JP5354673B2 - Optical film with adhesive and optical laminate using the same - Google Patents

Abstract

Disclosed is an optical film with adhesive wherein an adhesive layer (20) formed from a composition that contains (A), (B), and (C) is provided on an optical film (10). (A) 100 parts by weight of an acrylic resin that is a copolymer of a monomer mixture that contains: (A-1) 80-96 wt% of a (meth)acrylic acid ester with formula (I) (I) (R1 is hydrogen or a methyl, and R2 is a C1-14 alkyl), (A-2) 3-15 wt% of an unsaturated monomer that has an aromatic ring and one olefinic double bond in the molecule, and (A-3) 0.1-5 wt% of an unsaturated monomer that has a polar functional group, where the weight average molecular weight (Mw) of the acrylic resin is 1,000,000 to 2,000,000 and the molecular weight distribution (Mw/Mn) is 3 to 7. (B) 0.2-8 parts by weight of an ionic compound that has ionic cations and the melting point of which is no more than 80ºC. (C) 0.01-5 parts by weight of a crosslinking agent.

Description

  The present invention relates to an optical film having a pressure-sensitive adhesive layer formed thereon. Examples of the optical film to be used in the present invention include a polarizing plate and a retardation film. The present invention also relates to an optical laminate for liquid crystal display using an optical film in which the pressure-sensitive adhesive layer is formed.

  A polarizing plate is mounted on a liquid crystal display device and is widely used. A transparent protective film is laminated on both surfaces of a polarizer, and an adhesive layer is formed on the surface of at least one protective film. It is distributed in the state where the release film is stuck to. In addition, a retardation film may be laminated on a polarizing plate in which a protective film is bonded to both surfaces of the polarizer to form an elliptical polarizing plate, and an adhesive layer / release film may be attached to the retardation film side. is there. Furthermore, an adhesive layer / release 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 plate, elliptical polarizing plate, retardation film, etc., and bonded to the liquid crystal cell via the exposed adhesive layer. Such a polarizing plate, elliptical polarizing plate, 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 for the prevention is desired.

  As one of the countermeasures, in JP-A-6-313807 (Patent Document 1), in a polarizing plate 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 an ion conductive composition comprising an electrolyte salt and an organopolysiloxane and a composition containing an acrylic copolymer. By using such a pressure-sensitive adhesive, although antistatic properties are exhibited, its performance is not necessarily sufficient, and it cannot be said that adhesion durability is sufficient.

  On the other hand, in Japanese translations of PCT publication No. 2004-536940 (Patent Document 2), an organic salt-based antistatic agent is blended with a pressure-sensitive adhesive (adhesive) to impart antistatic properties to the adhesive. It is disclosed. Japanese Patent Application Laid-Open No. 2004-114665 (Patent Document 3) contains a salt composed of a quaternary ammonium cation having 4 to 20 carbon atoms and a fluorine atom-containing anion in an adhesive or the like, and has antistatic properties. It is described to give. Furthermore, Japanese Patent Application Laid-Open No. 2006-307238 (Patent Document 4) describes that an ionic liquid that becomes liquid at room temperature (25 ° C.) is contained in an adhesive to prevent charging. However, when the polarizing plate coated with an adhesive is left for a long time, the antistatic property is still deteriorated due to a change with time. Since the distribution and storage period of a general polarizing plate is about six months at the maximum from the production, it is required to maintain the antistatic performance until the customer uses it.

  In addition, the 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 also 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, resulting in a phenomenon called whitening that causes the outer periphery to become whitish when displaying black. In some cases, color unevenness may occur, and suppression of such white spots and color unevenness is also required. Furthermore, when there is a deficiency when bonding an optical film with an adhesive to a liquid crystal cell, the optical film will be peeled off once and then a new film will be pasted again. A so-called rework property is also required in which the pressure-sensitive adhesive layer is peeled off along with the optical film, and the pressure-sensitive adhesive does not remain on the cell glass and no fogging occurs.

  In JP-A-2007-138056 (Patent Document 5), a ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of a resin obtained by copolymerizing an acrylic acid alkyl ester with an aromatic ring-containing monomer ( A method for suppressing light leakage by widening the molecular weight distribution represented by (Mw / Mn) to 10 to 50 is described. By using such an adhesive, light leakage is reduced, but it is not always sufficient, and due to the wide molecular weight distribution, foaming may occur under high temperature conditions.

JP-A-6-313807 Special Table 2004-536940 JP 2004-114665 A JP 2006-307238 A JP 2007-138056 A

  An object of the present invention is to provide a high antistatic property, and the antistatic property hardly changes with time, and is provided with a pressure sensitive adhesive layer on the surface of an optical film that is excellent in suppressing white spots even when the size is increased. It is to provide an optical film. As a result of intensive studies to solve such problems, the present inventors have found that an acrylic ester containing a structural unit derived from an unsaturated monomer having an acrylic ester as a main component and an aromatic ring in the molecule. By blending a resin and a specific ionic compound and providing this composition as an adhesive layer on the surface of the optical film, an optical film with an adhesive excellent in whitening prevention, antistatic properties and durability can be obtained. As a result, the present invention was reached.

That is, the present invention is an optical film with an adhesive in which an adhesive layer is formed on at least one surface of the optical film, and the adhesive layer is
(A) (A-1) The following formula (I)

(Wherein R ₁ represents a hydrogen atom or a methyl group, and R ₂ represents an alkyl group having 1 to 14 carbon atoms which may be substituted with an alkoxy group having 1 to 10 carbon atoms)
(Meth) acrylic acid ester represented by 80 to 96% by weight,
(A-2) 3 to 15% by weight of an unsaturated monomer having one olefinic double bond and at least one aromatic ring in the molecule, and
(A-3) 0.1 to 5% by weight of unsaturated monomer having polar functional group
A weight average molecular weight (Mw) of 1,000,000 to 2,000,000, and a ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn). 100 parts by weight of an acrylic resin whose molecular weight distribution is 3-7,
(B) Adhesive having an organic cation, a melting point of 80 ° C. or less, and 0.2 to 8 parts by weight of an ionic compound that is solid at room temperature, and (C) 0.01 to 5 parts by weight of a crosslinking agent The pressure-sensitive adhesive layer is an optical film with a pressure-sensitive adhesive, characterized in that the pressure-sensitive adhesive layer has a gel fraction of 70 to 99% by weight.

  Moreover, according to this invention, the optical laminated body by which said optical film with an adhesive is laminated | stacked on the glass substrate by the adhesive layer side is also provided.

  In the present invention, an unsaturated monomer (A-2) having one olefinic double bond and at least one aromatic ring in the molecule is used as the pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer. By using a composition containing an acrylic resin (A) as an ingredient and an ionic compound (B) having an organic cation and a melting point of 80 ° C. or lower, optical components resulting from uneven stress distribution Since white defects are prevented, charging of optical members can be effectively suppressed, and the initial antistatic performance is maintained even after storage for a long time after production. Is possible.

  Further, the optical film with pressure-sensitive adhesive of the present invention is once laminated on a glass substrate, and if there is any inconvenience, even if it is peeled off from the glass substrate together with the pressure-sensitive adhesive, adhesive residue or There is little fogging, and it can be used again as a glass substrate, and has excellent reworkability.

  Furthermore, the optical film with pressure-sensitive adhesive of the present invention uses an acrylic resin (A) having a molecular weight distribution (Mw / Mn) of 3 to 7 as a pressure-sensitive adhesive composition for forming a pressure-sensitive adhesive layer. White spots when an optical laminate is effectively prevented and defects such as foaming are prevented even under high temperature conditions. Furthermore, the durability of the pressure-sensitive adhesive layer is improved by setting the gel fraction of the pressure-sensitive adhesive layer to be in the range of 70 to 99% by weight, and this optical film with pressure-sensitive adhesive is attached to the glass substrate of the liquid crystal cell. When the test such as heat resistance, moisture heat resistance, heat shock resistance is performed, the appearance change is suppressed.

  For example, this optical film with an adhesive is laminated on a glass substrate of a liquid crystal cell to give an optical laminate for liquid crystal display. In this optical laminate, the pressure-sensitive 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 pressure-sensitive adhesive layer floats on the glass substrate. And peeling are suppressed.

It is a cross-sectional schematic diagram which shows the example of the suitable layer structure of the optical laminated body which concerns on this invention.

Hereinafter, the present invention will be described in detail. The optical film with pressure-sensitive adhesive of the present invention is one in which a pressure-sensitive adhesive layer is formed on at least one side of the optical film, and the pressure-sensitive adhesive composition forming the pressure-sensitive adhesive layer is
(A) acrylic resin,
(B) It is formed from a composition containing an ionic compound having an organic cation and a melting point of 80 ° C. or lower, and (C) a crosslinking agent. First, each component which comprises an adhesive composition is demonstrated.

[Acrylic resin (A)]
In the optical film with a pressure-sensitive adhesive of the present invention, the acrylic resin (A) used in the pressure-sensitive adhesive composition is mainly composed of a structural unit derived from the (meth) acrylic acid ester represented by the formula (I). Specifically, in addition to the structural unit derived from the (meth) acrylic acid ester, it is derived from an unsaturated monomer having one olefinic double bond and at least one aromatic ring in the molecule. An unsaturated monomer having a polar functional group such as a structural unit, a free carboxyl group, a hydroxyl group, an amino group, a heterocyclic group such as an epoxy ring, preferably a (meth) acrylic acid compound having a polar functional group Includes derived structural units. Here, (meth) acrylic acid means that either acrylic acid or methacrylic acid may be used, and “(meth)” when referred to as (meth) acrylate or the like has the same meaning.

