive layer is released from the release liner. The image may be transferred onto a support substrate or an optical film of the image display device. Moreover, when an optical film is a composite filter, it can also be used for adhesion | attachment of each functional layer in a composite filter.

  The polymerizable compound represented by the general formula (I) has a high refractive index of 1.60 to 1.70, and a refractive index of 1.45 to 1.70 is appropriately copolymerized with the monomer having the unsaturated bond. An adhesive composition having an arbitrary value between 1.60 can be obtained. Thereby, the refractive index of the pressure-sensitive adhesive composition of the present invention can be made close to the refractive index of the transparent support described later, the ratio of total reflection of light can be reduced, and the light transmittance can be improved. This is effective when used in an image display device because the light transmission efficiency from the backlight can be improved. In consideration of the refractive index of a transparent support used for a general image display device, the refractive index of the pressure-sensitive adhesive composition of the present invention is preferably 1.45 to 1.60, and more preferably 1.48 to 1.58. preferable.

  In addition, the polymerizable compound represented by the general formula (I) has a structure in which the benzene rings in the molecule are orthogonal to each other and the refractive index anisotropy cancels out. When the pressure-sensitive adhesive composition of the present invention is cured, white unevenness and white spots can be prevented even if misalignment or orientation due to stretching / shrinking with time occurs.

Next, the pressure-sensitive adhesive sheet of the present invention will be described.
The pressure-sensitive adhesive sheet of the present invention has a pressure-sensitive adhesive layer (pressure-sensitive adhesive film) formed from the (co) polymer-containing pressure-sensitive adhesive composition of the present invention. The pressure-sensitive adhesive sheet of the present invention is used by applying it on a target surface such as a transparent support, which will be described later, constituting a support substrate or an optical film of an image display device by known means. Moreover, after once applying on support bases, such as a film, it can also transfer on another support base | substrate, There is no restriction | limiting in the application method. In the pressure-sensitive adhesive sheet of the present invention, the thickness of the pressure-sensitive adhesive layer can be appropriately selected depending on the application and is not particularly limited, but is preferably selected from a range of 10 to 100 μm.

  In the pressure-sensitive adhesive sheet of the present invention, the pressure-sensitive adhesive surface of the pressure-sensitive adhesive layer may be protected with a release liner. As the release liner, one having both sides of the release surface may be used, or one having only one side being the release surface may be used.

  Such a release liner is not particularly limited and can be appropriately selected from known release liners. For example, a plastic film having high peelability is preferably used. Examples of the material of the plastic film include ethylene (α-olefin copolymer) such as polyethylene (low density polyethylene, linear low density polyethylene, etc.), polypropylene, ethylene-propylene copolymer (block copolymer or random). Copolymer), polyolefin resins composed of a mixture thereof; polyester such as polyethylene terephthalate; polyvinyl chloride; polyimide; thermoplastic resin such as polycarbonate; and Teflon (registered trademark). The plastic film may be either an unstretched film or a stretched (uniaxially stretched or biaxially stretched) film.

In addition to the plastic film, a release liner having a structure in which a release treatment layer is formed on the surface (one side or both sides) of a film made of a material mentioned as a material for a transparent support described later can also be suitably used. Further, it may be paper (for example, Japanese paper, western paper, glassine paper, etc.), non-woven fabric, cloth, foamed body, metal foil, composite base material (for example, metal-deposited plastic film, etc.) using various base materials.
The thickness of the release liner can be appropriately selected according to the purpose, but is generally about 10 to 500 μm.

  In addition, as the release treatment agent for forming the release treatment layer in the release liner, a known or conventional release treatment agent (for example, a silicone release agent, a fluorine release agent, a long-chain alkyl release agent, etc.) is used. Can do. In addition, the peeling process layer may be formed by laminating or coating the various materials mentioned as a raw material of the said plastic film on the surface of the film which consists of the material mentioned as a material of the below-mentioned transparent support body. In the release liner, the release treatment layer can be provided on one side or both sides of the substrate as described above.

