WO2007139173A1 - Optical film with adhesive - Google Patents

Abstract

Disclosed is an optical film with adhesive which is obtained by forming an adhesive layer on at least one side of an optical film. The adhesive layer is composed of a composition containing an acrylic resin, an ionic compound containing cations, and a crosslinking agent.

Description

 Specification

 Optical film with adhesive technology

 The present invention relates to an optical film with an adhesive. Examples of the optical film targeted in the present invention include a polarizing film and a retardation film. The present invention also relates to an optical laminated body for liquid crystal display using the optical film with an adhesive. Background art

 A polarizing film is mounted on a liquid crystal display device and widely used. A transparent protective film is laminated on both sides of a polarizer, and an adhesive layer is formed on the surface of at least one protective film. It is distributed with a release film stuck on top. Alternatively, a retardation film may be laminated on a polarizing film with a protective film bonded to both sides of the polarizer to form an elliptical polarizing film, and an adhesive layer / release film may be attached to the retardation film side. is there.

Furthermore, an adhesive layer peeling film may be stuck on the surface of the retardation film. Prior to bonding to the liquid crystal cell, the release film is peeled off from these polarizing film, elliptical polarizing film, retardation film, etc., and bonded to the liquid crystal cell via the exposed adhesive layer. Such a polarizing film, elliptically polarizing film, or retardation film generates static electricity when the release film is peeled off and bonded to a liquid crystal cell, and therefore development of a countermeasure to prevent it is desired.

As one of countermeasures, Japanese Patent No. 3012860 (Patent Document 1) discloses a polarizing film in which a protective film is laminated on the surface of a polarizer film and an adhesive layer is provided on the surface of the protective film. As an adhesive, it has been proposed to use a ionic conductive composition comprising an electrolyte salt and an organopolysiloxane and a composition containing an acryl-based copolymer. By using such an adhesive, antistatic properties are expressed. However, the performance was not necessarily sufficient, and the adhesion durability was not sufficient.

 On the other hand, JP 2004-536940 A (Patent Document 2) discloses that an organic salt antistatic agent is blended with a pressure sensitive adhesive (adhesive) to impart antistatic properties to the adhesive. It is disclosed. Further, in JP-A-2004-114665 (Patent Document 3), a salt composed of a quaternary ammonium cation having a total carbon number of 4 to 20 and a fluorine atom-containing anion is contained in an adhesive or the like. It is described that the antistatic property is imparted.

 Now, an optical film with an adhesive as described above is bonded to a liquid crystal cell on the adhesive layer side to form a liquid crystal display device. In this state, the optical film is placed under high temperature or high temperature and high humidity conditions, or heated. When cooling is repeated, foaming occurs in the pressure-sensitive adhesive layer as the optical film changes in size, or it floats or peels between the optical film and the pressure-sensitive adhesive layer, or between the pressure-sensitive adhesive layer and the liquid crystal cell glass. Therefore, it is required to have excellent durability without causing such problems. In addition, when exposed to high temperatures, the distribution of residual stress acting on the optical film becomes non-uniform, and stress concentration occurs on the outer periphery of the optical film. Such white spots are also required to be suppressed. Furthermore, if there is a defect when an optical film with an adhesive is bonded to a liquid crystal cell, the optical film must be peeled off and then re-applied. The film is peeled off with the optical film, so that the adhesive is not left on the cell glass, and so-called reworkability that does not cause fogging is also required.

An object of the present invention is to provide an optical film with an adhesive in which an antistatic property is improved and an adhesive layer having excellent durability is provided on the surface of the optical film. As a result of intensive studies to solve such problems, the present inventors have formulated a specific ionic compound into a pressure-sensitive adhesive containing a specific acrylic resin, and this composition is applied to the surface of the optical film. It was found that an optical film with an adhesive having excellent antistatic properties and durability can be obtained by providing it as a pressure-sensitive adhesive layer. Disclosure of the invention

 That is, according to the present invention, the pressure-sensitive adhesive layer is formed on at least one surface of the optical film, and the pressure-sensitive adhesive layer is formed from the composition containing the following components (A), (B) and (C). A formed optical film with a pressure-sensitive adhesive is provided.

 [0 0 0 9]

 (A) The following formula (I)

In the formula, R 1 represents a hydrogen atom or a methyl group, and R 2 represents an alkyl group or aralkyl group having 1 to 14 carbon atoms which may be substituted with an alkoxy group having 1 to 10 carbon atoms, respectively. ) Derived from an unsaturated carboxylic acid having a structural unit derived from a (meth) acrylic acid ester as the main component, and further having one olefinic double bond and at least one force loxyl group in the molecule. The first acrylic resin having a weight average molecular weight of 800,000 to 2,000,000 is contained, and the content of the structural unit derived from the unsaturated force sulfonic acid is 1 Acrylic resin in an amount of 0.5 to 10 parts by weight with respect to 0 part by weight;

 (Wherein R3 represents an alkyl group having 1 to 12 carbon atoms, R4, R5 and R6 are each independently carbon

Represents an alkyl group having a prime number of 6 to 12)

An ionic compound containing a cation represented by:

(C) Crosslinker. The above acrylic resin (A) can be composed of only the first acrylic resin specified above, or in addition to the first acrylic resin, a different acrylic resin (referred to as the second acrylic resin). ) And a mixture thereof. As the second acrylic resin, for example, a structural unit derived from the (meth) acrylic acid ester represented by the formula (I) as a main component and having a weight average molecular weight of 50,000 to 500,000 is used. Can be mentioned.

 Further, according to the present invention, there is also provided an optical laminate in which this optical film with an adhesive is laminated on a glass substrate on the adhesive layer side. BEST MODE FOR CARRYING OUT THE INVENTION

 Hereinafter, the present invention will be described in detail. In the present invention, the acrylic resin (A) serving as a resin component constituting the pressure-sensitive adhesive has a structural unit derived from the (meth) acrylic acid ester represented by the formula (I) as a main component, and further includes 1 in the molecule. A first acryl having a weight average molecular weight of 800,000 to 2,000,000, comprising a structural unit derived from an unsaturated carboxylic acid having one olefinic double bond and at least one forceful loxyl group It contains a resin. The acrylic resin (A) can be composed only of the first acrylic resin specified here, or in addition to the first acrylic resin, an acrylic resin different from that (referred to as the second acrylic resin) It can also be composed of a mixture containing. The structural unit derived from the unsaturated carboxylic acid is contained in the first acrylic resin at a ratio of 0.5 to 10 parts by weight with respect to 100 parts by weight of the entire acrylic resin (A). In addition, (meth) acrylic acid means that either acrylic acid or methacrylic acid may be used, and “(me)” in the case of (meth) acrylate is the same meaning.

In the above formula (I), which is the main structural unit of the first acrylic resin, R 1 is a hydrogen atom or a methyl group, and R 2 is an alkyl group or aralkyl group having 1 to 14 carbon atoms, preferably an alkyl group. It is a group. In the alkyl group or aralkyl group represented by R2, the hydrogen atom in each group is substituted by an alkoxy group having 1 to 10 carbon atoms. It may be.

 Specific examples of the (meth) acrylic acid ester represented by the formula (I) include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, n-butyl acrylate, and lauryl acrylate. Linear alkyl acrylates; branched alkyl alkyl esters such as isobutyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate; methyl methacrylate, ethyl methacrylate, propyl methacrylate Linear methacrylic acid alkyl esters such as ri-butyl methacrylate, n-octyl methacrylate, lauryl methacrylate; isoptyl methacrylate, 2-ethylhexyl methacrylate, methacrylate Examples include branched alkyl methacrylates such as isooctyl acid. It is.