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

Of the (meth) acrylic acid ester (A-1) represented by the formula (I), as R ₂ is an unsubstituted alkyl group, specifically, methyl acrylate, ethyl acrylate, propyl acrylate, Linear alkyl acrylate esters such as n-butyl acrylate, n-octyl acrylate, lauryl acrylate; branched alkyl acrylates such as isobutyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate Esters; linear alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, n-octyl methacrylate, lauryl methacrylate; isobutyl methacrylate, 2-ethylhexyl methacrylate Branches such as isooctyl methacrylate Methacrylic acid alkyl esters are illustrated.

  Among these, n-butyl acrylate is preferable. Specifically, among all the monomers constituting the acrylic resin (A), n-butyl acrylate is 50% by weight or more and is described above. It is preferable to use it so that the prescription | regulation regarding (meth) acrylic acid ester (A-1) may be satisfy | filled.

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

  These (meth) acrylic acid esters can be used alone or in combination with a plurality of different ones.

  The unsaturated monomer (A-2) having one olefinic double bond and at least one aromatic ring in the molecule has a (meth) acryloyl group as a group containing an olefinic double bond. Preferably there is. Examples thereof include benzyl (meth) acrylate, neopentyl glycol benzoate (meth) acrylate, and the like, and an unsaturated monomer represented by the following formula (II) is particularly preferable.

In the formula, R ₃ represents a hydrogen atom or a methyl group, n is an integer of 1 to 8, and R ₄ represents a hydrogen atom, an alkyl group, an aralkyl group, or an aryl group. When R ₄ is an alkyl group, its carbon number can be about 1 to 9, and when it is an aralkyl group, its carbon number is about 7 to 11, and when it is an aryl group, its carbon number is It can be about 6-10.

  Examples of the alkyl group having 1 to 9 carbon atoms include a methyl group, a butyl group, and a nonyl group, and examples of the aralkyl group having 6 to 11 carbon atoms include a benzyl group, a phenethyl group, and a naphthylmethyl group. Examples of the aryl group include a phenyl group, a tolyl group, and a naphthyl group.

  Specific examples of the unsaturated monomer of the formula (II) include 2-phenoxyethyl (meth) acrylate, 2- (2-phenoxyethoxy) ethyl (meth) acrylate, (meth) acrylate of ethylene oxide-modified nonylphenol, 2 -(O-phenylphenoxy) ethyl (meth) acrylate and the like can be mentioned. These unsaturated monomers having one olefinic double bond and at least one aromatic ring in these molecules may be used alone or in combination with a plurality of different monomers.

  Among these, 2-phenoxyethyl (meth) acrylate or 2- (o-phenylphenoxy) ethyl (meth) acrylate is used as an aromatic ring-containing unsaturated monomer (A-2) constituting the acrylic resin (A). It is preferable to use as one of these.

  Examples of the unsaturated monomer (A-3) having a polar functional group include unsaturated monomers having a free carboxyl group such as acrylic acid, methacrylic acid, and β-carboxyethyl acrylate; (meth) acrylic acid Unsaturated monomers having a hydroxyl group such as 2-hydroxyethyl, 2-hydroxypropyl (meth) acrylate, 2- or 3-chloro-2-hydroxypropyl (meth) acrylate, and diethylene glycol mono (meth) acrylate; Acryloylmorpholine, vinylcaprolactam, N-vinyl-2-pyrrolidone, tetrahydrofurfuryl (meth) acrylate, caprolactone-modified tetrahydrofurfuryl acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, glycidyl (meth) acrylate, 2,5 -Dihydrof Such emission of unsaturated monomer having a heterocyclic group; N, such as N- dimethylaminoethyl (meth) acrylate, and the like unsaturated monomer having a different amino group and heterocyclic. These unsaturated monomers having a polar functional group may be used singly or a plurality of different monomers may be used.

  Among these, the polar functional group of the unsaturated monomer (A-3) is preferably a free carboxyl group, a hydroxyl group, an amino group, or an epoxy ring. In particular, an unsaturated monomer having a hydroxyl group is preferably used as one of the polar functional group-containing unsaturated monomers (A-3) constituting the acrylic resin (A). In addition to the unsaturated monomer having a hydroxyl group, it is also effective to use an unsaturated monomer having another polar functional group, for example, an unsaturated monomer having a free carboxyl group.

  The content of the (meth) acrylic acid ester (A-1) represented by the formula (I) in the acrylic resin (A) is 80 to 96% by weight, preferably 82% by weight or more, and more preferably 85%. % By weight or more, preferably 94% by weight or less, and more preferably 92% by weight or less. The content of the unsaturated monomer (A-2) having one olefinic double bond and at least one aromatic ring in the molecule in the acrylic resin (A) is 3 to 15% by weight. Preferably 5% by weight or more, more preferably 5.5% by weight or more, especially 7% by weight or more, and preferably 12% by weight or less, more preferably 9.9% by weight or less, especially 9.5% by weight or less, More preferably, it is 9% by weight or less. The content of the unsaturated monomer (A-3) having a polar functional group in the acrylic resin (A) is 0.1 to 5% by weight, preferably 0.5% by weight or more. Preferably it is 3 weight% or less.

  The acrylic resin (A) used in the present invention is a (meth) acrylic acid ester (A-1) represented by the formula (I) described above, and at least one olefinic double bond in the molecule. It may contain a structural unit derived from a monomer other than the unsaturated monomer (A-2) having one aromatic ring and the unsaturated monomer (A-3) having a polar functional group. . Examples of these include structural units derived from (meth) acrylic acid esters having an alicyclic structure in the molecule, structural units derived from styrene monomers, structural units derived from vinyl monomers, molecules Examples thereof include a structural unit derived from a monomer having a plurality of (meth) acryloyl groups.

  The alicyclic structure is a cycloparaffin structure having usually 5 or more carbon atoms, preferably about 5 to 7 carbon atoms. Specific examples of the acrylate ester having an alicyclic structure include isobornyl acrylate, cyclohexyl acrylate, dicyclopentanyl acrylate, cyclododecyl acrylate, methyl cyclohexyl acrylate, trimethyl cyclohexyl acrylate, tert-butyl acrylate Examples of methacrylic acid esters having an alicyclic structure include cyclohexyl, α-ethoxyacrylic acid cyclohexyl, cyclohexyl phenyl acrylate, etc. Specific examples of methacrylic acid esters having an alicyclic structure include isobornyl methacrylate, cyclohexyl methacrylate, dicyclopentanyl methacrylate, Such as cyclododecyl, methyl cyclohexyl methacrylate, trimethyl cyclohexyl methacrylate, tert-butyl cyclohexyl methacrylate, cyclohexyl phenyl methacrylate And so on.

  Examples of styrenic monomers include styrene, alkyl styrene such as methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, triethyl styrene, propyl styrene, butyl styrene, hexyl styrene, heptyl styrene, octyl styrene. Halogenated styrenes such as fluorostyrene, chlorostyrene, bromostyrene, dibromostyrene, iodostyrene; and nitrostyrene, acetylstyrene, methoxystyrene, divinylbenzene and the like.

  Examples of vinyl monomers include: vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl laurate; vinyl halides such as vinyl chloride and vinyl bromide; vinylidene chloride Examples thereof include vinylidene halides such as: nitrogen-containing aromatic vinyl such as vinylpyridine, vinylpyrrolidone and vinylcarbazole; conjugated diene monomers such as butadiene, isoprene and chloroprene; and acrylonitrile and methacrylonitrile.

  Examples of monomers having a plurality of (meth) acryloyl groups in the molecule include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and 1,9-nonanediol. 2 (meth) in the molecule, such as di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate Monomers having an acryloyl group; monomers having three (meth) acryloyl groups in the molecule, such as trimethylolpropane tri (meth) acrylate, can be mentioned.

  (Meth) acrylic acid ester (A-1) represented by the above formula (I), unsaturated monomer (A-2) having one olefinic double bond and at least one aromatic ring in the molecule Monomers other than the unsaturated monomer (A-3) having a polar functional group can be used alone or in combination of two or more. The structural unit derived from the monomer other than (A-1) to (A-3) is usually 0 to 20 parts by weight, preferably 0 to 100 parts by weight of the nonvolatile content of the acrylic resin (A). It is contained at a ratio of 10 parts by weight.

  The active ingredient of the pressure-sensitive adhesive is the (meth) acrylic acid ester (A-1) represented by the formula (I) as described above, having one olefinic double bond and at least one aromatic ring in the molecule. Two or more types of acrylic resins containing a structural unit derived from the unsaturated monomer (A-2) having and the unsaturated monomer (A-3) having a polar functional group may be included. Further, the acrylic resin is mixed with an acrylic resin different from the acrylic resin, specifically, for example, an acrylic resin having a structural unit derived from the (meth) acrylic ester of the formula (I) and containing no polar functional group. It may be what you did. (Meth) acrylic acid ester (A-1) represented by formula (I), unsaturated monomer (A-2) having one olefinic double bond and at least one aromatic ring in the molecule, The acrylic resin containing a structural unit derived from the unsaturated monomer (A-3) having a polar functional group is preferably 80% by weight or more, more preferably 90% by weight or more, based on the whole acrylic resin.

