KR20100070336A - Resin film with adhesive and optical laminate using the same - Google Patents

Abstract

Disclosed is a resin film with adhesive, which is obtained by forming an adhesive layer on the surface of a resin film. The adhesive layer is excellent in durability and provided with high antistatic properties which hardly change over time. Specifically disclosed is a resin film with adhesive, which is obtained by forming an adhesive layer on at least one side of a resin film such as an optical film or a surface protection film. The adhesive layer is made from a composition containing 0.2-8 parts by weight of an ionic compound having an organic cation, which is in a solid state at room temperature, per 100 parts by weight of an acrylic resin mainly composed of a structural unit derived from a (meth)acrylate represented by the following formula (I). In the formula (I), Rrepresents a hydrogen atom or a methyl group; and Rrepresents an alkyl or aralkyl group having 1-14 carbon atoms which may be substituted by an alkoxy group having 1-10 carbon atoms.

Description

Resin film with adhesive and optical laminated body using the same {RESIN FILM WITH ADHESIVE AND OPTICAL LAMINATE USING THE SAME}

This invention relates to the resin film in which the adhesive layer was formed. As a resin film made into object by this invention, it is bonded, for example to the optical film containing a polarizing film and / or retardation film, and the surface on the opposite side to the adhesive layer of this optical film, and protects the surface until use. And a surface protective film. This invention also relates to the optical laminated body for liquid crystal displays using the resin film in which this adhesive layer was formed.

The polarizing film is attached to a liquid crystal display device and is widely used, the transparent protective film is laminated | stacked on both surfaces of a polarizer, the adhesive layer is formed in the surface of at least one protective film, and the peeling film adhered on the adhesive layer. It is in circulation. Moreover, retardation film is laminated | stacked on the polarizing film of the state in which the protective film was bonded on both surfaces of the polarizer, and it is set as an elliptical polarizing film, and the adhesive layer / peeling film may be adhere | attached on this retardation film side in this order. Moreover, an adhesive layer / peeling film may be adhere | attached in this order on the surface of retardation film. Before bonding to a liquid crystal cell, a peeling film is peeled from these polarizing films, an elliptically polarizing film, retardation film, etc., and it is bonded to a liquid crystal cell through the exposed adhesive layer. Since the static electricity generate | occur | produces such a polarizing film, an elliptically polarizing film, or a retardation film, when peeling a peeling film and bonding to a liquid crystal cell, development of the prevention measures is calculated | required.

As one of the countermeasures, Japanese Patent No. 3012860 discloses a polarizing film in which a protective film is laminated on the surface of a polarizer film and an adhesive layer is formed on the surface of the protective film, wherein the adhesive contains an electrolyte salt and an organopolysiloxane. It is proposed to use a composition containing an ion conductive composition and an acrylic copolymer. By using such an adhesive, although antistatic property is expressed, the performance is not necessarily enough, and also the adhesive durability was not sufficient performance.

Therefore, Japanese Patent Laid-Open No. 2004-536940 (W02003 / 011958) discloses blending an organic salt-based antistatic agent in a pressure-sensitive adhesive (adhesive) to impart antistatic properties to the pressure-sensitive adhesive. Japanese Unexamined Patent Application Publication No. 2004-114665 describes that a salt containing 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 to impart antistatic properties. In addition, Japanese Patent Laid-Open No. 2006-307238 discloses that an ionic liquid, which becomes a liquid at room temperature (25 ° C), is contained in the pressure-sensitive adhesive to promote antistatic charge. However, when the polarizing film coated with the adhesive is left for a long time, the antistatic property sometimes deteriorates with time. Since the distribution and storage period of a general polarizing film is about 6 months from manufacture, it is required to maintain antistatic performance for the time until a customer uses it.