 When R 2 is an alkyl group substituted with an alkoxy group, that is, when R 2 is an alkoxyalkyl group, as the (meth) acrylic acid ester represented by the formula (I), specifically, Examples include 2-methoxyethyl acrylate, ethoxymethyl acrylate, 2-methoxyethyl methacrylate, ethoxymethyl methacrylate, and the like. Specific examples of the (meth) acrylic acid ester represented by the formula (I) when R 2 is an aralkyl group include benzyl acrylate and benzyl acrylate.

 In the production of the first acrylic resin, as the (meth) acrylic acid ester represented by the formula (I), one kind of compound may be used, or two or more kinds of compounds may be used. Among them, it is preferable to use butyl acrylate as at least one monomer. Therefore, it is a preferred form that the structural unit derived from the (meth) acrylate ester constituting the first acrylic resin contains a unit derived from butyl acrylate.

The unsaturated carboxylic acid, which is another structural unit of the first acrylic resin, is a compound having one olefinic double bond and at least one force group in the molecule. Examples include acrylic acid, methacrylic acid, maleic acid, itako An acid etc. are mentioned. Of these, acrylic acid or methacrylic acid is preferred. Further, the first acrylic resin may contain a structural unit derived from a monomer having a polar functional group other than a carboxyl group. Examples of the polar functional group other than the strong lpoxyl group include a hydroxyl group, an amide group, an epoxy group, an oxenyl group, an amino group, an isocyanato group, and an aldehyde group.

 Examples of the monomer whose polar functional group is a hydroxyl group include (meth) acrylic acid 2-hydroxychetyl, (meth) acrylic acid 2-hydroxypropyl, and (meth) acrylic acid 4-hydroxybutyl. Examples of the monomer whose polar functional group is an amide group include acrylamide, methyl acrylamide, N, N-dimethylaminopropyl acrylamide, N, N-dimethyl acrylamide, N, N-dimethyl acrylamide, and N-methylol acrylamide. Etc. Examples of monomers whose polar functional group is an epoxy group include glycidyl acrylate, glycidyl methacrylate, 3, 4-epoxycyclohexyl methyl acrylate, and 3, 4-epoxycyclohexyl. Examples include methyl methacrylate. Examples of monomers whose polar functional group is an oxetanyl group include, for example, oxetanyl (meth) acrylate, 3-oxetanylmethyl (meth) acrylate, (3_methyl-1-3-oxenanyl) methyl (meta ) Acrylate, (3_ethyl 3-oxene) methyl (meth) acrylate, and the like. Examples of the monomer whose polar functional group is an amino group include N, N-dimethylaminoethyl acrylate and arylamine. Examples of the monomer whose polar functional group is an isocyanato group include 2-methacryloyloxychetyl isocyanate. Examples of the monomer whose polar functional group is an aldehyde group include acrylic aldehyde.

In the first acrylic resin, the structural unit derived from the (meth) acrylic acid ester represented by the formula (I) based on the weight of the entire nonvolatile content is usually 60 to 99.5% by weight, preferably Is contained in an amount of 80 to 99.5% by weight. The structural unit derived from unsaturated carboxylic acid is usually about 0.5 to 10% by weight, preferably 1 to 6% by weight. Contained. The structural unit derived from the unsaturated carboxylic acid is 100 parts by weight of the entire acrylic resin (A), that is, when the acrylic resin (Ά) is composed of only the first acrylic resin. 0.5 to 10 parts by weight with respect to 100 parts by weight, and when composed of the first acrylic resin and a second acrylic resin different from the first acrylic resin, It is contained in a proportion by weight. The ratio of the structural unit derived from the unsaturated carboxylic acid to 100 parts by weight of the acrylic resin (A) is preferably 0.5 to 6 parts by weight. Acrylic resin (A) When the amount of the structural unit derived from unsaturated carboxylic acid is 100% by weight or more with respect to 100 parts by weight, the pressure-sensitive adhesive layer containing the structural unit is bonded to the glass substrate. Furthermore, it is preferable because floating and peeling between the glass substrate and the pressure-sensitive adhesive layer tend to be suppressed. Also, if the amount is 10 parts by weight or less, even if the dimensions of the optical film change due to temperature changes, etc., the pressure-sensitive adhesive layer fluctuates following the change in dimensions, so the brightness of the peripheral edge of the liquid crystal cell And the brightness of the central portion disappears, and white unevenness tends to suppress uneven color. Furthermore, if the amount of the structural unit derived from the unsaturated carboxylic acid is in the range of 0.5 to 10 parts by weight relative to 100 parts by weight of the acrylic resin (A), an ionic compound (described later) From the viewpoint of compatibility with B).

 The first acrylic resin may contain a structural unit derived from a monomer other than the (meth) acrylic acid ester represented by the formula (I) and the unsaturated carboxylic acid described above. Examples of such a monomer that can be optionally used include, for example, a heterocyclic monomer having one olefinic double bond and at least one heterocyclic group of 5 or more members in the molecule. Can be mentioned. Here, the 5- or more-membered heterocyclic group is an alicyclic hydrocarbon group having 5 or more carbon atoms, preferably 5 to 7 carbon atoms, and at least one of them is a nitrogen atom or an oxygen atom. A group substituted by a heteroatom such as a sulfur atom.

Specific examples of heterocyclic monomers include acryloylmorpholine, vinylcaprolactam, N-vinyl_2-pyrrolidone, tetrahydryl furfuryl acrylate, tetrahydrofurfuryl methacrylate, force prolactone-modified tetraoctyl Examples include full furyl acrylate. In addition, monomers such as 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, etc., in which heteroatoms constitute a three-membered ring and a seven-seven ring, Since it has a 7-membered heterocyclic group, it can be treated as a heterocyclic monomer. Furthermore, an olefinic double bond may be included in the heterocyclic group, such as 2,5-dihydrofuran. Two or more different monomers may be used as the heterocyclic monomer. Among these, N-vinylpyrrolidone, vinylcaprolactam, acryloylmorpholine or a mixture thereof is preferable as the heterocyclic monomer. When a structural unit derived from a heterocyclic monomer is contained in the first acrylic resin, the amount is usually up to about 30% by weight based on the first acrylic resin, preferably 2 0% by weight or less. If the first acrylic resin contains 0.1% by weight or more of a structural unit derived from a heterocyclic monomer, the pressure-sensitive adhesive layer follows the dimensional change even if the optical film changes in size. As a result, there is no difference between the brightness of the periphery of the liquid crystal cell and the brightness of the center, and there is a tendency that white unevenness is suppressed 6