  (Meth) acrylic acid ester (A-1) represented by formula (I), unsaturated monomer (A-2) having one olefinic double bond and at least one aromatic ring in the molecule, And acrylic resin (A), which is a copolymer obtained from a monomer mixture containing an unsaturated monomer (A-3) having a polar functional group, is converted into standard polystyrene by gel permeation chromatography (GPC). Those having a weight average molecular weight (Mw) in the range of 1 million to 2 million are employed. When the weight average molecular weight in terms of standard polystyrene is 1,000,000 or more, the adhesiveness under high temperature and high humidity is improved, and the possibility of occurrence of floating or peeling between the glass substrate and the pressure-sensitive adhesive layer is reduced. And reworkability tends to be improved. In addition, when the weight average molecular weight is 2 million or less, even if the dimension of the optical film bonded to the pressure-sensitive adhesive layer changes, the pressure-sensitive adhesive layer fluctuates following the dimensional change. This is preferable because there is no difference between the brightness of the peripheral edge and the brightness of the center, and white spots and color unevenness tend to be suppressed. The molecular weight distribution represented by the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) is in the range of 3-7.

  Moreover, it is preferable that the glass transition temperature of the said acrylic resin (A) exists in the range of -10-60 degreeC for adhesive expression. The glass transition temperature of the resin can generally be measured with a differential scanning calorimeter.

  The acrylic resin (A) constituting the pressure-sensitive adhesive layer can be produced by various known methods such as a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, and a suspension polymerization method. In the production of this acrylic resin, a polymerization initiator is usually used. The polymerization initiator is used in an amount of about 0.001 to 5 parts by weight with respect to a total of 100 parts by weight of all monomers used in the production of the acrylic resin.

  As the polymerization initiator, a thermal polymerization initiator, a photopolymerization initiator, or the like is used. Examples of the photopolymerization initiator include 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone. Examples of the thermal polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl-2,2'-azobis (2-methylpropio) Azo) compounds such as 2,2'-azobis (2-hydroxymethylpropionitrile); lauryl peroxide, tert-butyl hydroperoxide, benzoyl peroxide, tert-butyl peroxybenzoate, cumene hydroperoxide , Diisopropyl peroxydicarbonate, dipropyl peroxydicarbonate, tert-butyl peroxy Organic peroxides such as neodecanoate, tert-butyl peroxypivalate, (3,5,5-trimethylhexanoyl) peroxide; inorganic peroxides such as potassium persulfate, ammonium persulfate and hydrogen peroxide Can do. A redox initiator using a peroxide and a reducing agent in combination can also be used as the polymerization initiator.

As a method for producing the acrylic resin, the solution polymerization method is preferable among the methods shown above.
A specific example of the solution polymerization method will be described. A desired monomer and an organic solvent are mixed, and a thermal polymerization initiator is added in a nitrogen atmosphere, and the temperature is about 40 to 90 ° C., preferably 60 to 80. A method of stirring at about 0 ° C. for about 3 to 10 hours can be mentioned. In order to control the reaction, a monomer or a thermal polymerization initiator may be added continuously or intermittently during the polymerization, or may be added in a state dissolved in an organic solvent. Examples of the organic solvent include aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate and butyl acetate; aliphatic alcohols such as propyl alcohol and isopropyl alcohol; acetone, methyl ethyl ketone, and methyl isobutyl ketone. Ketones such as can be used.

[Ionic compound (B)]
In the present invention, in addition to the acrylic resin (A) as described above, an ionic compound (B) having a melting point of 80 ° C. or lower is used. This ionic compound (B) has an organic cation.

  The cation component constituting the ionic compound (B) is not particularly limited as long as it is an organic cation satisfying that it becomes an ionic compound having a melting point of 80 ° C. or lower. For example, imidazolium cation, pyridinium cation, ammonium cation, sulfonium cation, phosphonium cation, etc. are mentioned, but when used in the adhesive layer of an optical film, it is difficult to be charged when peeling the release film provided on it. From the viewpoint, a pyridinium cation and an imidazolium cation are preferable. The molecular weight of the ionic compound (B) is not particularly limited, but for example, the molecular weight is preferably 700 or less, and more preferably 500 or less.

  On the other hand, in the ionic compound (B), the anion component serving as the counter ion of the cation component is not particularly limited as long as it satisfies that the melting point is an ionic compound having a melting point of 80 ° C. or less. It may be an organic anion, and examples thereof include the following.

Chloride anion [Cl ⁻ ],
Bromide anion [Br ⁻ ],
Iodide anion [I ⁻ ],
Tetrachloroaluminate anion [AlCl ₄ ⁻ ],
Heptachlorodialuminate anion [Al ₂ Cl ₇ ⁻ ],
Tetrafluoroborate anion [BF ₄ ⁻ ],
Hexafluorophosphate anion [PF ₆ ⁻ ],
Perchlorate anion [ClO ₄ ⁻ ],
Nitrate anion [NO ₃ ⁻ ],
Acetate anion [CH ₃ COO ⁻ ],
Trifluoroacetate anion [CF ₃ COO ⁻ ],
Methanesulfonate anion [CH ₃ SO ₃ ⁻ ],
Trifluoromethanesulfonate anion [CF ₃ SO ₃ ⁻ ],
p-toluenesulfonate anion [p-CH ₃ C ₆ H ₄ SO ₃ ⁻ ],
Bis (trifluoromethanesulfonyl) imide anion [(CF ₃ SO ₂ ) ₂ N ⁻ ],
Tris (trifluoromethanesulfonyl) methanide anion [(CF ₃ SO ₂ ) ₃ C ⁻ ], hexafluoroarsenate anion [AsF ₆ ⁻ ],
Hexafluoroantimonate anion [SbF ₆ ⁻ ],
Hexafluoroniobate anion [NbF ₆ ⁻ ],
Hexafluorotantalate anion [TaF ₆ ⁻ ],
Dimethyl phosphinate anion [(CH ₃ ) ₂ POO ⁻ ],
(Poly) hydrofluorofluoride anion [F (HF) _n ⁻ ] (n is about 1 to 3), dicyanamide anion [(CN) ₂ N ⁻ ],
Thiocyan anion [SCN ⁻ ],
Perfluorobutanesulfonate anion [C ₄ F ₉ SO ₃ ⁻ ],
Bis (pentafluoroethanesulfonyl) imide anion [(C ₂ F ₅ SO ₂ ) ₂ N ⁻ ], perfluorobutanoate anion [C ₃ F ₇ COO ⁻ ],
(Trifluoromethanesulfonyl) (trifluoromethanecarbonyl) imide anion [(CF ₃ SO ₂ ) (CF ₃ CO) N ⁻ ] and the like.

  Among these, an anion component containing a fluorine atom is preferably used because it provides an ionic compound having excellent antistatic performance, and a hexafluorophosphate anion or a bis (trifluoromethanesulfonyl) imide anion 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 examples of the compound that is a combination of a cation component and an anion component include the following.

N-hexylpyridinium hexafluorophosphate,
N-octylpyridinium hexafluorophosphate,
N-butyl-4-methylpyridinium hexafluorophosphate,
N-octyl-4-methylpyridinium hexafluorophosphate,
N-methyl-4-hexylpyridinium hexafluorophosphate,
N-butyl-N-methylpyrrolidinium hexafluorophosphate,
1-ethyl-3-methylimidazolium hexafluorophosphate,
Tetrabutylammonium hexafluorophosphate,
1-ethyl-3-methylimidazolium p-toluenesulfonate,
Tetrabutylammonium p-toluenesulfonate,
1-butyl-3-methylimidazolium methanesulfonate,
(2-hydroxyethyl) trimethylammonium dimethylphosphinate,
(2-hydroxyethyl) trimethylammonium bis (trifluoromethanesulfonyl) imide,
N-methyl-4-hexylpyridinium bis (trifluoromethanesulfonyl) imide,
N-hexyl-4-methylpyridinium bis (trifluoromethanesulfonyl) imide,
Tetrahexylammonium bis (trifluoromethanesulfonyl) imide,
Trioctylmethylammonium bis (trifluoromethanesulfonyl) imide,
Tributylmethylammonium bis (trifluoromethanesulfonyl) imide and the like.

  Such ionic compounds (B) can be used alone or in combination of two or more. Examples of the ionic compound (B) are not limited to the substances listed above.

  As described above, the ionic compound (B) having a melting point of 80 ° C. or lower imparts antistatic properties to the pressure-sensitive adhesive layer formed from the composition containing the acrylic resin (A) and has various physical properties as a pressure-sensitive adhesive. It is effective in keeping. When the melting point of the ionic compound is too high, the compatibility with the acrylic resin (A) is deteriorated. Therefore, the ionic compound preferably has a melting point of 80 ° C. or lower, more preferably 70 ° C. or lower. Further, from the viewpoint of antistatic long-term stability, the ionic compound (B) preferably has a melting point of preferably 30 ° C. or higher, more preferably 35 ° C. or higher. Thus, the ionic compound (B) that is solid at room temperature (25 ° C.) retains the antistatic performance of the pressure-sensitive adhesive layer in which it is mixed for a long period of time compared to the ionic compound that is liquid at room temperature. Can do.

  The ionic compound (B) is 0.2 parts per 100 parts by weight of the non-volatile content of the acrylic resin (A) (total amount of structural units derived from the above A-1, A-2 and A-3). It is contained at a ratio of ˜8 parts by weight. When the ionic compound (B) is contained in an amount of 0.2 parts by weight or more with respect to 100 parts by weight of the nonvolatile content of the acrylic resin (A), the antistatic performance is improved, and the amount is 8 parts by weight or less. It is preferable because durability is easy to maintain. The amount of the ionic compound (B) with respect to 100 parts by weight of the acrylic resin (A) is preferably 0.5 parts by weight or more and 3 parts by weight or less.

[Crosslinking agent (C)]
A crosslinking agent (C) is further blended into 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 structural units derived from the polar monomer-containing unsaturated monomer in the acrylic resin (A). Examples of the compound include an isocyanate compound, an epoxy compound, a metal chelate compound, and an aziridine compound.