  Although the formation method of the adhesive layer by the (co) polymer containing adhesive composition of this invention is not restrict | limited in particular, For example, the following method is mentioned. On the release liner, the (co) polymer-containing pressure-sensitive adhesive composition of the present invention is applied and dried by a method such as cast coating, screen coating, or spin coating. For example, the drying may be performed at 80 to 150 ° C. for 1 to 30 minutes. Further, aging is preferably performed at 40 to 70 ° C. for 50 to 100 hours. In addition, when the above-mentioned crosslinking agent is added to the (co) polymer-containing pressure-sensitive adhesive composition, crosslinking by the crosslinking agent can be formed in this drying to aging process.

Examples of the material for the transparent support include inorganic materials such as glass; cellulose esters such as diacetylcellulose, triacetylcellulose (TAC), propionylcellulose, butyrylcellulose, acetylpropionylcellulose, and nitrocellulose; polyamide; polyimide; polyurethane Epoxy resin; polycarbonate; polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4′-dicarboxylate, polybutylene terephthalate Polyester such as polystyrene, polyethylene, polypropylene, polymethylpentene, cycloolefin, ethylene-propylene copolymer, poly Polyolefins such as tetrafluoroethylene; Vinyl compounds such as polyvinyl acetate, polyvinyl chloride, and polyvinyl fluoride; Acrylic resins such as polymethyl methacrylate and polyacrylate; Polycarbonate; Polysulfone; Polyethersulfone; Polyetherketone; Etherimide; polystyrene; polymer materials such as polyoxyethylene, norbornene resin, and silicon. The transmittance of the transparent support is preferably 80% or more, and more preferably 86% or more. The haze is preferably 2% or less, and more preferably 1% or less. The refractive index is preferably 1.45 to 1.70.

  As a method for applying the pressure-sensitive adhesive composition of the present invention to the transparent support, known methods can be used, such as curtain coating, extrusion coating, roll coating, spin coating, dip coating, bar coating, and the like. A coating method, a die coating, a spray coating method, a slide coating method, various screen printings, ink jet printings, dipping and casting film forming methods, and the like can be used. After application, it is preferable to heat and age according to the case where the pressure-sensitive adhesive layer is formed on the release liner.

  In the transparent support, ultraviolet absorbers, phenolic and phosphorous antioxidants, flame retardants, lubricants, antistatic agents, inorganic fine particles, and the like are added. Surface treatment can be applied.

  Examples of the inorganic fine particles include silicon dioxide, titanium dioxide, barium sulfate, and calcium carbonate.

  Examples of the various surface treatments include chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, ozone oxidation treatment, and the like. It is done.

Below, typical embodiment of the adhesive composition of this invention and an adhesive sheet is put together. The contents described in detail above can be appropriately applied to points not specifically described here.
First, the polymerizable compound represented by the above general formula (I) and, if necessary, the monomer having an unsaturated bond and a thermal polymerization initiator are added to a solvent to obtain the pressure-sensitive adhesive composition of the present invention. . Next, the pressure-sensitive adhesive composition is subjected to a (co) polymerization reaction, the polymerizable compound represented by the general formula (I) contained in the pressure-sensitive adhesive composition, and the unsaturated added as necessary. The (co) polymer-containing pressure-sensitive adhesive composition of the present invention is obtained by (co) polymerizing a monomer having a bond. If necessary, a solvent is added to the (co) polymer-containing pressure-sensitive adhesive composition of the present invention to adjust the viscosity. The viscosity of the (co) polymer-containing pressure-sensitive adhesive composition here is preferably adjusted to a range of 1000 to 10,000 mPs · s from the viewpoint of handling properties when a subsequent pressure-sensitive adhesive layer is formed. Subsequently, arbitrary additives, such as a crosslinking agent and a silane coupling agent, are added as needed.
Next, the (co) polymer-containing pressure-sensitive adhesive composition of the present invention containing the optional additives obtained as described above is applied on a release liner, dried by heating, and then aged. To make the pressure-sensitive adhesive sheet of the present invention.