Moreover, although the optical film with an adhesive as mentioned above is bonded to a liquid crystal cell by the adhesive layer side, and becomes a liquid crystal display device, when it is placed in high temperature or high temperature and high humidity conditions in this state, or when heating and cooling are repeated, an optical film Depending on the dimensional change of the foam, foaming may occur in the pressure-sensitive adhesive layer, or lifting or peeling may occur between the optical film and the pressure-sensitive adhesive layer or between the pressure-sensitive adhesive layer and the liquid crystal cell glass. This excellent thing is also required. In addition, when exposed to high temperature, the distribution of residual stress acting on the optical film becomes uneven, and stress concentration occurs in the outer peripheral part of the optical film, so that a phenomenon called whitening in which the outer peripheral part turns white at the time of black display occurs, or the color unevenness occurs. Since this may occur, suppression of such whitening and color unevenness is also required. In addition, when there is a problem when bonding the optical film with pressure-sensitive adhesive to the liquid crystal cell, the optical film is once peeled off, and then a new film is adhered again. The so-called reworking property which peels and does not leave an adhesive on cell glass and does not generate | occur | produce cloudy etc. is also calculated | required.

On the other hand, a surface protection film is generally bonded to the optical film etc. which are a to-be-protected body via the adhesive formed in the one surface, and is used in order to prevent the damage, contamination, etc. which arise at the time of processing and conveyance of a to-be-protected body. For example, an optical film such as a polarizing film or a retardation film to be applied to a liquid crystal display device has such a surface on a surface on the side opposite to the pressure-sensitive adhesive layer for the liquid crystal cell for the purpose of preventing damage or contamination. It is circulated in the state which the protective film bonded. The surface protective film is peeled off after the optical film is bonded to the liquid crystal cell, and static electricity is generated during the peeling, and when a voltage is applied to the liquid crystal cell while the static electricity remains, the orientation of the liquid crystal molecules is damaged or Since there exist problems, such as a defect of a panel, various antistatic treatment is given to the surface protection film.

An object of the present invention is to provide a resin film with a pressure-sensitive adhesive having a high antistatic property, the antistatic property of which does not change well with time, and which forms a pressure-sensitive adhesive layer having excellent durability on the surface of the resin film. It is in doing it. MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to solve such a subject, the present inventors mix | blended the specific ionic compound which becomes solid at room temperature (25 degreeC) with respect to the adhesive which has an acrylic resin as a main component, and this composition is made into the surface of a resin film. By forming it as an adhesive layer in the present invention, the inventors have found that a resin film with a pressure-sensitive adhesive having excellent antistatic and antistatic properties over time and excellent durability can be obtained.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to achieve this objective, the present inventors comprised the acrylic resin which becomes a main component of an adhesive with what has a specific molecular weight and molecular weight distribution, mix | blends two specific types as a crosslinking agent, and also a specific functional group as a silane compound. It was found that excellent results can be obtained by forming the pressure-sensitive adhesive layer formed of the pressure-sensitive adhesive composition containing an oligomer having a compound on the surface of the optical film.

That is, according to this invention, an adhesive layer is formed in at least one surface of a resin film, The adhesive layer is a resin film with an adhesive formed from the composition containing the next component (A) and (B). Is provided.

(A) the following formula (I)

(In formula, R <_1> represents a hydrogen atom or a methyl group, and R <_2> represents the C1-C14 alkyl group or aralkyl group which may respectively be substituted by the C1-C10 alkoxy group.)

100 weight part of acrylic resin which has a structural unit derived from the (meth) acrylic acid ester represented by as a main component, and

(B) 0.2-8 weight part of ionic compounds which have an organic cation and are solid at room temperature.

Thus, in this invention, it is room temperature as an antistatic agent to give antistatic property to the adhesive layer formed with this adhesive to the acrylic resin (A) which comprises an adhesive, and to suppress the change over time of antistatic property. It was found that the ionic compound (B) which is a solid at (25 ° C) was particularly effective.

The resin film which forms such an adhesive layer may be an optical film containing a polarizing film and / or retardation film. Moreover, it may be a surface protection film joined to the surface on the opposite side to the adhesive layer of such an optical film, and protecting the surface until use.