Another monomer that can be optionally used includes an alicyclic monomer having one olefinic double bond and at least one alicyclic structure in the molecule. The alicyclic structure is usually a paraffin structure or a cycloolefin structure having 5 or more carbon atoms, preferably about 5 to 7 carbon atoms. In the cycloolefin structure, an olefinic double bond is added to the alicyclic structure. Have. Specific examples of acrylates having an alicyclic structure include isobornyl acrylate, cyclohexyl acrylate, dicyclopentyl acrylate, cyclododecyl acrylate, methyl cyclohexyl acrylate, and trimethylcycloacrylate acrylate. Hexyl, tert-butyl cyclohexyl acrylate, cyclohexyl ethoxy acrylate, cyclohexyl phenyl acrylate, and the like, and methacrylic acid ester having an alicyclic structure, isopornyl methacrylate, Cyclohexyl methacrylate, dicyclopentyl methacrylate, cyclododecyl methacrylate, methylcyclomethacrylate Hexyl, trimethylcyclohexyl methacrylate, tert-butyl cyclohexyl methacrylate, cyclohexylphenyl methacrylate, and the like. Examples of the acrylate having a plurality of alicyclic structures in the molecule include biscyclohexylmethyl ether, dicyclooctylate, dicyclododecylmethyl succinate, and the like. Furthermore, vinyl cyclohexyl acetate having a vinyl group can also be an alicyclic monomer. Of these, isopornyl acrylate, cyclohexyl acrylate, isopornyl methacrylate, cyclohexyl methacrylate, and dicyclopentanyl acrylate are preferred because they are readily available. As the alicyclic monomer, two or more different compounds may be used in combination. When the first acrylic resin contains a structural unit derived from an alicyclic monomer, the amount is usually up to about 30% by weight, preferably 15% by weight, based on the first acrylic resin. % Or less. If the structural unit derived from the alicyclic monomer is contained in the first acrylic resin in an amount of 0.1% by weight or more, and further 1% by weight or more, the floating or peeling between the glass substrate and the pressure-sensitive adhesive layer is caused. Tend to be suppressed.

 As another monomer, a vinyl monomer different from any of the (meth) acrylic acid ester represented by the formula (I), the heterocyclic monomer, and the alicyclic monomer may be used. Examples of such vinyl monomers include fatty acid vinyl esters, vinyl halides, vinylidene halides, (meth) acrylonitrile, conjugated phene compounds, and aromatic vinyls.

Examples of the fatty acid vinyl ester include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, and vinyl laurate. Examples of the vinyl halide include vinyl chloride and vinyl bromide, examples of the vinylidene halide include vinylidene chloride, and examples of the (meth) acrylonitrile include acrylonitrile and methacrylonitrile. Conjugated compounds are olefins having a conjugated double bond in the molecule, and specific examples include isoprene, butadiene, and black-opened plane. Aromatic vinyl is a compound having an aromatic ring and a vinyl group. Lene, Methyl styrene, Dimethyl styrene, Trimethyl styrene, Edyl styrene, Jetyl styrene, Polyethyl styrene, Propyl styrene, Butyl styrene, Hexyl styrene, Heptyl styrene, Octyl styrene, Fluorostyrene, Chlorostyrene, Bromostyrene, Dive mouth Examples thereof include styrene monomers such as styrene styrene, nitro styrene, acetyl styrene, and methoxy styrene, and nitrogen-containing aromatic vinyl such as vinyl pyridine and vinyl carbazole. These vinyl monomers may be used in combination of two or more different compounds.

 When the first acrylic resin contains the structural unit derived from the vinyl monomer as described above, the amount is usually 5% by weight or less, preferably 0.0, based on the first acrylic resin. Although it is 5% by weight or less, it is more preferable that these are not substantially contained.

 Even when introducing a plurality of structural units derived from heterocyclic monomers, structural units derived from alicyclic monomers, and structural units derived from vinyl monomers, The total amount is preferably 30% by weight or less, more preferably 20% by weight or less, based on the first acrylic resin.

Examples of the method for producing the first acrylic resin described above include a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, a suspension polymerization method, and the like. Among these, the solution polymerization method is preferable. As a specific example of the solution polymerization method, a desired monomer and an organic solvent are mixed, and the monomer concentration is adjusted to 50% by weight or more, preferably 50 to 60% by weight. After that, in a nitrogen atmosphere, about 0.01 to 5 parts by weight of a polymerization initiator is added per 100 parts by weight of the total monomer, and about 40 to 90, preferably about 50 to 7 For example, a method of stirring for about 8 hours or more, preferably about 8 to 12 hours, may be mentioned. As the polymerization initiator, a thermal polymerization initiator or a photopolymerization initiator is used. Examples of the photopolymerization initiator include 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone. Examples of thermal polymerization initiators include 2,2'-azobisisoptyronitrile, 2,2'-azobis (2-methyl Ptyronitrile), 1,1'-azobis (cyclohexane-1), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl) —4—Mexoxyvaleronitrile), dimethyl _ 2, 2 ′ — azobis (2-methylpropionate), 2, 2 ′ — azobis (2-hydroxymethylpropionitryl); Lauryl peroxide, ter t-butyl hydride peroxide, benzoyl peroxide, ter t-butyl peroxybenzoate, cumene hydride peroxide, diisopropyl peroxide dicarbonate, di-n-propyl peroxide Force ponate, t ter t-butyl peroxyneodecanoate, ter t-butyl peroxypivalate, (3,5,5-trimethylhexanoyl) Such organic peroxides Okishido; persulfate force Riumu, persulfate acid Anmoniumu, and the like such as inorganic peroxides of hydrogen peroxide. A redox initiator using a peroxide and a reducing agent in combination may also be used as a polymerization initiator.

 Examples of the organic solvent used in the polymerization reaction include aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate and butyl acetate; aliphatic alcohols such as n-propyl alcohol and isopropyl alcohol; acetone and methyl ethyl And ketones such as luketone and methyl isobutyl ketone.

The molecular weight of the first acrylic resin is in the range of 800,000 to 2,000,000 in terms of weight average molecular weight (Mw) in terms of standard polystyrene by gel permeation chromatography (GPC). When the weight average molecular weight is 800,000 or more, the adhesiveness under high temperature and high humidity is improved, and the possibility of floating or peeling between the glass substrate and the pressure-sensitive adhesive layer tends to be reduced. Moreover, it is preferable because it tends to improve reworkability. If the weight average molecular weight is 2,000, 000 or less, the dimensions of the optical film bonded to the adhesive layer change with temperature. The adhesive layer fluctuates in accordance with the dimensional change, so there is no difference between the brightness at the periphery of the liquid crystal cell and the brightness at the center, and white unevenness is suppressed. It is preferable because of its tendency. Weight average molecular weight (Mw) and number average molecular weight (Mn) ratio (Mw / Mn) The fabric is usually in the range of 2-10.

 The pressure-sensitive adhesive used in the present invention may contain a second acrylic resin different from the first acrylic resin as the acrylic resin (A). Examples of the second acryl resin that can be separately contained include, for example, a structural unit derived from a (meth) acrylic acid ester represented by the formula (I) as a main component, and a weight average molecular weight in terms of standard polystyrene by GPC. A low molecular weight substance having (Mw) in the range of about 50,000 to 500,000 can be mentioned.

 When the second acrylic resin having a low molecular weight is used, the amount is usually 10 to 50 parts by weight, preferably 20 to 40 parts per 100 parts by weight of the total nonvolatile content of the acrylic resin (A). About parts by weight. If the amount of the second acrylic resin relative to 100 parts by weight of the total acrylic resin is 10 parts by weight or more, even if the dimension of the optical film changes, the adhesive layer changes following the change in dimension. Therefore, it is preferable that there is no difference between the brightness of the peripheral edge of the liquid crystal cell and the brightness of the central part, and the white unevenness tends to be suppressed, and the amount of the second acrylic resin is 5 If it is 0 parts by weight or less, the adhesiveness at high temperature and high humidity will improve, and the possibility of floating or peeling between the glass substrate and the adhesive layer will tend to decrease, and reworkability will improve. This is preferable.