EXAMPLES Hereinafter, although an Example etc. are shown and this invention is demonstrated further in detail, this invention is not limited by these Examples. Hereinafter, “parts” means parts by mass.
In addition, Production Examples 1-4 show the Example of the polymeric compound of this invention represented by the said general formula (I). Examples 1 to 5 and Comparative Examples 1 to 4 show examples of the pressure-sensitive adhesive composition and the comparative pressure-sensitive adhesive composition of the present invention and pressure-sensitive adhesive sheets using them. In the evaluation examples, the pressure-sensitive adhesive sheet made of the pressure-sensitive adhesive composition of Examples 1 to 5 and the pressure-sensitive adhesive sheet made of the comparative pressure-sensitive adhesive composition of Comparative Examples 1 to 4 are tacky, adhesive durability and optical properties. Was evaluated.

[Production Example 1] Production of 9,9-bis (4- (4-vinylbenzyloxy) phenyl) fluorene (hereinafter referred to as Compound No. 1) 1 was produced by the following procedure.

  9,9-bis (4-hydroxyphenyl) fluorene (35.0 g), potassium hydroxide (14.0 g) and dimethylacetamide (150 g) were mixed and heated at 110 ° C. for 2 hours. 4-Chloromethylstyrene 38.1g was dripped at 70 degreeC over 30 minutes. Furthermore, after making it react at 70 degreeC for 1 hour, oil-water separation was carried out at 40 degreeC with 500 g of ethyl acetate and 1000 g of water. It was dried over sodium sulfate and treated with silica gel to remove the solvent, and recrystallized from methanol to obtain 36 g of white crystals (yield 62%). As a result of various analyses, the target compound No. 1 was confirmed. The obtained Compound No. 1 was a crystalline organic compound showing a clear melting point.

(result of analysis)
(1) Chemical shift (ppm) of ¹ H-NMR (CDCl ₃ -d)
4.98 (m: 4H), 5.21-5.24 (m: 2H), 5.70-5.75 (m: 2H), 6.65-6.72 (m: 2H), 6. 78-7.84 (m: 4H), 7.08-7.12 (m: 4H), 7.20-7.25 (m: 2H), 7.29-7.39 (m: 10H), 7.71-7.73 (m: 2H)
(2) IR spectrum (cm ^-1 )
3065, 3008, 2892, 1907, 1630, 1607, 1602, 1581, 1505, 1447, 1407, 1379, 1292, 1275, 1244, 1178, 1115, 1036, 1015, 990, 909
(3) Melting point: 114.5 ° C, 125.6 ° C

[Production Example 2] Production of 1,1-bis (4-benzyloxyphenyl) -1-phenylethane (hereinafter referred to as Compound No. 2) 2 was prepared by the following procedure.

  8.7 g of 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 4.71 g of potassium hydroxide and 47 g of dimethylacetamide were mixed and heated at 110 ° C. for 1 hour. 4-chloromethylstyrene 11.9g was dripped at 65 degreeC over 30 minutes. The reaction was further carried out at 65 ° C. for 1 hour, followed by oil-water separation at 40 ° C. with 200 g of ethyl acetate and 1000 g of water. Furthermore, the oil layer was washed with 300 g of water three times. The extract was dried over sodium sulfate and treated with silica gel to remove the solvent, and recrystallized from a mixed solvent of ethyl acetate and methanol to obtain 8.1 g of white crystals (yield 52%). As a result of various analyses, the target compound No. 2 was confirmed. The obtained Compound No. 2 was a crystalline organic compound showing a clear melting point.

(result of analysis)
(1) Chemical shift (ppm) of ¹ H-NMR (CDCl ₃ -d)
2.12 (m: 3H), 4.98 (m: 6H), 5.23-5.25 (m: 2H), 5.72-5.77 (m: 2H), 6.67-6. 74 (m: 2H), 6.82-7.86 (m: 4H), 6.94-7.01 (m: 4H), 7.06-7.09 (m: 2H), 7.16- 7.21 (m: 2H), 7.33-7.42 (m: 7H)
(2) IR spectrum (cm ^-1 )
3060, 2980, 1629, 1607, 1602, 1579, 1508, 1491, 1467, 1445, 1407, 1377, 1292, 1246, 1228, 1181, 1119, 1061, 1034, 1027, 1014, 990, 909

[Production Example 3] Production of 1,1-bis [4- (4-vinylbenzyloxy) phenyl] -3-phenylindane (hereinafter referred to as Compound No. 3) 3 was prepared by the following procedure.