  Isocyanate compounds are compounds having at least two isocyanato groups (-NCO) in the molecule, such as tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, Examples thereof include hydrogenated diphenylmethane diisocyanate, naphthalene diisocyanate, and triphenylmethane triisocyanate. In addition, adducts obtained by reacting these isocyanate compounds with polyols such as glycerol and trimethylolpropane, and those obtained by converting isocyanate compounds into dimers, trimers, and the like can also be used as crosslinking agents for pressure-sensitive adhesives. Two or more isocyanate compounds can be mixed and used.

  The epoxy compound is a compound having at least two epoxy groups in the molecule, for example, bisphenol A type epoxy resin, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether. 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, N, N-diglycidylaniline, N, N, N ′, N′-tetraglycidyl-m-xylenediamine, 1,3-bis ( N, N-diglycidylaminomethyl) cyclohexane and the like. Two or more types of epoxy compounds can be mixed and used.

  Examples of the metal chelate compound include compounds in which acetylacetone or ethyl acetoacetate is coordinated to a polyvalent metal such as aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium and zirconium. Can be mentioned.

  An aziridine-based compound is a compound having at least two skeletons of a three-membered ring composed of one nitrogen atom and two carbon atoms, also called ethyleneimine, for example, diphenylmethane-4,4′-bis ( 1-aziridinecarboxamide), toluene-2,4-bis (1-aziridinecarboxamide), triethylenemelamine, isophthaloylbis-1- (2-methylaziridine), tris-1-aziridinylphosphine oxide, hexamethylene Examples include -1,6-bis (1-aziridinecarboxamide), trimethylolpropane-tri-β-aziridinylpropionate, tetramethylolmethane-tri-β-aziridinylpropionate, and the like.

  Among these crosslinking agents, isocyanate compounds, particularly xylylene diisocyanate, tolylene diisocyanate or hexamethylene diisocyanate, or adducts obtained by reacting these isocyanate compounds with polyols such as glycerol and trimethylolpropane, and isocyanate compounds A dimer, trimer or the like, or a mixture of these isocyanate compounds is preferably used. In particular, when the polar functional group-containing unsaturated monomer (A-3) has a polar functional group selected from a free carboxyl group, a hydroxyl group, an amino group, and an epoxy ring, as at least one of the crosslinking agent (C), It is preferable to use an isocyanate compound. Preferred isocyanate compounds include tolylene diisocyanate, adducts obtained by reacting tolylene diisocyanate with polyol, tolylene diisocyanate dimer, and tolylene diisocyanate trimer, hexamethylene diisocyanate, hexamethylene diisocyanate. Examples include adducts reacted with polyols, dimers of hexamethylene diisocyanate, and trimers of hexamethylene diisocyanate.

  A crosslinking agent (C) is mix | blended in the ratio of 0.01-5 weight part with respect to 100 weight part of acrylic resins (A). The amount of the crosslinking agent (C) is preferably about 0.1 to 5 parts by weight, more preferably about 0.2 to 3 parts by weight, with respect to 100 parts by weight of the acrylic resin (A). It is preferable that the amount of the crosslinking agent (C) with respect to 100 parts by weight of the acrylic resin (A) is 0.01 parts by weight or more, particularly 0.1 parts by weight or more because the durability of the pressure-sensitive adhesive layer tends to be improved. Moreover, when it is 5 parts by weight or less, it is preferable because white spots are not noticeable when the optical film with an adhesive is applied to a liquid crystal display device.

[Other components constituting the adhesive]
The pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer in the present invention preferably contains a silane-based compound (D) in order to improve the adhesion between the pressure-sensitive adhesive layer and the glass substrate. It is preferable to contain the silane compound (D) in the acrylic resin before blending the agent.

  Examples of the silane compound (D) include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- ( 2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxy (Cyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimeth Shishiran, 3-glycidoxypropyl triethoxysilane, 3-glycidoxypropyl dimethoxymethyl silane, such as 3-glycidoxypropyl ethoxy dimethyl silane. Two or more silane compounds (D) may be used.

  The silane compound (D) may be of a silicone oligomer type. Examples of the silicone oligomer in the form of a copolymer include the following.

3-mercaptopropyltrimethoxysilane-tetramethoxysilane copolymer,
3-mercaptopropyltrimethoxysilane-tetraethoxysilane copolymer,
3-mercaptopropyltriethoxysilane-tetramethoxysilane copolymer,
A copolymer containing mercaptopropyl groups, such as a 3-mercaptopropyltriethoxysilane-tetraethoxysilane copolymer;
Mercaptomethyltrimethoxysilane-tetramethoxysilane copolymer,
Mercaptomethyltrimethoxysilane-tetraethoxysilane copolymer,
Mercaptomethyltriethoxysilane-tetramethoxysilane copolymer,
A copolymer containing a mercaptomethyl group, such as a mercaptomethyltriethoxysilane-tetraethoxysilane copolymer;
3-methacryloyloxypropyltrimethoxysilane-tetramethoxysilane copolymer,
3-methacryloyloxypropyltrimethoxysilane-tetraethoxysilane copolymer,
3-methacryloyloxypropyltriethoxysilane-tetramethoxysilane copolymer,
3-methacryloyloxypropyltriethoxysilane-tetraethoxysilane copolymer,
3-methacryloyloxypropylmethyldimethoxysilane-tetramethoxysilane copolymer,
3-methacryloyloxypropylmethyldimethoxysilane-tetraethoxysilane copolymer,
3-methacryloyloxypropylmethyldiethoxysilane-tetramethoxysilane copolymer,
Copolymers containing methacryloyloxypropyl groups, such as 3-methacryloxyyl propylmethyldiethoxysilane-tetraethoxysilane copolymer;
3-acryloyloxypropyltrimethoxysilane-tetramethoxysilane copolymer,
3-acryloyloxypropyltrimethoxysilane-tetraethoxysilane copolymer,
3-acryloyloxypropyltriethoxysilane-tetramethoxysilane copolymer,
3-acryloyloxypropyltriethoxysilane-tetraethoxysilane copolymer,
3-acryloyloxypropylmethyldimethoxysilane-tetramethoxysilane copolymer,
3-acryloyloxypropylmethyldimethoxysilane-tetraethoxysilane copolymer,
3-acryloyloxypropylmethyldiethoxysilane-tetramethoxysilane copolymer,
A copolymer containing acryloyloxypropyl groups, such as 3-acryloyloxypropylmethyldiethoxysilane-tetraethoxysilane copolymer;
Vinyltrimethoxysilane-tetramethoxysilane copolymer,
Vinyltrimethoxysilane-tetraethoxysilane copolymer,
Vinyltriethoxysilane-tetramethoxysilane copolymer,
Vinyltriethoxysilane-tetraethoxysilane copolymer,
Vinylmethyldimethoxysilane-tetramethoxysilane copolymer,
Vinylmethyldimethoxysilane-tetraethoxysilane copolymer,
Vinylmethyldiethoxysilane-tetramethoxysilane copolymer,
A vinyl group-containing copolymer, such as vinylmethyldiethoxysilane-tetraethoxysilane copolymer;
3-aminopropyltrimethoxysilane-tetramethoxysilane copolymer,
3-aminopropyltrimethoxysilane-tetraethoxysilane copolymer,
3-aminopropyltriethoxysilane-tetramethoxysilane copolymer,
3-aminopropyltriethoxysilane-tetraethoxysilane copolymer,
3-aminopropylmethyldimethoxysilane-tetramethoxysilane copolymer,
3-aminopropylmethyldimethoxysilane-tetraethoxysilane copolymer,
3-aminopropylmethyldiethoxysilane-tetramethoxysilane copolymer,
Amino group-containing copolymers such as 3-aminopropylmethyldiethoxysilane-tetraethoxysilane copolymer.

  These silane compounds (D) are often liquids. The compounding amount of the silane compound in the pressure-sensitive adhesive is usually about 0.01 to 10 parts by weight with respect to 100 parts by weight of the nonvolatile content of the acrylic resin (A) (the total weight when two or more types are used), preferably Is used in a proportion of 0.03 to 1 part by weight. It is preferable that the amount of the silane compound with respect to 100 parts by weight of the acrylic resin is 0.01 parts by weight or more, particularly 0.03 parts by weight or more because adhesion between the pressure-sensitive adhesive layer and the glass substrate is improved. Moreover, it is preferable for the amount to be 10 parts by weight or less, particularly 1 part by weight or less, 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 weather resistance stabilizer, a tackifier, a plasticizer, a softener, a dye, a pigment, an inorganic filler, a resin other than the acrylic resin (A), and the like. It is also useful to blend a UV curable compound with the pressure-sensitive adhesive and to cure it by irradiating it with ultraviolet light after forming the pressure-sensitive adhesive layer to form a harder pressure-sensitive adhesive layer. Above all, if a cross-linking catalyst and a cross-linking catalyst are added to the pressure-sensitive adhesive, the pressure-sensitive adhesive layer can be prepared by aging in a short time, and the resulting resin film with pressure-sensitive adhesive floats between the resin film and the pressure-sensitive adhesive layer. Occurrence of peeling or peeling or foaming in the pressure-sensitive adhesive layer can be suppressed, and reworkability can be further improved. Examples of the crosslinking catalyst include amine compounds such as hexamethylenediamine, ethylenediamine, polyethyleneimine, hexamethylenetetramine, diethylenetriamine, triethylenetetramine, isophoronediamine, trimethylenediamine, polyamino resin, and melamine resin. When an amine compound is added to the adhesive as a crosslinking catalyst, an isocyanate compound is suitable as the crosslinking agent.