 The acrylic resin (A) used for the adhesive is only the acrylic resin (if only the first acrylic resin is used, the acrylic resin, or if the first acrylic resin and the second acrylic resin are used in combination) A solution prepared by dissolving a mixture thereof in ethyl acetate to a non-volatile content of 20% by weight exhibits a viscosity of 1 O Pa · s or less at a temperature of 25, or 0.1 to 7 Pa · s. preferable. If the viscosity is 10 Pa's or less, the adhesiveness under high temperature and high humidity is improved, and the possibility of floating or peeling between the glass substrate and the adhesive layer tends to be reduced. Moreover, it is preferable because reworkability tends to be improved. Viscosity can be measured with a Brookfield viscometer.

In the present invention, in addition to the acrylic resin (A) as described above, an ionic compound (B) Is used. This ionic compound (B) contains a cation represented by the above formula (II). In this formula (II), R 3 represents an alkyl group having 1 to 12 carbon atoms, and R 4, R 5 And R 6 each independently represents an alkyl group having 6 to 12 carbon atoms. Therefore, the cation represented by the formula (II) is a tetraalkylammonium cation. This ionic compound (B) is advantageously liquid at room temperature (around 2 3). From the viewpoint of compatibility with the acrylic resin (A), the tetraalkylammonium cation represented by the formula (II) has a total carbon number of 15 or more, more preferably 20 or more, especially 22 or more. preferable. The total carbon number is preferably 36 or less, more preferably 30 or less.

 Specific examples of the tetraalkylammonium cation represented by the formula (I I) include the following.

 Tetrahexyl ammonium cation,

 Tetraoctyl ammonium cation,

 Trihexylmethyl ammonium cation,

 Trioctylmethylammonium cation,

 Tridecylmethyl ammonium cation,

 Trihexylethylammonium cation,

 Trioctylchetilammonium cation.

 On the other hand, it is preferable that the anion component constituting the ionic compound (B) satisfies the fact that it becomes an ionic liquid, and the others are not particularly limited, but examples thereof include the following. Can do.

 Chloride anion [C 1—],

 Professional Myonion [B],

 One-door two-on [1—],

Tetrachloroaluminate anion [A 1 C 1 ₄ —],

Hep evening chlorodialuminescence anion [A l ₂ C l ₇ —],

Tetrafluoroporate anion [BF ₄ —], Hexafluorophosphate anion (PF ₆ :),

Park opening Retanion [C 1_Rei ₄ -],

Knightley Tonion [N0 ₃ —],

Acetate anion [CH ₃ CO〇-],

Trifluoroacetate anion [CF ₃ CO〇-],

Methanesulfonate anion [CH ₃ S0 ₃ —],

Trifluoromethanesulfonate anion [CF ₃ S ○ _3- ],

Bis (trifluoromethanesulfonyl) imidoanion ((CF ₃ S0 ₂ ) ₂ N-], Tris (trifluoromethanesulfonyl) metadionic dione [(CF ₃ S0 ₂ ) 3],

Hexafluoroarsenate anion [As F ₆ —],

Hexafluoroantimonate anion [SbF ₆ —],

Hexafluororoniobe anion [NbF ₆ —J,

Hexafluororotantale anion [TaF ₆ —],

 (Poly) Hyde mouth fluorofluoride anion [F (HF) n—] (n is about 1 to 3),

Dishnami Doonion [(CN) ₂ N-],

Perfluorobutanesulfonate anion [C ₄ F ₉ S〇 ₃ —],

Bis (Pen evening fluorethansulfonyl) imidoanion t (C ₂ F ₅ S 0 ₂ ) ₂ N-],

Perfluorolob Yunoe 1 canyon [C ₃ F ₇ COO-],

 (Trifluoromethanesulfonyl) (Trifluoromethane power luponyl) Imido anion

[(CF ₃ S 0 ₂ ) (CF ₃ C 0) N-] etc.

Among these, an anion component containing a fluorine atom is preferably used because an ionic compound having a low melting point is obtained, and bis (trifluoromethylsulfonyl) imidoanion is particularly preferable. Specific examples of the ionic compound used in the present invention can be appropriately selected from the combination of the cation component and the anion component. Specific compounds that are a combination of a cation component and an anion component include the following.

 Tetrahexylammonium bis (trifluoromethanesulfonyl) imide, trihexylmethylammonium bis (trifluoromethanesulfonyl) imide, trioctylmethylammonium bis (trifluoromethanesulfonyl) imide, tetrahexyl Ammonium hexafluorophosphate, trihexylmethylammonium hexaphosphate, trioctylmethyl ammonium hexafluorophosphate, tetrahexyl ammonium perchlorate, trihexylmethyl Ammonium Park Mouth Rate, Trioctyl Methyl Ammonium Park Mouth Rate, etc.

 The ionic compound (B) is preferably contained at a ratio of about 0.5 to 10 parts by weight with respect to 100 parts by weight of the non-volatile content of the acrylic resin (A). It is more preferable to make it contain in the ratio of 6 weight part. When the ionic compound (B) is contained in an amount of 0.5 parts by weight or more with respect to 100 parts by weight of the non-volatile content of the acrylic resin (A), the antistatic performance is preferably improved. When present, the ionic compound (B) is preferred because it is difficult to bleed out.

 A crosslinking agent (C) is further blended with the acrylic resin (A) and the ionic compound (B) as described above to obtain a pressure-sensitive adhesive composition. The crosslinking agent (C) is a compound having in the molecule at least two functional groups capable of crosslinking with the structural unit derived from the unsaturated carboxylic acid in the acrylic resin (A), particularly in the first acrylic resin. Specifically, an isocyanate compound, an epoxy compound, a metal chelate compound, an aziridine compound and the like are exemplified.

An isocyanate compound is a compound having at least two isocyanato groups (one NCO) in the molecule. For example, tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate. Hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, water Examples thereof include diphenylmethane diisocyanate, naphthenic diisocyanate, and triphenylmethane triisocyanate. Adducts obtained by reacting these isocyanate compounds with polyols such as glycerol and trimethylolpropane, and those obtained by converting isocyanate compounds into dimers and trimers are also crosslinking agents used in adhesives. sell. Two or more isocyanate compounds can also be mixed and used.

 Epoxy compounds are compounds having at least two epoxy groups in the molecule, such as bisphenol A type epoxy resin, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl. Ether, 1,6-hexanehexanediglycidyl ether, trimethylolpropane tridaricidyl ether, N, N-diglycidyl dilin, N, N, N ', N'-tetraglycidyl m-xylenediamine, 1,3- Examples include bis (Ν, — '-diglycidylaminomethyl) and hexane. Two or more epoxy compounds can be mixed and used.

 As the metal chelate compound, for example, acetyl acetylacetonate acetyl acetate is coordinated to a polyvalent metal such as aluminum, iron, copper, zinc, zinc, titanium, nickel, antimony, magnesium, vanadium, chromium and zirconium. Compounds.

Aziridine-based compounds are compounds that have at least two 3-membered ring skeletons consisting of one nitrogen atom and two carbon atoms, also called ethyleneimine, such as diphenylmethane-4,4'-bis (1 -Aziridine power lupoxamide), Toluene-2,4-bis (1_Aziridinecarboxamide), Triethylenemelamine, Isophthaloylbis-11- (2-methylaziridine), Tris-11-aziridinylphosphine oxide, To Xamethylene-1,6-bis (1-aziridin carboxamide), trimethylolpropane-tri-; 3-aziridinylpropionate, tetramethylolmethane-tree) 3-aziridinylpropionate And so on.