  5.00 g of 1,1-bis (4-hydroxyphenyl) -3-phenylindane, 20.0 g of acetone, 4.00 g of methanol and 1.16 g of sodium hydroxide were mixed and heated to 55 ° C., and 4-chloromethyl Styrene 4.23 g was slowly added dropwise. After further reacting at 55 ° C. for 4 hours, 50 mL of methanol was added to this reaction solution and stirred well, and the viscous liquid supernatant that had settled to the bottom was removed by decantation. The remaining liquid was dissolved by adding 50 mL of acetone, and then the solvent was distilled off to obtain a yellow crystalline solid. This was washed with acetone to obtain 3.31 g (yield 41%) of yellow crystals. As a result of various analyses, the target compound No. 3 was confirmed.

(result of analysis)
(1) Chemical shift (ppm) of ¹ H-NMR (DMSO-d ₆ )
2.66-2.73 (m: 1H), 3.16-3.25 (m: 1H), 4.14 (dd: 1H), 5.03-5.10 (m: 4H), 5. 23-5.31 (m: 2H), 5.81-5.86 (m: 2H), 6.68-6.81 (m: 3H), 6.91-7.10 (m: 7H), 7.11-7.30 (m: 7H), 7.31-7.39 (m: 2H), 7.39-7.46 (m: 4H), 7.46-7.54 (m: 4H) )
(2) IR spectrum (cm ^-1 )
3025, 2964, 2940, 2868, 1629, 1606, 1579, 1507, 1457, 1407, 1381, 1291, 1245, 1179, 1117, 1045, 1012, 912, 877, 829, 758, 732, 700

[Production Example 4] Production of 9,9-bis (4- (4-vinylbenzyloxy) phenyl) fluorene (hereinafter referred to as Compound No. 4) 4 was prepared by the following procedure.

  A mixture of 7.56 g of 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 2.92 g of potassium hydroxide and 18.3 g of methanol was heated at 60 ° C. for 30 minutes. At 60 ° C., 7.32 g of 4-chloromethylstyrene was added dropwise over 30 minutes. After further reaction at 60 ° C. for 2 hours, oil-water separation was performed at 40 ° C. with 100 g of ethyl acetate and 100 g of water. It was dried over sodium sulfate and treated with silica gel to remove the solvent, and recrystallized from methanol to obtain 8.3 g of white crystals (yield 68%). As a result of various analyses, the target compound No. 4 was confirmed.

(result of analysis)
(1) Chemical shift (ppm) of ¹ H-NMR (CDCl ₃ -d ₆ )
2.15 (m: 6H), 4.96 (m: 2H), 5.21-5.24 (m: 2H), 5.71-5.75 (m: 2H), 6.63-6. 73 (m: 4H), 6.92-7.03 (m: 4H), 7.15-7.22 (m: 2H), 7.24-7.43 (m: 10H), 7.71- 7.73 (m: 2H)
(2) IR spectrum (cm ^-1 )
2948, 2937, 1741, 1630, 1607, 1502, 1447, 1406, 1378, 1305, 1251, 1222, 1178, 1150, 1311, 1032, 1016, 990, 908
(3) Melting point: 150 ° C