When a resin film is an optical film, it can be laminated | stacked on a glass substrate at the adhesive layer side, and it can be set as the optical laminated body for liquid crystal displays. Therefore, according to this invention, the optical laminated body by which the optical film with an adhesive with which the said adhesive layer was formed on the optical film is laminated | stacked on the glass substrate at the adhesive layer side is also provided.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail. In the resin film with an adhesive of this invention, an adhesive layer was formed in at least one surface of the resin film, The adhesive layer is

(A) acrylic resin and

(B) An ionic compound having an organic cation and solid at room temperature

It is formed into a composition containing. First, each component which comprises an adhesive composition is demonstrated.

Acrylic Resin (A)

In the resin film with an adhesive of this invention, the acrylic resin (A) used for an adhesive layer has a structural unit derived from the (meth) acrylic acid ester represented by said Formula (I), but is specifically, In addition to the structural unit derived from such (meth) acrylic acid ester, the monomer which has polar functional groups, such as a heterocyclic group, such as a free carboxyl group, a hydroxyl group, an amino group, and an epoxy ring, Preferably (meth) acryl which has a polar functional group It may be a thing containing the structural unit derived from an acid type compound. Here, (meth) acrylic acid means that any of acrylic acid or methacrylic acid may be sufficient, and "(meth)" at the time of (meth) acrylate etc. is also the same meaning.

In said Formula (I) which becomes a main structural unit of an acrylic resin (A), R <_1> is a hydrogen atom or a methyl group, R <_2> is a C1-C14 alkyl group or an aralkyl group, Preferably it is an alkyl group. In the alkyl group or aralkyl group represented by R ₂ , the hydrogen atom in each group may be substituted with an alkoxy group having 1 to 10 carbon atoms.

As a (meth) acrylic acid ester represented by Formula (I), Specifically, linear alkyl acrylate, such as methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, n-octyl acrylate, lauryl acrylate; Branched alkyl acrylate esters such as isobutyl acrylate, 2-ethylhexyl acrylate and isooctyl acrylate; Linear alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, n-octyl methacrylate, and lauryl methacrylate; Branched methacrylic acid alkyl esters, such as isobutyl methacrylate, 2-ethylhexyl methacrylate, and isooctyl methacrylate, etc. are illustrated.

When R <_2> is the alkyl group substituted by the alkoxy group, ie, when (R <_2>) is the alkoxyalkyl group, it is specifically (meth) acrylic acid ester represented by Formula (I), Specifically, 2-methoxyethyl acrylate and ethoxy acrylate Methyl, methacrylate 2-methoxyethyl, ethoxy methacrylate methyl, etc. are illustrated. Specific examples of the (meth) acrylic acid ester represented by formula (I) when R ₂ is an aralkyl group include benzyl acrylate and benzyl methacrylate.

These (meth) acrylic acid esters may be used alone, or may be copolymerized using a plurality of different ones.

Examples of the monomer having a polar functional group include monomers having free carboxyl groups such as acrylic acid, methacrylic acid and β-carboxyethyl acrylate; Hydroxyl groups such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2- or 3-chloro-2-hydroxypropyl (meth) acrylate, and diethylene glycol mono (meth) acrylate Monomer having; Acryloylmorpholine, vinyl caprolactam, N-vinyl-2-pyrrolidone, tetrahydrofurfuryl (meth) acrylate, caprolactone modified tetrahydrofurfuryl acrylate, 3,4-epoxycyclohexylmethyl (meth Monomers having a heterocyclic group such as acrylate, glycidyl (meth) acrylate and 2,5-dihydrofuran; The monomer etc. which have an amino group different from heterocycles, such as N, N- dimethylaminoethyl (meth) acrylate, are mentioned. The monomer which has such a polar functional group may be used independently, respectively and may use several different things.

Among these, it is preferable to use the monomer which has a hydroxyl group as one of the polar functional group containing monomers which comprise an acrylic resin (A). Moreover, in addition to the monomer which has a hydroxyl group, it is also effective to use together the monomer which has another polar functional group, for example, the monomer which has a free carboxyl group.

As for the acrylic resin (A) used for an adhesive layer, 60-99.9 weight part of structural units derived from the (meth) acrylic acid ester represented by said Formula (I) with respect to 100 weight part of non volatile matters are preferable normally Preferably it is contained in the ratio of 80-99.9 weight part, and the structural unit derived from the monomer which has a polar functional group is normally contained in the ratio of 0.1-20 weight part, Preferably it is 0.4-10 weight part.