  Each of these components constituting the pressure-sensitive adhesive is made into a pressure-sensitive adhesive composition in a state dissolved in a solvent, and is applied onto a suitable substrate and dried to form a pressure-sensitive adhesive layer.

[Gel fraction of adhesive layer]
In the present invention, as described above, the pressure-sensitive adhesive layer has a gel fraction of 70 to 99% by weight. Here, the gel fraction is a value measured according to the following (I) to (IV).

  (I) An adhesive layer having an area of about 8 cm × about 8 cm and a metal mesh made of SUS304 (its weight is Wm) of about 10 cm × about 10 cm are bonded together.

  (II) Weigh the pasted product obtained in (I) above, weigh it Ws, then fold it 4 times so as to wrap the adhesive layer and weigh it with a stapler (stapler) The weight is Wb.

  (III) The mesh stapled in (II) above is placed in a glass container, and 60 mL of ethyl acetate is added and immersed, and then the glass container is stored at room temperature for 3 days.

(IV) The mesh is taken out from the glass container, dried at 120 ° C. for 24 hours, weighed, and its weight is defined as Wa.
Gel fraction (% by weight) = [{Wa− (Wb−Ws) −Wm} / (Ws−Wm)] × 100
Calculate the gel fraction based on

  The gel fraction of the pressure-sensitive adhesive layer is set to 70 to 99% by weight. When the gel fraction is 70% by weight or more, the durability of the pressure-sensitive adhesive layer is improved, and when the gel fraction is 99% by weight or less, it is preferable because the production is easy.

  The gel fraction of an adhesive layer can be adjusted with the kind of acrylic resin (A) which is an active ingredient of an adhesive layer, and the quantity of a crosslinking agent, for example. Specifically, if the amount of the unsaturated monomer (A-3) having a polar functional group in the acrylic resin (A) is increased or the amount of the crosslinking agent (C) in the pressure-sensitive adhesive composition is increased. Since the gel fraction becomes high, the gel fraction may be adjusted by the amount of the unsaturated monomer having a polar functional group and / or the crosslinking agent. Therefore, for the unsaturated monomer (A-3) having a polar functional group, the amount of units derived from the unsaturated monomer (A-3) having the polar functional group in the acrylic resin (A) is determined. From a range of 0.1 to 5% by weight, a combination with other components constituting the acrylic resin (A) and a combination with the kind and amount of the crosslinking agent are selected so that the gel fraction falls within the above range. And adjust. Moreover, about the quantity of a crosslinking agent (C), the compounding quantity of the crosslinking agent with respect to 100 weight part (the total amount when using 2 or more types) of the non volatile matter of the acrylic resin (A) which comprises an adhesive layer is 0.1. It is preferable to select from the range of about 5 parts by weight according to the type of acrylic resin.

[Optical film with adhesive]
The optical film with a pressure-sensitive adhesive of the present invention is obtained by providing a pressure-sensitive adhesive layer formed of the above pressure-sensitive adhesive composition on at least one surface of an optical film. The optical film used here is a film having optical characteristics, and examples thereof include a polarizing plate and a retardation film.

  A polarizing plate is an optical film having a function of emitting polarized light with respect to incident light such as natural light. The polarizing plate absorbs linearly polarized light having a vibrating surface in a certain direction and reflects linearly polarized light having a vibrating surface in a certain direction, and reflects linearly polarized light having a vibrating surface in a certain direction. There are a polarizing separation film having a property of transmitting linearly polarized light having a vibration plane orthogonal to the polarizing plate, an elliptically polarizing plate in which a polarizing plate and a retardation film described later are laminated. As a suitable specific example of a polarizing plate, particularly a linearly polarizing film (sometimes called a polarizer or a polarizer film), a dichroic dye such as iodine or a dichroic dye is added to a uniaxially stretched polyvinyl alcohol resin film. Are adsorbed and oriented.

  The retardation film is an optical film exhibiting optical anisotropy, for example, polyvinyl alcohol, polycarbonate, polyester, polyarylate, polyimide, polyolefin, cyclic polyolefin, polystyrene, polysulfone, polyethersulfone, polyvinylidene fluoride. / Stretched film obtained by stretching a polymer film composed of polymethyl methacrylate, liquid crystal polyester, acetyl cellulose, saponified ethylene-vinyl acetate copolymer, polyvinyl chloride, etc. to about 1.01 to 6 times It is done. Among these, a polymer film obtained by uniaxially or biaxially stretching a polycarbonate film or a cyclic polyolefin film is preferable. Although there exist what is called a uniaxial phase difference film, a wide viewing angle phase difference film, a low photoelasticity phase difference film, etc., it is applicable to all.

  Moreover, the film which expressed optical anisotropy by application | coating and orientation of a liquid crystalline compound, and the film which expressed optical anisotropy by application | coating of an inorganic layered compound can also be used as retardation film. Such retardation films include what are called temperature-compensated retardation films, and films with a twisted orientation of rod-like liquid crystals sold under the trade name “LC film” by Nippon Oil Corporation. Also, a film with a tilted orientation of a rod-shaped liquid crystal sold under the trade name “NH film” by Nippon Oil Corporation, and a disk-shaped liquid crystal sold under the trade name “WV film” by FUJIFILM Corporation. Is a film with a tilt orientation, a fully biaxially oriented film sold under the trade name “VAC film” by Sumitomo Chemical Co., Ltd., and also sold under the trade name “new VAC film” by Sumitomo Chemical Co., Ltd. There are biaxially oriented films.

  Further, those obtained by attaching a protective film to these optical films can also be used as the optical film. As the protective film, a transparent resin film is used, and as the transparent resin, for example, an acetyl cellulose resin typified by triacetyl cellulose or diacetyl cellulose, a methacrylic resin typified by polymethyl methacrylate, a polyester resin, or a polyolefin Resin, polycarbonate resin, polyether ether ketone resin, polysulfone resin and the like. The resin constituting the protective film may contain an ultraviolet absorber such as a salicylic acid ester compound, a benzophenone compound, a benzotriazole compound, a triazine compound, a cyanoacrylate compound, or a nickel complex salt compound. As the protective film, an acetyl cellulose resin film such as a triacetyl cellulose film is preferably used.

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

  In the optical film with an adhesive, it is preferable to stick a release film on the surface of the adhesive layer and protect the surface of the adhesive layer until use. In this way, the optical film with the adhesive provided with the release film is formed by, for example, applying the above-mentioned adhesive composition on the release film to form an adhesive layer, and further optically applying the obtained adhesive layer. By a method of laminating a film, a method of applying a pressure-sensitive adhesive composition on an optical film to form a pressure-sensitive adhesive layer, attaching a release film to the surface of the pressure-sensitive adhesive to protect it, and making an optical film with a pressure-sensitive adhesive Can be manufactured. The release film used here is, for example, a film made of various resins such as polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyarylate, and the like, and the bonding surface with the pressure-sensitive adhesive layer of the substrate is separated by a silicone treatment. It can be one that has undergone mold processing.

  Although the thickness of an adhesive layer is not specifically limited, Usually, it is preferable that it is 30 micrometers or less, it is preferable that it is 10 micrometers or more, More preferably, it is 15-25 micrometers. When the thickness of the pressure-sensitive adhesive layer is 30 μm or less, the adhesiveness under high temperature and high humidity is improved, and there is a tendency that the possibility of floating or peeling between the glass substrate and the pressure-sensitive adhesive layer is reduced. It is preferable because the reworkability tends to improve, and if the thickness is 10 μm or more, even if the dimension of the optical film bonded thereto changes, the adhesive layer follows the change in dimension and fluctuates. Therefore, it is preferable because there is no difference between the brightness of the peripheral edge of the liquid crystal cell and the brightness of the center, and white spots and color unevenness tend to be suppressed. Conventionally, in general, the thickness of the pressure-sensitive adhesive layer adhered to the liquid crystal cell glass has been 25 μm as standard, but in the present invention, even if the thickness is 20 μm or less, sufficient performance as the pressure-sensitive adhesive layer is exhibited. To do.

  The optical film with pressure-sensitive adhesive of the present invention is attached to a glass substrate to form an optical laminate, and when there is some inconvenience and the optical film is peeled off from the glass substrate, the pressure-sensitive adhesive layer is accompanied by the optical film. Since the surface of the glass substrate that has been peeled off and is in contact with the pressure-sensitive adhesive layer hardly causes fogging or adhesive residue, it is easy to re-attach the optical film with the pressure-sensitive adhesive again to the glass substrate after peeling. That is, it is excellent in so-called reworkability.

[Optical laminate]
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. 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 surface of the glass substrate. You just have to stick together. Here, as a glass substrate, the glass substrate of a liquid crystal cell, the glass for glare-proof, the glass for sunglasses etc. can be mentioned, for example. Among them, an optical film with an adhesive (upper polarizing plate) 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 plate) on the glass substrate on the back side of the liquid crystal cell. The optical laminated body formed by laminating is preferable because it can be used as a panel (liquid crystal panel) for a liquid crystal display device. Examples of the material for the glass substrate include soda lime glass, low alkali glass, and non-alkali glass.

  Examples of some suitable layer configurations of the optical laminate according to the present invention are shown in cross-sectional schematic views in FIG. In the example shown in FIG. 1 (A), a polarizing plate 5 is configured by sticking a protective film 3 having a surface treatment layer 2 on one side of a linear polarizing film 1 on the surface opposite to the surface treatment layer 2. Has been. In this example, the polarizing plate 5 is also the optical film 10 referred to in the present invention. The pressure-sensitive adhesive layer 20 containing the ionic compound described above is provided on the surface of the linearly polarizing film 1 opposite to the protective film 3 to form an optical film 25 with a pressure-sensitive adhesive. And the surface on the opposite side to the polarizing plate 5 of the adhesive layer 20 is bonded to the liquid crystal cell 30 which is a glass substrate, and the optical laminated body 40 is comprised.