[Example 1] Adhesive composition No. 1 and adhesive sheet no. Production of Compound No. 1 obtained in Production Example 1 1 part, 50 parts of butyl acrylate, 45 parts of benzyl acrylate, 1 part of acrylic acid, 0.1 part of 2-hydroxyethyl acrylate, 50 parts of ethyl acetate and 50 parts of methyl ethyl ketone, 60 ° C. under nitrogen atmosphere For 2 hours to remove oxygen in the polymerization system. Add 0.2 part of azobisisobutyronitrile to add adhesive composition no. It was set to 1.
The pressure-sensitive adhesive composition was heated to 65 ° C. and reacted for 10 hours, and then heated to 75 ° C. and reacted for 2 hours. 100 parts of ethyl acetate was added to the reaction solution, and the copolymer-containing pressure-sensitive adhesive composition No. 1A (Mw = 800,000, viscosity 2700 mPs · s) was obtained.
The obtained copolymer-containing pressure-sensitive adhesive composition No. To 1A, 0.5 part of trimethylolpropane tolylene diisocyanate as a crosslinking agent and 0.1 part of γ-mercaptopropylmethyltrimethoxysilane (trade name: KBM-803, manufactured by Shin-Etsu Chemical Co., Ltd.) as a coupling agent were added. The copolymer-containing pressure-sensitive adhesive composition No. 1B was obtained.
The copolymer-containing pressure-sensitive adhesive composition No. 1 was dried on a silicon-coated release liner made of a PET film having a thickness of 38 μm so that the thickness after drying was about 25 μm. 1B was cast applied, dried by heating at 100 ° C. for 3 minutes, the surface was then covered with a release liner, and further aged at 50 ° C. for 72 hours to form a crosslinked structure. 1 was obtained.

[Examples 2 to 5 and Comparative Examples 1 to 4] Adhesive composition No. 2-5 and comparative adhesive composition No. 1-4 and adhesive sheet No. 2-5 and comparative adhesive sheet no. Production of 1-4
The adhesive composition No. was changed in the same manner as in Example 1 except that the formulation in [Table 1] was changed. 2-5 and comparative adhesive composition No. After preparing 1-4, each adhesive composition was copolymerized, ethyl acetate was added, and copolymer-containing adhesive composition No. 1 was added. 2A-5A and comparative copolymer-containing pressure-sensitive adhesive composition No. 1A to 4A, a crosslinking agent and a coupling agent were added thereto, and the copolymer-containing pressure-sensitive adhesive composition No. 2B-5B and comparative copolymer-containing pressure-sensitive adhesive composition No. 2 It was set to 1B-4B. Then, using them, the adhesive sheet No. 2-5 and comparative adhesive sheet no. 1-4 were obtained. In addition, the polyisocyanate described in Table 1 below is a trade name “Coronate L” (manufactured by Nippon Polyurethane Co., Ltd.).

[Evaluation example]
Adhesive sheet No. 1-5 and comparative adhesive sheet No.1. The following <Adhesion evaluation>, <Adhesion durability evaluation>, and <Optical characteristic evaluation> were performed about 1-4. The results are shown in [Table 2].

<Adhesion evaluation>
(1) Adhesive strength About the obtained adhesive sheet, it peeled 180 degree | times according to JISZ-0237, and measured the adhesive strength. A glass plate was used as the adherend.
(2) Holding power About the obtained adhesive sheet, the shift | offset | difference amount was measured according to the holding power measuring method of JISZ-0237. In the measurement, the pressure-sensitive adhesive sheet was cut into 25 mm × 55 mm so that the absorption axis was 90 ° with respect to the long side of the polarizing plate, and 5 kg / cm ² at 50 ° C. on the glass plate so that the adhesion area was 25 mm × 10 mm. A test sample was prepared by applying a pressure of 2 and holding for 18 minutes and pasting it, hanging a load of 9.8 N on the test sample in an atmosphere of 90 ° C., and measuring the deviation after 1 hour.

<Adhesion durability evaluation>
The adhesive sheet was subjected to heat resistance (80 ° C., 500 hours) and moisture heat resistance (60 ° C., 90% RH, 500 hours) tests, and then visually evaluated for foaming and peeling according to the following evaluation criteria.
(1) Foam evaluation criteria ○: Foaming is not confirmed in the pressure-sensitive adhesive sheet.
(Triangle | delta): Foaming was confirmed slightly in the adhesive sheet.
X: Foaming was confirmed in the adhesive sheet.
(2) Peeling evaluation criteria ○: Peeling is not confirmed on the adhesive sheet.
Δ: Slight peeling was confirmed on the adhesive sheet.
X: Peeling was confirmed on the adhesive sheet.