 Among these cross-linking agents, isocyanate-based compounds, especially xylylene diisocyanate or tolylene disocyanate, or adducts obtained by reacting polyols such as glycerol trimethylolpropane with these isocyanate compounds. In addition, mixtures of isocyanate compounds made into dimers, trimers, etc., and mixtures of these isocyanate compounds are preferably used. Suitable isocyanate compounds include tolylene diisocyanate, adducts obtained by reacting tolylene diisocyanate with polyol, tolylene diisocyanate dimers, and tolylene diisocyanate trimers. . The crosslinking agent (C) is usually blended at a ratio of about 0.1 1 to 10 parts by weight, preferably about 0.1 to 7 parts by weight with respect to 100 parts by weight of the acrylic resin (A). The amount of the crosslinking agent (C) relative to 100 parts by weight of the acrylic resin (A) is preferably not less than 0.01 parts by weight because the durability of the pressure-sensitive adhesive layer tends to be improved. Part or less is preferred because white spots are not noticeable when the optical film with an adhesive is applied to a liquid crystal display device.

 The pressure-sensitive adhesive for forming the pressure-sensitive adhesive layer in the present invention preferably contains a silane compound in order to improve the adhesion between the pressure-sensitive adhesive layer and the glass substrate. It is preferable to contain a silane compound in the acrylic resin.

Examples of silane compounds include vinyltrimethoxysilane, vinyltriethoxysilane, vinylyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl). 1) 3-Aminoprovir trimethoxysilane, 3-Aminopropyltriethoxysilane, 3-Glycidoxypropyl trimethoxysilane, 3-Glycidoxypyrumethyldimethoxysilane, 2- (3, 4-Epoxycyclo) Hexyl) Ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyl trimethoxysilane 3-mercaptopropyl trimethoxysilane, 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, 3-glycidoxypropylethoxydi Examples include methylsilane. Two or more silane compounds may be used. The silane compound may be of a silicone oligomer type. Examples of silicone oligomers in the form of (monomer) oligomers include the following.

 3-mercaptopropyl trimethoxysilane, tetramethoxysilane copolymer,

3-mercaptopropyltrimethoxysilane-tetraethoxysilane copolymer, 3-mercaptopropyltriethoxysilane-tetramethoxysilane copolymer,

A copolymer containing a mercaptopropyl group, such as 3-mercaptopropyltriethoxysilane-tetraethoxysilane copolymer;

 Contains mercaptomethyl groups, such as mercaptomethyltrimethoxysilane-tetramethoxysilane copolymer, mercaptomethyltrimethoxysilane / tetraethoxysilane copolymer, mercaptomethyltriethoxysilane / tetramethoxysilane copolymer, mercaptomethyltriethoxysilane / tetraethoxysilane copolymer A copolymer of

 3-methacryloyloxypropyltrimethoxysilane-tetramethoxysilane copolymer,

 3—Metriacryloyloxypropyl trimethoxysilane-tetraethoxysilane copolymer,

 3-methacryloyloxypropyltriethoxysilane-tetramethoxysilane copolymer,

 3-methacryloyloxypropyltriethoxysilane-tetraethoxysilane copolymer,

3-methacryloyloxypropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-methacryloyloxypropylmethyldimethoxysilane-tetraethoxy silane copolymer, silane copolymer,

 3 _Methacryloxy propyl methyl jetoxy silane-tetraethoxy silane copolymer

A copolymer containing a methacryloyloxypropyl group, such as

 3-acryloyloxypropyl trimethoxysilane, tetramethoxysilane copolymer,

 3-acryloyloxypropyltrimethoxysilane-tetraethoxysilane copolymer,,

 3-acryloyloxypropyltriethoxysilane-tetramethoxysilane copolymer,

 3-acryloyloxypropyltriethoxysilane-tetraethoxysilane copolymer,

 3-acryloyloxypropylmethyldimethoxysilane-tetramethoxysilane copolymer,,

 3-acryloyloxypropylmethyldimethoxysilane-tetraethoxysilane copolymer,

 3 —acryloyloxypropyl tiljetoxysilane-tetramethoxysilane copolymer,

 3-Atalyloxypropylmethyljetoxysilane-tetraethoxysilane copolymer

A copolymer containing acryloyloxypropyl groups, such as

 Vinyltrimethoxysilane-tetramethoxysilane copolymer,

 Vinyltrimethoxysilane-tetraethoxysilane copolymer,

Vinyltriethoxysilane-tetramethoxysilane copolymer, Vinyl group such as vinyl-polyethoxysilane-tetraethoxysilane copolymer, vinylmethyldimethyloxysilane-tetramethoxysilane copolymer, vinylmethyldimethoxysilane-tetraethoxysilane copolymer, vinylmethyljetoxysilane-tetramethoxysilane copolymer Containing copolymers;

 3-Aminopropyl trimethoxysilane-tetramethoxysilane copolymer, 3-Aminopropyltrimethoxysilane-tetraethoxysilane copolymer, 3-Aminopropyltriethoxysilane-tetramethoxysilane copolymer, 3-Aminopropyl Triethoxysilane, tetraethoxysilane copolymer, '3-aminopropylmethyldimethoxysilane, tetramethoxysilane copolymer, 3-aminopropylmethyldimethoxysilane, tetraethoxysilane copolymer, 3-aminopropylmethyljetoxysilane Examples include tetramethoxysilane copolymers and amino group-containing copolymers such as 3-aminopropylmethyljetoxysilane-tetraethoxysilane copolymer.

 These silane compounds are often liquids. The compounding amount of the silane compound in the pressure-sensitive adhesive is usually 0.000 to 1 to 10 weights with respect to 100 parts by weight of the nonvolatile content of the acrylic resin (A) (the total weight when two or more kinds are used). About 0.1 part, preferably 0.1 to 5 parts by weight. The amount of the silane compound relative to 100 parts by weight of the nonvolatile content of the acrylic resin is preferably 0.001 part by weight or more because the adhesiveness between the pressure-sensitive adhesive layer and the glass substrate is improved. Further, when the amount is 10 parts by weight or less, it is preferable because the silane compound tends to be suppressed from bleeding out from the pressure-sensitive adhesive layer.

The pressure-sensitive adhesive described above may further contain a crosslinking catalyst, a weathering stabilizer, an evening fire, a plasticizer, a softening agent, a dye, a pigment, an inorganic filler, and the like. Among them, when a crosslinking catalyst is blended with an adhesive in addition to a crosslinking agent, the pressure-sensitive adhesive layer can be prepared by aging in a short time, and in the obtained optical optical film with a pressure-sensitive adhesive, Occurrence of floating or peeling between the pressure-sensitive adhesive layer and foaming in the pressure-sensitive adhesive layer can be suppressed, and reworkability can be further improved. Examples of the bridge catalyst include hexamethylenediamine, ethylenediamine, polyethyleneimine, hexamethylenetetramine, diethylenetriamine, triethylenetetramine, isophoronediamine, trimethylenediamine, polyamino resin, and melamine resin. A compound etc. can be mentioned. When an amine compound is blended in the pressure-sensitive adhesive as a crosslinking catalyst, an isocyanate compound is suitable as the crosslinking agent.

 The optical film used for the optical film with a pressure-sensitive adhesive of the present invention is a film having optical characteristics, and examples thereof include a polarizing film and a retardation film.