  In the example shown in FIG. 1 (B), a first protective film 3 having a surface treatment layer 2 is attached to one side of a linear polarizing film 1 on the surface opposite to the surface treatment layer 2, and the linear polarizing film A polarizing plate 5 is configured by sticking a second protective film 4 to the other surface of 1. Also in this example, the polarizing plate 5 is simultaneously the optical film 10 referred to in the present invention. On the outer side of the second protective film 4 constituting the polarizing plate 5, the pressure-sensitive adhesive layer 20 containing the ionic compound described above is provided, and the optical film 25 with pressure-sensitive adhesive is formed. And the surface on the opposite side to the polarizing plate 5 of the adhesive layer 20 is bonded to the liquid crystal cell 30 which is a glass substrate, and the optical laminated body 40 is comprised.

  In the example shown in FIG. 1C, a polarizing film 5 is configured by sticking a protective film 3 having a surface treatment layer 2 on one surface of a linearly polarizing film 1 on the surface opposite to the surface treatment layer 2. Has been. On the surface of the linearly polarizing film 1 opposite to the protective film 3, a retardation film 7 is stuck via an interlayer adhesive 8 to constitute an optical film 10. On the outside of the retardation film 7 constituting the optical film 10, the pressure-sensitive adhesive layer 20 containing the ionic compound described above is provided, and the optical film 25 with pressure-sensitive adhesive is formed. And the surface on the opposite side to the optical film 10 of the adhesive layer 20 is bonded to the liquid crystal cell 30 which is a glass substrate, and the optical laminated body 40 is comprised.

  In the example shown in FIG. 1 (D), the first protective film 3 having the surface treatment layer 2 is attached to one surface of the linearly polarizing film 1 on the surface opposite to the surface treatment layer 2 to form a straight line. On the other surface of the polarizing film 1, a second protective film 4 is stuck to form a polarizing plate 5. On the outer side of the second protective film 4 constituting the polarizing plate 5, a retardation film 7 is stuck via an interlayer adhesive 8 to constitute an optical film 10. On the outside of the retardation film 7 constituting the optical film 10, the pressure-sensitive adhesive layer 20 containing the ionic compound described above is provided, and the optical film 25 with pressure-sensitive adhesive is formed. And the surface on the opposite side to the optical film 10 of the adhesive layer 20 is bonded to the liquid crystal cell 30 which is a glass substrate, and the optical laminated body 40 is comprised.

  In these examples, the first protective film 3 and the second protective film 4 are generally composed of a triacetyl cellulose film, but are composed of the various transparent resin films described above. You can also. The surface treatment layer formed on the surface of the first protective film 3 can be a hard coat layer, an antiglare layer, an antireflection layer, an antistatic layer, or the like. Of these, a plurality of layers may be provided.

  When laminating the retardation film 7 on the polarizing plate 5 as in the example shown in FIGS. 1C and 1D, as a suitable example of the retardation film 7 as long as it is a medium-sized liquid crystal display device, A quarter wave plate can be mentioned. In this case, it is general that the absorption axis of the polarizing plate 5 and the slow axis of the retardation film 7 which is a quarter wavelength plate are arranged so as to intersect at about 45 degrees. Depending on the characteristics, the angle may be shifted from 45 degrees to some extent. On the other hand, in the case of a large liquid crystal display device such as a television, a retardation film having various retardation values in accordance with the characteristics of the liquid crystal cell 30 is used for the purpose of phase difference compensation and viewing angle compensation of the liquid crystal cell 30. . In this case, the polarizing plate 5 and the retardation film 7 are generally arranged so that the absorption axis and the slow axis of the retardation film 7 are substantially orthogonal or substantially parallel. When the retardation film 7 is composed of a quarter wavelength plate, a uniaxial or biaxial stretched film is preferably used. When the retardation film 7 is provided for the purpose of retardation compensation or viewing angle compensation of the liquid crystal cell 30, in addition to the uniaxial or biaxially stretched film, it is also oriented in the thickness direction in addition to the uniaxial or biaxially stretched film. What is called an optical compensation film, such as a film or a film obtained by coating and fixing a retardation-expressing substance such as liquid crystal on a support film, can also be used as the retardation film 7.

  Similarly, when the polarizing plate 5 and the retardation film 7 are bonded via the interlayer adhesive 8 as in the example shown in FIGS. 1C and 1D, the interlayer adhesive 8 includes An antistatic agent such as the ionic compound described above can be blended and an antistatic agent can be used. However, since there is usually not much antistatic property desired in this part, It is customary to use a general acrylic adhesive that does not contain an inhibitor. Further, as in the large liquid crystal display device described above, the polarizing axis 5 and the slow axis of the retardation film 7 are arranged so that the slow axis is substantially orthogonal or substantially parallel. In applications where the plate 5 and the retardation film 7 can be roll-to-roll bonded and re-peelability between them is not required, the interlayer adhesive 8 shown in FIGS. 1 (C) and (D). Instead, it is also possible to use an adhesive that, once bonded, can be firmly bonded and cannot be peeled off. Examples of such an adhesive include an aqueous adhesive that is composed of an aqueous solution or an aqueous dispersion and exhibits adhesive strength by evaporating water as a solvent, and UV curing that is cured by UV irradiation and exhibits adhesive strength. Examples thereof include a mold adhesive.

  1C and 1D in which the pressure-sensitive adhesive layer 20 containing an ionic compound is formed on the retardation film 7 itself can be circulated by itself and is referred to in the present invention. It can be an optical film with an adhesive. An optical film with a pressure-sensitive adhesive in which a pressure-sensitive adhesive layer containing an ionic compound is formed on a retardation film can be bonded to a liquid crystal cell as a glass substrate to form an optical laminate, and the phase difference film. A polarizing plate can be bonded to the side to make another optical film with an adhesive.

  FIG. 1 shows an example in which the optical film 25 with an adhesive is arranged on the viewing side of the liquid crystal cell 30, but the optical film with an adhesive according to the present invention is the back side of the liquid crystal cell, that is, the back. It can also be placed on the light side. When the optical film with pressure-sensitive adhesive of the present invention is disposed on the back side of the liquid crystal cell, a protective film having no surface treatment layer is employed instead of the protective film 3 having the surface treatment layer 2 shown in FIG. Others can be configured similarly to (A) to (D) of FIG. In this case, various optical films known to be disposed on the back side of the liquid crystal cell, such as a brightness enhancement film, a light collecting film, and a diffusion film, may be provided outside the protective film constituting the polarizing plate. Is possible.

  As described above, the optical layered body of the present invention can be suitably used for a liquid crystal display device. The liquid crystal display device formed from the optical laminate of the present invention includes, for example, a notebook type, a desktop type, a personal computer liquid crystal display including a PDA (Personal Digital Assistance), a television, an in-vehicle display, an electronic dictionary, and a digital camera. It can be used for digital video cameras, electronic desk calculators, watches, etc.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited by these examples. In the examples, “parts” and “%” representing the amount used or content are based on weight unless otherwise specified.

  In the following examples, the nonvolatile content is a value measured by a method according to JIS K 5407. Specifically, the adhesive solution was taken in a petri dish at an arbitrary weight, and the residual non-volatile content after drying for 2 hours at 115 ° C. in an explosion-proof oven was expressed as a percentage of the weight of the solution first measured. It is. For weight average molecular weight measurement, four “TSK gel XL” manufactured by Tosoh Corp. and one “GPC KF-802” manufactured by Shodex Corp. are arranged in series on the GPC device. Tetrahydrofuran was used as the eluent, and the sample concentration was 5 mg / mL, the sample introduction amount was 100 μL, the temperature was 40 ° C., and the flow rate was 1 mL / min.

  First, the example which manufactured the acrylic resin (A) prescribed | regulated by this invention used as the main component of an adhesive composition, and the acrylic resin similar to it but remove | deviated from the prescription | regulation of this invention is shown.

[Polymerization Example 1]
In a reaction vessel equipped with a condenser, a nitrogen inlet tube, a thermometer and a stirrer, 81.8 parts of ethyl acetate, 93.6 parts of butyl acrylate as (A-1), and 2-phenoxy acrylate as (A-2) 5.0 parts of ethyl and (A-3) are charged with a mixed solution of 1.0 part of 2-hydroxyethyl acrylate and 0.4 part of acrylic acid, and the air in the apparatus is replaced with nitrogen gas so as not to contain oxygen. The internal temperature was raised to 55 ° C. Thereafter, a total amount of a solution prepared by dissolving 0.14 part of azobisisobutyronitrile (polymerization initiator) in 10 parts of ethyl acetate was added. One hour after the addition of the initiator, the inner temperature was 54 to 56 ° C. while ethyl acetate was continuously added into the reaction vessel at an addition rate of 17.3 parts / hr so that the concentration of the acrylic resin excluding the monomer would be 35%. For 12 hours, 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 in terms of polystyrene by GPC of 1,710,000 and Mw / Mn of 4.3. This is designated as acrylic resin A. The structural unit derived from 2-hydroxyethyl acrylate which is a hydroxyl group-containing unsaturated monomer in the acrylic resin A is 1%, and the structural unit derived from acrylic acid which is a carboxyl group-containing unsaturated monomer is 0.4%.