<Optical characteristic evaluation>
(1) Refractive index The refractive index was measured by irradiating sodium D line at 25 ° C with an Abbe refractometer.
(2) Total light transmittance The total light transmittance (%) of 35 points | pieces was measured using the NDH2000 haze meter by Nippon Denshoku Industries Co., Ltd., and the difference of the total light transmittance was computed from the following [Formula 1].
[Formula 1]
Difference in total light transmittance Δ = maximum total light transmittance−minimum total light transmittance

(3) White Leakage Each of the obtained pressure-sensitive adhesive sheets was bonded in a crossed Nicol state, placed on the backlight of a liquid crystal monitor, and the state of white omission was visually observed and evaluated according to the following criteria.
-Evaluation criteria O: No white spots were found on the optical film.
Δ: Slight white spots were confirmed on the optical film.
X: White spots were confirmed on the optical film.

(4) Total reflection angle A right-angle prism (material BK-7: nD1.517) and a glass substrate (material BK-7: nD1.517) are bonded together through the obtained adhesive sheet, and light is transmitted from the edge of the glass substrate. The incident angle and the presence / absence of light exiting through the adhesive sheet and the prism were examined, and the angle θ at which light did not come out was evaluated as the total reflection angle (°). In addition, it processed so that the upper and lower surfaces of a glass substrate might be parallel, and an up-and-down surface and an end surface (side surface) might become vertical. Further, a single mode He—Ne laser was used as the light source, and the polarization direction was 45 ° with respect to the end face.

(5) Output light intensity ratio Using a matching oil that has been adjusted in advance to have a refractive index of 1.517 through the obtained adhesive sheet, a right-angle prism (nd = 1.517) and a glass substrate (nd = 1.517) ), The light is made incident from the edge of the glass substrate, and the intensity of the emitted light from the right-angle prism is measured while changing the angle of the laser light, and the light passes through the adhesive layer and the prism depending on the incident angle. The total sum of incident light (incident light intensity) was measured, and the outgoing light intensity ratio was calculated by outgoing light intensity / incident light intensity × 100.

From the results of [Table 2], it can be seen that the pressure-sensitive adhesive sheet made of the pressure-sensitive adhesive composition of the present invention has a high holding power while having a sufficient pressure-sensitive adhesive force as compared with the comparative pressure-sensitive adhesive sheet.
Furthermore, it is clear that the pressure-sensitive adhesive sheet of the present invention exhibits higher heat resistance and moist heat resistance than the comparative pressure-sensitive adhesive sheet.
Moreover, the adhesive sheet of this invention can be adjusted so that arbitrary refractive indexes may be taken between 1.48-1.58.
In addition, the difference Δ in the total light transmittance of the pressure-sensitive adhesive sheet of the present invention is 0.05 or less, and when used in a polarizing plate, uneven color and white spots can be suppressed, and the transparency is high.
In addition, the pressure-sensitive adhesive sheet of the present invention has a refractive index that is substantially the same as that of the optical member to be bonded, and thus has a high ratio of emitted light intensity and low total reflection, making it difficult to reflect light coming from the backlight direction. It is possible to effectively use light.

Claims (10)

The adhesive composition containing the polymeric compound represented by the following general formula (I).

(In the formula, L is a direct bond or a substituent represented by any one of the following general formulas (II) to (IV), and X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ and X ⁸ are each independently a halogen atom-substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryl having 7 to 20 carbon atoms. Represents an alkyl group or a heterocyclic group having 2 to 20 carbon atoms, a hydrogen atom, or a halogen atom, and the methylene group in the alkyl group, aryl group and arylalkyl group is an unsaturated bond, -O-, -S-, (It may be interrupted by -CO-, -COO- or -OCO-).