A polarizing film is an optical film having a function of emitting polarized light with respect to incident light such as natural light. The polarizing film absorbs linearly polarized light having a vibrating surface in a certain direction and transmits linearly polarized light having a vibrating surface perpendicular to the polarizing film, and reflects linearly polarized light having a vibrating surface in a certain direction. There are a polarizing film having a property of transmitting linearly polarized light having a vibration plane orthogonal to the polarizing film, and an elliptically polarizing film in which a polarizing film and a retardation film described later are laminated. As a preferred specific example of a polarizing film, particularly a linear polarizing film (sometimes called a polarizer or a polarizer film), a dichroic dye such as iodine or a dichroic dye is applied to a uniaxially stretched polyvinyl alcohol resin film. Are adsorbed and oriented. Retardation film is an optical film showing optical anisotropy, for example, polyvinyl alcohol, polycarbonate, polyester, polyarylate, polyimide, polyolefin, cyclic polyolefin, polystyrene, polysulfone, polyethersulfone, polysulfone A polymer film made of vinylidene fluoride / polymethyl methacrylate, liquid crystal polyester, acetyl cellulose, ethylene vinyl acetate copolymer genide, polyvinyl chloride, etc. should be stretched by about 1.0 to 6 times. The stretched film etc. which are obtained by these are mentioned. Above all, polycarbonate A polymer film obtained by uniaxially or biaxially stretching a cyclic polyolefin-based film is preferable. Although there are what are called a uniaxial retardation film, a wide viewing angle retardation film, a low light retardation film, etc., they can be applied to any of them.

 In addition, a film that exhibits optical anisotropy by applying a liquid crystal compound by orientation and a film that exhibits optical anisotropy by applying an inorganic layered compound can also be used as the retardation film. Such retardation films include what are called temperature-compensated phase difference films, and films with a twisted orientation of rod-like liquid crystals sold by Nippon Oil Corporation under the product name “LC film”. Also, a film with a tilted orientation of the rod-shaped liquid crystal sold under the product name “NH film” by Shin Nippon Oil Co., Ltd., and the product name “WV film” by Fuji Photo Film Co., Ltd. A film with a disc-shaped liquid crystal tilt-aligned, a fully biaxially oriented film sold under the trade name “VAC film” by Sumitomo Chemical Co., Ltd., and a “new VAC film” product from Sumitomo Chemical Co., Ltd. Biaxially oriented film sold under the name.

 Further, those having a protective film attached to these optical films can also be used as optical films. As the protective film, a transparent resin film is used. Examples of the transparent resin include acetyl cellulose resins represented by triacetyl cellulose and diacetyl cellulose, and methyl methacrylate represented by polymethyl methacrylate. Resin, polyester resin, polyolefin resin, polycarbonate resin, polyether ether ketone resin, polysulfone resin and the like. Even if the resin constituting the protective film contains an ultraviolet absorber such as a salicylic acid ester compound, a benzophenone compound, a benzotriazol compound, a triazine compound, a cyanoacrylate compound, or a nickel complex compound. Good. As the protective film, a acetyl cellulose resin film such as a triacetyl cellulose film is preferably used.

Among the optical films described above, the linearly polarizing film is the polarization that forms it. It is often used in a state in which a protective film is attached to one or both sides of a photon, for example, a polarizer film made of a polyvinyl alcohol-based resin. The elliptically polarizing film described above is a laminate of a linearly polarizing film and a retardation film, and the polarizing film is also in a state where a protective film is attached to one or both sides of the polarizer film. There are many cases. When the pressure-sensitive adhesive layer according to the present invention is formed on such an elliptically polarizing film, the pressure-sensitive adhesive layer is usually formed on the retardation film side.

 The optical film with pressure-sensitive adhesive of the present invention can be laminated on a glass substrate with the pressure-sensitive adhesive layer to form an optical laminate. Examples of the glass substrate include a liquid crystal cell glass substrate, an antiglare glass, and a glass for sunglasses. Above all, an optical film with adhesive (upper polarizing film) is laminated on the glass substrate on the front side (viewing side) of the liquid crystal cell, and another optical film with adhesive (lower polarizing film) on the glass substrate on the rear side of the liquid crystal cell. The optical laminate formed by laminating is preferable because it can be used as a liquid crystal display device. Examples of the glass substrate material include soda lime glass, low alkali glass, and non-alkali glass.

An optical film with an adhesive is, for example, a method in which an adhesive is laminated on a release film, an optical film is further laminated on the obtained adhesive layer, an adhesive is laminated on the optical film, and the adhesive surface It can be manufactured by a method such as attaching a release film to protect the film and forming an optical film with an adhesive. Here, as the release film, for example, a film made of various resins such as polyethylene terephthalate, polybutylene terephthalate, polystrength, polyarylate, etc. is used as a base material, and the adhesive layer of this base material is bonded. Examples of the surface include those subjected to release treatment such as silicone treatment. In order to laminate an optical film with an adhesive on a glass substrate to form an optical laminate, for example, the release film is peeled off from the optical film with an adhesive obtained as described above, and the exposed adhesive layer is removed from the glass substrate. What is necessary is just to stick together on the surface. The optical film with pressure-sensitive adhesive of the present invention is bonded to a glass substrate to form an optical laminate, and then the optical film is peeled off from the glass substrate due to some inconvenience. In addition, the pressure-sensitive adhesive layer is peeled off along with the optical film, and almost no fogging or adhesive residue is generated on the surface of the glass substrate that has been in contact with the pressure-sensitive adhesive layer. It is easy to reattach the attached optical film. That is, it is excellent in so-called reworkability.

 The liquid crystal display device formed from the optical laminate of the present invention is, for example, a personal computer liquid crystal display including a notebook type, a desktop type, a PDA (Personal Digital Assistant), a television, It can be used for in-vehicle displays, electronic dictionaries, digital cameras, digital video cameras, electronic desk calculators, and watches. EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In the examples, “parts” and “%” used to represent “amount” or “amount” are based on weight unless otherwise specified. The nonvolatile content is a value measured by a method according to I IS K 5407. Specifically, the adhesive solution was taken in a petri dish at an arbitrary weight, and the weight of the residual nonvolatile content after drying for 2 hours at 1 15 in an explosion-proof oven was expressed as a percentage of the weight of the solution first measured. Is. The weight average molecular weight was measured by placing two “TSK gel G6000HXL” and two “TSK gel G5000HXL” manufactured by Tosoh Corporation in series on the GPC device as the eluent. Tetrahydrofuran was used and converted into standard polystyrene under conditions of a sample concentration of 5 mg / mK, a sample introduction amount of 100, a temperature of 40, and a flow rate of 1 mlZ. First, an example in which the first acryl resin having a high molecular weight defined in the present invention is produced is shown.