The acrylic resin (A) used for this invention may contain the structural unit derived from monomers other than the monomer which has the (meth) acrylic acid ester of Formula (I) and polar functional group demonstrated above. Examples thereof include a structural unit derived from a (meth) acrylic acid ester having an alicyclic structure in a molecule, a structural unit derived from a styrene monomer, a structural unit derived from a vinyl monomer, and a plurality of (meth) acryloyl groups in the molecule. Structural units derived from the monomer which has a etc. are mentioned.

The alicyclic structure is a cycloparaffin structure having usually 5 or more carbon atoms, preferably 5 to 7 carbon atoms. Specific examples of the acrylate ester having an alicyclic structure include isobornyl acrylate, cyclohexyl acrylate, dicyclopentanyl acrylate, cyclododecyl acrylate, methylcyclohexyl acrylate, trimethylcyclohexyl acrylate, tert-butylcyclohexyl acrylate, α Cyclohexyl ethoxy acrylate, cyclohexyl acrylate, etc. are mentioned, As a specific example of the methacrylic acid ester which has an alicyclic structure, isobornyl methacrylate, cyclohexyl methacrylate, and dicyclopentanyl methacrylate And cyclododecyl methacrylate, methylcyclohexyl methacrylate, trimethylcyclohexyl methacrylate, tert-butylcyclohexyl methacrylate, cyclohexyl methacrylate and the like.

Examples of styrene monomers include, in addition to 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, and iodine styrene; Moreover, nitro styrene, acetyl styrene, methoxy styrene, divinyl benzene, etc. are mentioned.

Examples of the vinyl monomers include fatty acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate and vinyl laurate; Vinyl halides such as vinyl chloride and vinyl bromide; Vinylidene halides such as vinylidene chloride; Nitrogen-containing aromatic vinyls such as vinylpyridine, vinylpyrrolidone and vinylcarbazole; Conjugated diene monomers such as butadiene, isoprene and chloroprene; Furthermore, acrylonitrile, methacrylonitrile, etc. are mentioned.

Examples of the monomer having a plurality of (meth) acryloyl groups in the molecule include 1,4-butanedioldi (meth) acrylate, 1,6-hexanedioldi (meth) acrylate, and 1,9-nonanedioldi ( Two molecules in the molecule such as meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate Monomers having a meth) acryloyl group; The monomer etc. which have three (meth) acryloyl groups in the same molecule as a trimethylol propane tri (meth) acrylate are mentioned.

Monomers other than the monomer which has the (meth) acrylic acid ester of Formula (I) and a polar functional group can be used individually or in combination of 2 or more types, respectively. In the acrylic resin (A) used for an adhesive, the structural unit derived from monomers other than the monomer which has the (meth) acrylic acid ester of Formula (I) and a polar functional group is 0 normally with respect to 100 weight part of non volatile matters of the resin. It is contained in the ratio of -20 weight part, Preferably it is 0-10 weight part.

The active ingredient of an adhesive has two types of acrylic resin containing the structural unit derived from the monomer which has a structural unit derived from the (meth) acrylic acid ester represented by Formula (I) as above as a main component, and having a polar functional group. The above may be included. Moreover, the acrylic resin different from it, specifically, the acrylic resin which has a structural unit derived from the (meth) acrylic acid ester of Formula (I), and does not contain a polar functional group is mixed with the said acrylic resin, for example. It may be one. The acrylic resin which has a structural unit derived from the (meth) acrylic acid ester of Formula (I) as a main component, and contains the structural unit derived from the monomer which has a polar functional group is 60 weight% or more in whole acrylic resin, Furthermore, 80 weight It is preferable to set it as% or more.