(In the formula, X ⁹ , X ¹⁰ , X ¹¹ , X ¹² , X ¹³ , X ¹⁴ , X ¹⁵ , X ¹⁶ , X ¹⁷ , X ¹⁸ , X ¹⁹ and X ²⁰ are each independently substituted with a halogen atom. Or an unsubstituted alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms, a hydrogen atom Or a methylene group in the alkyl group, aryl group and arylalkyl group is interrupted by an unsaturated bond, -O-, -S-, -CO-, -COO- or -OCO-. In X ⁹ , X ¹⁰ , X ¹¹ and X ¹² , adjacent substituents in X ¹³ , X ¹⁴ , X ¹⁵ and X ^{16 and} in X ¹⁷ , X ¹⁸ , X ¹⁹ and X ²⁰ May be formed,
Y is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or 2 to 20 carbon atoms. A methylene group in the alkyl group, aryl group and arylalkyl group is an unsaturated bond, -O-, -S-, -CO-, -COO- or -OCO-. May be interrupted,
s represents the number of 0-8, x represents the number of 0-4, y represents the number of 0-4, the sum of the number of x and y is 2-4,
R ¹ and R ² represent a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R ¹ and R ² form a ring together. It may be. )   The pressure-sensitive adhesive composition according to claim 1, wherein, in the general formula (I), L is a substituent represented by the general formula (II).   The pressure-sensitive adhesive composition according to claim 1, wherein, in the general formula (I), L is a substituent represented by the general formula (III). In the general formula (I), L is a substituent represented by the general formula (IV), R ¹ is an alkyl group having 1 to 10 carbon atoms, and R ² is an alkyl group having 6 to 20 carbon atoms. The pressure-sensitive adhesive composition according to claim 1, which is an aryl group.   Furthermore, the adhesive composition in any one of Claims 1-4 containing the monomer which has unsaturated bonds other than the polymeric compound represented by the said general formula (I).   Furthermore, the adhesive composition of Claim 5 containing a thermal-polymerization initiator.   A (co) polymer-containing pressure-sensitive adhesive composition obtained by (co) polymerizing the polymerizable compound represented by the general formula (I) contained in the pressure-sensitive adhesive composition according to claim 1. .   A copolymer-containing pressure-sensitive adhesive composition obtained by copolymerizing the polymerizable compound represented by the general formula (I) and the monomer having an unsaturated bond contained in the pressure-sensitive adhesive composition according to claim 5 or 6. object.   The adhesive sheet which has an adhesive layer formed from the (co) polymer containing adhesive composition of Claim 7 or 8. The polymerizable compound represented by the following general formula (I).

(In the formula, L is a direct bond or a substituent represented by any one of the following general formulas (II) to (IV), and X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ and X ⁸ are each independently a halogen atom-substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryl having 7 to 20 carbon atoms. Represents an alkyl group or a heterocyclic group having 2 to 20 carbon atoms, a hydrogen atom, or a halogen atom, and the methylene group in the alkyl group, aryl group and arylalkyl group is an unsaturated bond, -O-, -S-, (It may be interrupted by -CO-, -COO- or -OCO-).

(In the formula, X ⁹ , X ¹⁰ , X ¹¹ , X ¹² , X ¹³ , X ¹⁴ , X ¹⁵ , X ¹⁶ , X ¹⁷ , X ¹⁸ , X ¹⁹ and X ²⁰ are each independently substituted with a halogen atom. Or an unsubstituted alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms, a hydrogen atom Or a methylene group in the alkyl group, aryl group and arylalkyl group is interrupted by an unsaturated bond, -O-, -S-, -CO-, -COO- or -OCO-. In X ⁹ , X ¹⁰ , X ¹¹ and X ¹² , adjacent substituents in X ¹³ , X ¹⁴ , X ¹⁵ and X ^{16 and} in X ¹⁷ , X ¹⁸ , X ¹⁹ and X ²⁰ May be formed,
Y is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or 2 to 20 carbon atoms. A methylene group in the alkyl group, aryl group and arylalkyl group is an unsaturated bond, -O-, -S-, -CO-, -COO- or -OCO-. May be interrupted,
s represents the number of 0-8, x represents the number of 0-4, y represents the number of 0-4, the sum of the number of x and y is 2-4,
R ¹ and R ² represent a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R ¹ and R ² form a ring together. It may be. )