 [Polymerization Example 1]

In a reactor equipped with a condenser, a nitrogen inlet, a thermometer and a stirrer, 8 1-8 parts ethyl acetate, 77.0 parts butyl acrylate, 20.0 parts methyl acrylate and acrylic acid 3.0 parts of the mixed solution was charged, and the internal temperature was raised to 55 t while substituting the air inside the apparatus with nitrogen gas to make it oxygen-free. Thereafter, a total solution of 0.14 parts of azobisisoptyronitrile (polymerization initiator) dissolved in 10 parts of ethyl acetate was added. One hour after the addition of the initiator, 12% of the internal temperature was 54 to 56 while adding ethyl acetate continuously to the reactor at an addition rate of 17.3 parts hr so that the concentration of the acrylic resin excluding the monomer would be 35%. The temperature was kept for a while, and finally, ethyl acetate was added to adjust the concentration of the acrylic resin to 20%. The obtained acrylic resin had a weight average molecular weight Mw of 1,560,000 and Mw / Mn of 4.7 by polystyrene conversion by GPC. This is acryl resin A1. [Polymerization Example 2]

 An acrylic resin solution was obtained in the same manner as in Polymerization Example 1 except that the monomer composition was changed to 98.9 parts of butyl acrylate and 1.1 parts of acrylic acid. The obtained acrylic resin had a polystyrene equivalent weight average molecular weight Mw by GPC of 1,200,000 and Mw / Mn of 3.9. This is called acrylic resin A2. Next, the example which manufactured the low molecular weight 2nd acryl resin is shown. [Polymerization Example 3]

The same reactor used in Polymerization Example 1 was charged with 222 parts of ethyl acetate, 35 parts of methyl acrylate, 44 parts of butyl methacrylate, 20 parts of methyl acrylate and 1 part of 2-hydroxyethyl acrylate. After replacing the air in the reactor with nitrogen gas, the internal temperature was raised to 75. After adding a total amount of 0.55 parts of azobisisobutyronitrile (polymerization initiator) in 12.5 parts of ethyl acetate, the temperature was kept for 8 hours while maintaining the internal temperature at 69 to 71 to complete the reaction. The obtained acrylic resin had a polystyrene-reduced weight average molecular weight Mw by GPC of 90,000. This is called acrylic resin A3. Next, examples and comparative examples in which pressure-sensitive adhesives were produced using the acrylic resin produced above and applied to optical films are shown. In the following examples, the following were used as ionic compounds. The symbol for each compound is attached for later reference. Compound 1, Compound 4, Compound 5, and Compound 6 with bis (trifluoromethanesulfonyl) imide as anion were liquids at room temperature.

 Compound 1: Trioctylmethylammonium bis (trifluoromethane sulfol) 'imide (having the structure of the following formula)

(CF ₃ S0 ₂ ) ₂ N

Compound 2: Trioctylmethyl ammonium monochlorate (having the following structure)

CM ₃ ~ lst ~ {C ₂ ) ₇ 0H ₃ (GI0 ₄ )

(H2 7CH3 Compound 3: N—Hexyru 4 monomethylpyridinium park mouthpiece (having the following structure)

Compound 4: N-Hexiloux 4-Methylpyridinium bis (trifluoromethanesulfonyl) imide (having the structure of the following formula) CH3-^^ N- (CH2) 5CH3 (CF ₃ S0 ₂ ) ₂

Compound 5: Hexyltrimethylammo

Phonyl) imide (having the following structure)

Compound 6: N-Pitreux N-Methylpyrrolidinium Bis (trifluoromethyl sulfone

Nyl) imide (having the structure of the following formula)

In addition, the following were used as the crosslinking agent and the silane compound (both are trade names). Cross-linking agent

 Coronate L: Trimethylolpropane adduct of tolylene diisocyanate in an ethyl acetate solution (solid content 75%), obtained from Nippon Polyurethane Industry Co., Ltd. Silane compounds

X-41 -1805: Mercapto group-containing silane oligomer (liquid), obtained from Shin-Etsu Chemical Co., Ltd. [Examples 1 to 4, Comparative Examples 1 to 8]

 (a) Manufacture of adhesive

 Acrylic resin A1 obtained in Polymerization Example 1 alone or acryl resin obtained in Polymerization Example 2

A2 and the acrylic resin A3 obtained in Polymerization Example 3 were mixed at a weight ratio shown in Table 1 to obtain an ethyl acetate solution. Table 1 shows the ionic compounds 1 to 6 shown above, the cross-linking agent “Coronate L”, and the silane compound “X-4" 1805 ”with respect to 100 parts of the nonvolatile content of the obtained solution. It mixed in the ratio shown, and prepared the adhesive composition. However, in Table 1, the amount (parts) of the crosslinking agent “Coronate L” is the amount of solids. In the case where the acrylic resin A1 is used alone, the amount of the structural unit derived from the unsaturated carboxylic acid in the acrylic resin A1 is 3 parts with respect to 100 parts of the acrylic resin. In the example in which the fat A3 was mixed at a weight ratio of 70/30, the amount of the structural unit derived from the unsaturated carboxylic acid in the mixture was 0.77 parts relative to 100 parts of the acrylic resin. ing. ο

 Table 1 High molecular weight Low molecular weight Ionic compound Crosslinker Silane compound Acrylic resin Acrylic resin Coronate L X-41-1805 Example 1 A1 / 100 parts 1 Compound 1Z4. 5 parts 5 0

 "2 A1 / 100 parts 1 compound 2/6. 0 parts 5 0

(b) Production of optical film with adhesive Each of the above adhesive compositions is applied to the release treatment surface of a release-treated polyethylene terephthalate film (trade name "PET 3811", obtained from Lintec Corporation; called Separete Yuichi). The film was coated using an overnight so that the thickness after drying was 25 / zm, and dried at 90 ° C. for 1 minute to obtain a sheet-like pressure-sensitive adhesive. Next, both sides of a polyvinyl alcohol polarizer with iodine adsorbed and oriented are sandwiched between protective films made of triacetyl cellulose. One side of a polarizing film with a three-layer structure is opposite to the separator of the sheet-like adhesive obtained above. These surfaces (adhesive surface) were bonded together using a laminator, and then aged for 10 days under conditions of a temperature of 23 and a relative humidity of 65% to obtain a polarizing film with an adhesive.

(c) Antistatic evaluation of optical film with adhesive

When the separator of the obtained polarizing film with pressure-sensitive adhesive was peeled off, the surface resistance value of the pressure-sensitive adhesive was measured using a surface resistivity measuring device ["Hi res t-up MCP-HT450" manufactured by Mitsubishi Chemical Corporation (product Name)] to measure the antistatic property. If the surface resistance is 1 0 ¹² 0 b is below, antistatic correspondingly obtained, have more preferably not more than 1 Omicron ^eta Omega Zeta port.

(d) Fabrication and evaluation of optical laminates ''

The polarizing film with the adhesive prepared in (b) above is attached to both sides of a glass substrate for liquid crystal cells ["1737" (trade name) manufactured by Corning Co., Ltd.] so as to be crossed Nicol, thereby producing an optical laminate. did. When this optical laminate was stored for 96 hours under dry conditions at a temperature of 80 ° C. (heat resistance test), the appearance of white spots was visually observed. In addition, when the above heat resistance test is performed, when the temperature is 60, and when the relative humidity is 90%, it is stored for 96 hours (moisture and heat resistance test), from the state heated to 60, the temperature is decreased to _20, Next, the process of raising the temperature to 6 O: was defined as 1 cycle (1 hour). When this was repeated 100 cycles (heat shock resistance test), the optical laminate after the test was visually observed. The results were classified according to the following criteria and summarized in Table 2. <Expression of white spots>

 The appearance of white spots when light was incident from one polarizing film side was evaluated according to the following four levels.

 A: No white spots are observed.

 ◯: White spots are hardly noticeable.

 Δ: White spots are slightly noticeable.

 X: White spots are noticeable. <Heat resistance, heat and humidity resistance, and heat shock resistance (referred to as “HS resistance” in Table 2)> These evaluations were performed in the following four stages.

 A: No change in appearance such as floating, peeling or foaming is observed.