[Polymerization Example 2]
In the monomer composition, the ethyl acetate of the acrylic resin was used in the same manner as in Polymerization Example 1 except that the amount of butyl acrylate was changed to 90.6 parts and the amount of 2-phenoxyethyl acrylate was changed to 8.0 parts. A solution was obtained. The resulting acrylic resin had a polystyrene-equivalent weight average molecular weight Mw of 1,740,000 and Mw / Mn of 4.1 by GPC. This is designated as acrylic resin B. The structural unit derived from 2-hydroxyethyl acrylate which is a hydroxyl group-containing unsaturated monomer in the acrylic resin B is 1%, and the structural unit derived from acrylic acid which is a carboxyl group-containing unsaturated monomer is 0.4%.

[Polymerization Example 3]
Ethyl acetate solution of acrylic resin in the same manner as in Polymerization Example 1 except that the amount of butyl acrylate in the monomer composition was changed to 88.6 parts and the amount of 2-phenoxyethyl acrylate was changed to 10.0 parts. Got. The obtained acrylic resin had a polystyrene equivalent weight average molecular weight Mw of 1,560,000 and Mw / Mn of 4.5 by GPC. This is designated as acrylic resin C. The structural unit derived from 2-hydroxyethyl acrylate which is a hydroxyl group-containing unsaturated monomer in the acrylic resin C is 1%, and the structural unit derived from acrylic acid which is a carboxyl group-containing unsaturated monomer is 0.4%.

[Polymerization Example 4: for comparison]
Ethyl acetate solution of acrylic resin in the same manner as in Polymerization Example 1 except that the amount of butyl acrylate in the monomer composition was changed to 78.6 parts and the amount of 2-phenoxyethyl acrylate was changed to 20.0 parts. Got. The obtained acrylic resin had a polystyrene-equivalent weight average molecular weight Mw of 1,370,000 and Mw / Mn of 4.4 by GPC. This is designated as acrylic resin D. The structural unit derived from 2-hydroxyethyl acrylate which is a hydroxyl group-containing unsaturated monomer in the acrylic resin D is 1%, and the structural unit derived from acrylic acid which is a carboxyl group-containing unsaturated monomer is 0.4%.

[Polymerization Example 5: for comparison]
Ethyl acetate solution of acrylic resin in the same manner as in Polymerization Example 1 except that the amount of butyl acrylate in the monomer composition was changed to 58.6 parts, and the amount of 2-phenoxyethyl acrylate was changed to 40.0 parts. Got. The obtained acrylic resin had a polystyrene-reduced weight average molecular weight Mw of 1,270,000 and Mw / Mn of 4.4 by GPC. This is designated as acrylic resin E. The structural unit derived from 2-hydroxyethyl acrylate which is a hydroxyl group-containing unsaturated monomer in the acrylic resin E is 1%, and the structural unit derived from acrylic acid which is a carboxyl group-containing unsaturated monomer is 0.4%.

[Polymerization Example 6: for comparison]
Ethyl acetate solution of acrylic resin in the same manner as in Polymerization Example 1, except that the amount of butyl acrylate in the monomer composition was changed to 38.6 parts and the amount of 2-phenoxyethyl acrylate was changed to 60.0 parts. Got. The obtained acrylic resin had a polystyrene-equivalent weight average molecular weight Mw of 1,270,000 and Mw / Mn of 5.0 by GPC. This is designated as acrylic resin F. The structural unit derived from 2-hydroxyethyl acrylate which is a hydroxyl group-containing unsaturated monomer in the acrylic resin F is 1%, and the structural unit derived from acrylic acid which is a carboxyl group-containing unsaturated monomer is 0.4%.

[Polymerization Example 7: for comparison]
An ethyl acetate solution of an acrylic resin was obtained in the same manner as in Polymerization Example 1 except that the amount of butyl acrylate in the monomer composition was 98.6 parts and 2-phenoxyethyl acrylate was not used. The obtained acrylic resin had a polystyrene-equivalent weight average molecular weight Mw of 1,470,000 and Mw / Mn of 4.4 by GPC. This is referred to as an acrylic resin G. The structural unit derived from 2-hydroxyethyl acrylate which is a hydroxyl group-containing unsaturated monomer in the acrylic resin G is 1%, and the structural unit derived from acrylic acid which is a carboxyl group-containing unsaturated monomer is 0.4%.

[Polymerization Example 8]
In the monomer composition, Polymerization Example 1 except that the amount of butyl acrylate was changed to 88.4 parts, the amount of 2-phenoxyethyl acrylate was changed to 10.0 parts, and the amount of acrylic acid was changed to 0.6 parts. In the same manner, an ethyl acetate solution of an acrylic resin was obtained. The obtained acrylic resin had a polystyrene-reduced weight average molecular weight Mw by GPC of 1,530,000 and Mw / Mn of 4.8. This is designated as acrylic resin H. The structural unit derived from 2-hydroxyethyl acrylate which is a hydroxyl group-containing unsaturated monomer in the acrylic resin H is 1%, and the structural unit derived from acrylic acid which is a carboxyl group-containing unsaturated monomer is 0.6%.

[Polymerization Example 9]
The monomer composition is 78.4 parts of butyl acrylate and 10.0 parts of 2-methoxyethyl acrylate as (A-1), 10.0 parts of 2-phenoxyethyl acrylate as (A-2), (A -3) was changed to 1.0 part of 2-hydroxyethyl acrylate and 0.6 part of acrylic acid, and an ethyl acetate solution of an acrylic resin was obtained in the same manner as in Polymerization Example 1 except that. The obtained acrylic resin had a polystyrene-equivalent weight average molecular weight Mw by GPC of 1,540,000 and Mw / Mn of 4.9. This is designated as acrylic resin I. The structural unit derived from 2-hydroxyethyl acrylate which is a hydroxyl group-containing unsaturated monomer in the acrylic resin I is 1%, and the structural unit derived from acrylic acid which is a carboxyl group-containing unsaturated monomer is 0.6%.

[Polymerization Example 10: for comparison]
In the same reaction vessel as used in Polymerization Example 1, 81.8 parts of ethyl acetate, 90.6 parts of butyl acrylate as (A-1), and 8.0 parts of 2-phenoxyethyl acrylate as (A-2) , (A-3) was charged with a mixed solution of 1.0 part of 2-hydroxyethyl acrylate and 0.4 part of acrylic acid, the air in the apparatus was replaced with nitrogen gas, and the internal temperature was reduced to 55. Raised to ° C. Thereafter, a total amount of a solution prepared by dissolving 0.14 part of azobisisobutyronitrile (polymerization initiator) in 10 parts of ethyl acetate was added. One hour after the addition of the initiator, the inner temperature was 54 to 56 ° C. while ethyl acetate was continuously added into the reaction vessel at an addition rate of 17.3 parts / hr so that the concentration of the acrylic resin excluding the monomer would be 35%. And kept warm for 4 hours. Thereafter, a total solution of 0.2 part of azobisisobutyronitrile (polymerization initiator) dissolved in 10 parts of ethyl acetate was added and kept at the same temperature for 8 hours. Finally, ethyl acetate was added to the concentration of the acrylic resin. Was adjusted to 20%. The obtained acrylic resin had a polystyrene-equivalent weight average molecular weight Mw by GPC of 1,070,000 and Mw / Mn of 8.2. This is designated as acrylic resin J. The structural unit derived from 2-hydroxyethyl acrylate which is a hydroxyl group-containing unsaturated monomer in the acrylic resin J is 1%, and the structural unit derived from acrylic acid which is a carboxyl group-containing unsaturated monomer is 0.4%.

  Table 1 shows a list of monomer compositions, weight average molecular weights, and Mw / Mn of polymerization examples 1 to 10. In the table, BA means butyl acrylate, MEA means 2-methoxyethyl acrylate, PEA means 2-phenoxyethyl acrylate, HEA means 2-hydroxyethyl acrylate, and AA means acrylic acid.

  Next, examples and comparative examples in which pressure-sensitive adhesives were prepared using the acrylic resin produced above and applied to optical films are shown. In the following examples and comparative examples, the following compounds were used as ionic compounds.

  Ionic compound 1: N-octyl-4-methylpyridinium hexafluorophosphate (having the structure of the following formula, melting point: 44 ° C.)

  Ionic compound 2: N-hexyl-4-methylpyridinium bis (trifluoromethanesulfonyl) imide (having the structure of the following formula, melting point: 18 ° C.)

  Ionic compound 3: trioctylmethylammonium bis (trifluoromethanesulfonyl) imide (having the structure of the following formula and liquid at room temperature)

  Ionic compound 4: Tributylmethylammonium bis (trifluoromethanesulfonyl) imide (having the structure of the following formula, melting point: 28 ° C.)

  Moreover, what was shown below, respectively was used as a crosslinking agent and a silane type compound (all are brand names).

<Crosslinking agent>
Coronate L: Obtained from an ethyl acetate solution of trimethylolpropane adduct of tolylene diisocyanate (solid content concentration 75%), Nippon Polyurethane Co., Ltd.

<Silane compounds>
KBM-403: Glycidoxypropyltrimethoxysilane (liquid), obtained from Shin-Etsu Chemical Co., Ltd.

[Examples 1-8 and Comparative Examples 1-6] (Examples 5 and 6 are for reference only)
(A) Manufacture of an adhesive For each 100 parts of solid content of acrylic resin AJ obtained by polymerization examples 1-10, each quantity of ionic compound shown in Table 2, 0.5 part silane type compound ( KBM-403) and the respective amounts of the cross-linking agent shown in Table 2 (Coronate L) were mixed, and ethyl acetate was further added so that the solid content concentration was 13% to obtain a pressure-sensitive adhesive composition. The cross-linking agent (Coronate L) is an ethyl acetate solution having a solid concentration of 75% as described above, but the addition amount shown in Table 2 is the solid content.