 ◯: Almost no change in appearance such as floating, peeling, foaming, etc.

 Δ: Appearance changes such as floating, peeling and foaming are slightly noticeable.

 X: Appearance changes such as floating, peeling and foaming are noticeable.

(e) Reworkability evaluation of optical film with adhesive

 The reworkability was evaluated as follows. First, the above-mentioned polarizing film with an adhesive was cut into a test piece having a size of 25 mm × 150 mm. Next, the test piece was attached to the glass substrate for the liquid crystal cell on the adhesive side by using a sticking device ["Lamipacker" (trade name) manufactured by Fuji Plastic Machine Co., Ltd.]. The autoclave treatment was performed at kg / cm2 (49.3 kPa) for 20 minutes. Next, heat treatment was performed at 70 ° C. for 2 hours, followed by storage in an oven of 5 O t: for 48 hours, and then this sticking test in an atmosphere at a temperature of 23 t: relative humidity of 50%. The polarizing film was peeled from the piece in the direction of 180 ° at a speed of 300 mm / min, and the state of the glass plate surface was observed and classified according to the following criteria. The results are also shown in Table 2.

A: No fogging or the like is observed on the glass plate surface. ◯: Almost no fogging or the like is observed on the glass plate surface.

 Δ: Cloudiness or the like is observed on the glass plate surface.

 A A 8n mouth n mouth

 Physical property

 X: Remaining adhesive is observed on the glass plate surface.

Ionicity Surface resistance value White spot Heat resistance Moisture resistance HS resistance Compound Properties Properties Curability □ □□□ ◎◎◎◎◎◎◎ 〇 〇 ◎ ©

Comparative Example 1> 10 ¹⁴ Ω / mouth @ ®®® ◎◎◎◎ ®οχχ

a 2 Compound 3 6.0Χ10 ¹² Ω / ϋ

2.7X10 ¹³ Ω / mouth

4 5 2.0X10 ¹⁰ Ω / port ®ΔΔ ◎◎ ○ Ο ◎ ΧΧΧΧ

5 4 7.4X10 ¹⁰ Ω / mouth

6 5 7.5X10 ¹⁰ Ω / mouth

7 6 1.1X10 ¹¹ Ω / mouth ◎◎◎◎ ◎◎◎

4 6.1X10 ¹⁰ Ω / mouth ◎◎ ◎ ○

 8 <>

As can be seen from Tables 1 and 2, Examples 1 to 4 containing an ionic compound specified in the present invention have a low surface resistance value. In addition to being excellent in prevention, white spots were hardly generated, and almost satisfactory results were obtained in any of heat resistance, moist heat resistance, heat shock resistance and leakage resistance. On the other hand, Comparative Examples 1 and 3, which do not contain an ionic compound, have a high surface resistance value, so that antistatic properties cannot be expected. On the other hand, a compound that is ionic but does not satisfy the provisions of the present invention. In Comparative Example 2 in which 3 was blended, the decrease in the surface resistance value was small. Although Comparative Examples 4 to 8 containing Compound 4, Compound 5 or Compound 6 that are ionic but do not satisfy the provisions of the present invention have antistatic effects, they have heat resistance, heat and humidity resistance, heat shock resistance and In either case of reworkability, sufficient results were not obtained.

The optical film with pressure-sensitive adhesive of the present invention is provided with high antistatic properties and is enlarged. Even in this case, white spots hardly occur and the durability is excellent, so that it is suitably used for a liquid crystal display device. For example, it is suitable for a TN liquid crystal cell or the like, and can suppress white spots and improve durability while imparting antistatic properties. In addition, when this optical film with an adhesive is used in an STN liquid crystal cell, the occurrence of color unevenness can be suppressed. The optical film with a pressure-sensitive adhesive of the present invention can effectively suppress charging of the optical member.

 This optical film with an adhesive gives, for example, an optical laminate for liquid crystal display by laminating it on a glass substrate of a liquid crystal cell. In this optical laminate, the adhesive layer absorbs and relaxes stress caused by dimensional changes of the optical film and glass substrate under wet heat conditions, so that local stress concentration is reduced and the adhesive layer floats on the glass substrate. And peeling are suppressed. In addition, white spots are suppressed because optical defects due to non-uniform stress distribution are prevented. Furthermore, if there is any inconvenience after laminating the optical film with adhesive once on the glass substrate, even if the optical film is peeled off from the glass substrate together with the adhesive, adhesive residue or Fog is less likely to occur, and can be used again as a glass substrate, resulting in excellent reflexability.

Claims

The scope of the claims

 1. An optical film with an adhesive in which an adhesive layer is formed on at least one side of an optical film, the adhesive layer comprising:

 (A) The following formula (I)

In the formula, R1 represents a hydrogen atom or a methyl group, and R2 represents an alkyl group or aralkyl group having 1 to 14 carbon atoms which may be substituted with an alkoxy group having 1 to 10 carbon atoms. It contains a structural unit derived from an unsaturated carboxylic acid having a structural unit derived from (meth) acrylic acid ester as a main component and further having one olefinic double bond and at least one carboxyl group in the molecule. The first acrylic resin having a weight average molecular weight of 800,000 to 2,000,000 is contained, and the content of the structural unit derived from the unsaturated carboxylic acid is 0.5 to 10 weights with respect to 100 parts by weight of the whole resin. Part acrylic resin,

 (B) The following formula (II)

Wherein R3 represents an alkyl group having 1 to 12 carbon atoms, and R4, R5 and R6 each independently represents an alkyl group having 6 to 12 carbon atoms), and an ionic compound containing a cation represented by:

 (C) Cross-linking agent

An optical film with an adhesive formed from a composition containing

2. Structure derived from (meth) acrylic acid ester constituting the first acrylic resin 2. The optical film with an adhesive according to claim 1, wherein the unit comprises a unit derived from butyl acrylate.

3. In addition to the first acrylic resin, the acrylic resin (A) is mainly composed of a structural unit derived from the (meth) acrylic acid ester represented by the formula (I), and has a weight average molecular weight of 50. The optical film with a pressure-sensitive adhesive according to claim 1 or 2, comprising a second acryl resin having a viscosity of, 000 to 500,000.

4. The optical film with pressure-sensitive adhesive according to any one of claims 1 to 3, wherein the ionic compound (B) has an anion containing a fluorine atom.

5. The optical film with an adhesive according to claim 4, wherein the anion is bis (trifluoromethanesulfonyl) imide.

6. The optical film with an adhesive according to any one of claims 1 to 5, wherein the ionic compound (B) is present in an amount of 0.5 to 10 parts by weight with respect to 100 parts by weight of the acrylic resin (A).

7. The optical film with the pressure-sensitive adhesive according to any one of claims 1 to 6, wherein the crosslinking agent (C) is an isocyanate compound. '

8. Crosslinker (C) is tolylene diisocyanate, adducts obtained by reacting tolylene diisocyanate with polyol, tolylene diisocyanate dimer, and tolylene diisocyanate trimer. The optical film with an adhesive according to claim 7, which is selected from the group consisting of bodies.

 .

9. The optical film with an adhesive according to any one of claims 1 to 8, wherein the composition forming the adhesive layer further contains a silane compound.

10. The optical film with an adhesive according to any one of claims 1 to 9, wherein the optical film is selected from a polarizing film and a retardation film.

11. An optical laminate, wherein the optical film with an adhesive according to any one of claims 1 to 10 is laminated on a glass substrate on the adhesive layer side.