(B) Production of optical film with pressure-sensitive adhesive Each of the above pressure-sensitive adhesive compositions was subjected to mold release treatment of a polyethylene terephthalate film (trade name “PET 3811”, obtained from Lintec Co., Ltd., referred to as a separator) subjected to mold release treatment It applied to the surface so that the thickness after drying might be set to 20 micrometers using an applicator, and it dried at 90 degreeC for 1 minute, and obtained the sheet-like adhesive. Next, on one side of a polarizing plate having a three-layer structure in which both sides of a polyvinyl alcohol polarizer to which iodine is adsorbed and oriented are sandwiched between protective films made of triacetyl cellulose, the surface opposite to the separator of the sheet-like adhesive obtained above ( The pressure-sensitive adhesive surface) was pasted with a laminator and then cured for 7 days under conditions of a temperature of 23 ° C. and a relative humidity of 65% to obtain a polarizing plate with a pressure-sensitive adhesive.

(C) Evaluation of antistatic property of optical film with adhesive When the separator of the obtained polarizing plate with adhesive is peeled off, the surface resistance value of the adhesive is determined by a surface resistivity measuring device ["Mitsubishi Chemical Co., Ltd." Hirest-up MCP-HT450 "(trade name)] to evaluate the antistatic property. If the surface resistance value is on the order of 10 ¹¹ Ω / □ or less, good antistatic properties can be obtained.

(D) Production and Evaluation of Optical Laminate After separating the separator from the pressure-sensitive adhesive polarizing plate produced in (b) above, the pressure-sensitive adhesive surface was placed on a glass substrate for liquid crystal cells [“1737” (trade name, manufactured by Corning) )] Was pasted on both sides so as to be in a crossed Nicol state, thereby producing an optical laminate. This optical laminate was subjected to a heat resistance test that was stored for 96 hours under dry conditions at a temperature of 80 ° C. Thereafter, the appearance of white spots when light was incident from one polarizing plate side was visually observed. The results were classified according to the following criteria, and are shown in the column of “White Leakage (Dried at 80 ° C.)” in Table 2.

<Expression of white spots>
A: No white spots are observed.
○: White spots are hardly noticeable.
Δ: White spots are slightly noticeable.
X: White spots are noticeable.

  In addition, when a heat resistance test is performed for 300 hours under dry conditions at a temperature of 80 ° C. (indicated as “heat resistance” in Table 2), a heat resistance test is performed for 300 hours at a temperature of 60 ° C. and a relative humidity of 90%. In the case of the heat treatment (indicated as “moisture-resistant heat” in Table 2), the process of lowering the temperature from −70 ° C. to −30 ° C. and then raising the temperature to 70 ° C. is defined as 1 cycle (1 hour). In each case where the repeated heat shock resistance test was performed (indicated as “HS resistance” in Table 2), the optical laminate after the test was visually observed. The results were classified according to the following criteria and summarized in Table 2.

<Evaluation criteria for durability against heat, moist heat and heat shock (referred to as "heat resistance", "moisture heat resistance" and "HS resistance" in Table 2, respectively)>
A: No change in appearance such as floating, peeling or foaming is observed.
○: Almost no change in appearance such as floating, peeling or foaming.
Δ: Appearance changes such as floating, peeling and foaming are slightly noticeable.
X: Remarkable changes in appearance such as floating, peeling, foaming, etc.

(E) Reworkability evaluation of optical film with adhesive The reworkability was evaluated as follows. First, the polarizing plate with the adhesive obtained in (b) 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 liquid crystal cell on the adhesive side using a sticking device ["Lami Packer" (trade name) manufactured by Fuji Plastics Co., Ltd.], 50 ° C., 5 kg / cm ² ( 490.3 kPa) for 20 minutes. Next, it was heat-treated at 70 ° C. for 2 hours, and subsequently stored in an oven at 50 ° C. for 48 hours, and then the polarizing plate was removed from this sticking test piece at 300 mm / mm in an atmosphere of 23 ° C. and 50% relative humidity. The film was peeled in the direction of 180 ° at a speed of minutes, 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.

<Evaluation criteria for reworkability>
A: No fogging or the like is observed on the glass plate surface.
A: Almost no fogging or the like is observed on the glass plate surface.
(Triangle | delta): Cloudiness etc. are recognized by the glass plate surface.
X: The remainder of an adhesive is recognized by the glass plate surface.

  As can be seen from Tables 1 and 2, Examples 1 to 8 in which a predetermined amount of an ionic compound and a crosslinking agent were blended in the acrylic resin specified in the present invention to form an adhesive are antistatic properties and anti-whitening properties. In addition, it was excellent in reworkability, and almost satisfactory results were obtained in heat resistance, moist heat resistance and heat shock resistance. In particular, Example 2 has excellent performance in all of antistatic properties, anti-whitening properties, rework properties, heat resistance, moist heat resistance and heat shock resistance.

  On the other hand, Comparative Examples 1 to 3 using an acrylic resin containing 20 parts by weight or more of a structural unit derived from an unsaturated monomer having an aromatic ring, and a structural unit derived from an unsaturated monomer having an aromatic ring The comparative example 4 using the acrylic resin which does not contain is insufficient in white spot prevention. Further, Comparative Example 5, which did not reach the gel fraction as defined in the present invention, resulted in conspicuous changes in appearance such as floating, peeling and foaming in the heat resistance test, heat resistance test and heat shock test. On the other hand, in Comparative Example 6 using an acrylic resin having a large molecular weight distribution, a result that white spot prevention property was insufficient was obtained.

  It should be understood that the embodiments and examples disclosed herein are illustrative and non-restrictive in every respect. The scope of the present invention is defined by the terms of the claims, rather than the description above, and is intended to include any modifications within the scope and meaning equivalent to the terms of the claims.

  The optical film with a pressure-sensitive adhesive of the present invention is imparted with high antistatic property, and the antistatic property is maintained for a long period of time, and is excellent in durability. This optical film with an adhesive is suitably used for a liquid crystal display device.

  DESCRIPTION OF SYMBOLS 1 Linear polarizing film, 2 Surface treatment layer, 3 1st protective film, 4 2nd protective film, 5 Polarizing plate, 7 Phase difference film, 8 Interlayer adhesive, 10 Optical film, 20 Adhesive containing an ionic compound Layer, 25 optical film with adhesive, 30 liquid crystal cell (glass substrate), 40 optical laminate.

Claims (11)

An optical film with an adhesive in which an adhesive layer is formed on at least one surface of the optical film, the adhesive layer comprising:
(A) (A-1) The following formula (I)

(Wherein R ₁ represents a hydrogen atom or a methyl group, and R ₂ represents an alkyl group having 1 to 14 carbon atoms which may be substituted with an alkoxy group having 1 to 10 carbon atoms)
(Meth) acrylic acid ester represented by 80 to 96% by weight,
(A-2) 3 to 15% by weight of an unsaturated monomer having one olefinic double bond and at least one aromatic ring in the molecule, and
(A-3) 0.1 to 5% by weight of unsaturated monomer having polar functional group
A weight average molecular weight (Mw) of 1,000,000 to 2,000,000, and a ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn). 100 parts by weight of an acrylic resin whose molecular weight distribution is 3-7,
(B) Adhesive having an organic cation, a melting point of 80 ° C. or less, and 0.2 to 8 parts by weight of an ionic compound that is solid at room temperature, and (C) 0.01 to 5 parts by weight of a crosslinking agent is formed from a composition, the viscosity Chakuzaiso optical film pressure-sensitive adhesive characterized by having a gel fraction of 70 to 99 wt%. The unsaturated monomer (A-2) having one olefinic double bond and at least one aromatic ring in the molecule is represented by the following formula (II)

(Wherein R ₃ represents a hydrogen atom or a methyl group, n is an integer of 1 to 8, and R ₄ represents a hydrogen atom, an alkyl group, an aralkyl group, or an aryl group)
The optical film with an adhesive according to claim 1, which is an aromatic ring-containing (meth) acrylic monomer represented by:   The pressure-sensitive adhesive according to claim 1 or 2, wherein the polar functional group of the unsaturated monomer (A-3) having the polar functional group is selected from the group consisting of a free carboxyl group, a hydroxyl group, an amino group, and an epoxy ring. Optical film. Optical film-out pressure-sensitive adhesive of claim 3 wherein the crosslinking agent (C) containing isocyanate compound.   The optical film with an adhesive according to any one of claims 1 to 4, wherein the ionic compound (B) having an organic cation has a melting point of 30 ° C or higher. The ionic compound (B) which has the said organic cation is an optical film with an adhesive in any one of Claims 1-5 which has an anion component containing a fluorine atom. The optical film with an adhesive according to claim 6, wherein the ionic compound (B) having an organic cation has a hexafluorophosphate anion or a bis (trifluoromethanesulfonyl) imide anion. The pressure-sensitive adhesive composition further comprises (D) 0.03-1 part by weight of a silane compound, The optical film with pressure-sensitive adhesive according to any one of claims 1 to 7 . The optical film with an adhesive according to any one of claims 1 to 8 , wherein the optical film is selected from a polarizing plate and a retardation film. The optical film with an adhesive according to any one of claims 1 to 9 , wherein a release film is attached to the surface of the adhesive layer. An optical laminated body, wherein the optical film with the pressure-sensitive adhesive according to any one of claims 1 to 9 is laminated on a glass substrate on the pressure-sensitive adhesive layer side.

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