The acrylic resin containing the structural unit derived from the monomer which has a structural unit derived from the (meth) acrylic acid ester of Formula (I) as a main component, and which has a polar functional group of the standard polystyrene conversion by gel permeation chromatography (GPC) It is preferable that the weight average molecular weight (Mw) exists in the range of 1,000,000-2,000,000. 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 tends to be improved, and the possibility of lifting or peeling between the glass substrate and the pressure-sensitive adhesive layer tends to be lowered, and the reworkability tends to be improved. It is preferable because there is. Moreover, when this weight average molecular weight is 2,000,000 or less, even if the dimension of the optical film bonded to the adhesive layer changes, since an adhesive layer will fluctuate according to the dimension change, between the brightness of the peripheral part of a liquid crystal cell, and the brightness of a center part, It is preferable because there is a tendency that there is no difference and whitening and color unevenness are 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 usually in the range of about 2 to 10.

This acrylic resin may be comprised only by the comparatively high molecular weight mentioned above, and may be comprised by the mixture with the acrylic resin different from it in addition to such an acrylic resin. As an acrylic resin which can be mixed and used, For example, the structural unit derived from the (meth) acrylic acid ester represented by said Formula (I) is made into a main component, and the weight average molecular weight is what exists in the range of 50,000-300,000. Can be.

The acrylic resin (the mixture of both in the case of combining two or more kinds) is a solution prepared by dissolving it in ethyl acetate and adjusting the concentration to 20% by weight of a nonvolatile content, 20 Pa · s or less at 25 ° C., further 0.1 to 7 Pa · s It is preferable to show the viscosity of. When the viscosity at this time is 20 Pa · s or less, the adhesiveness under high temperature and high humidity tends to be improved, and the possibility of lifting or peeling between the glass substrate and the pressure-sensitive adhesive layer tends to be lowered, and the reworkability tends to be improved. It is preferable because there is. Viscosity can be measured with a Brookfield viscometer.

The acrylic resin which comprises an adhesive layer can be manufactured by well-known various methods, such as a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, suspension polymerization method, for example. In manufacture of this acrylic resin, a polymerization initiator is used normally. About 0.001-5 weight part of polymerization initiators are used with respect to a total of 100 weight part of all the monomers used for manufacture of an acrylic resin.

As a polymerization initiator, a thermal polymerization initiator, a photoinitiator, etc. are used. As a photoinitiator, 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2- propyl) ketone etc. are mentioned, for example. As the thermal polymerization initiator, for example, 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 Azo compounds such as' -azobis (2-methylpropionate) and 2,2'-azobis (2-hydroxymethylpropionitrile); Lauryl peroxide, tert-butylhydroperoxide, benzoyl peroxide, tert-butylperoxybenzoate, cumene hydroperoxide, diisopropylperoxydicarbonate, dipropylperoxydicarbonate, tert-butylperoxy neodecanoate organic peroxides such as tert-butylperoxypivalate, (3,5,5-trimethylhexanoyl) peroxide; Inorganic peroxides such as potassium persulfate, ammonium persulfate, hydrogen peroxide and the like. Moreover, the redox type initiator etc. which used a peroxide and a reducing agent together can also be used as a polymerization initiator.

As a manufacturing method of an acrylic resin, the solution polymerization method is preferable among the methods shown above. When the specific example of the solution polymerization method is given and demonstrated, a desired monomer and an organic solvent are mixed, and a thermal polymerization initiator is added in nitrogen atmosphere, about 40-90 degreeC, Preferably it is about 60 to 80 degreeC, about 3 to 10 hours. The method of stirring, etc. are mentioned. Moreover, in order to control reaction, you may add a monomer and a thermal polymerization initiator continuously or intermittently during superposition | polymerization, or may be added in the state dissolved in the organic solvent. Here, as an organic solvent, For example, aromatic hydrocarbons, such as toluene and xylene; Esters such as ethyl acetate and butyl acetate; Aliphatic alcohols such as propyl alcohol and isopropyl alcohol; Ketones, such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, etc. can be used.

Ionic Compound (B)

In this invention, in addition to the acrylic resin (A) mentioned above, the ionic compound (B) which is solid at room temperature (25 degreeC) is used as an antistatic agent. This ionic compound (B) has an organic cation. The ionic compound which is solid at such room temperature may be called an ionic solid in this specification.

The cation component constituting the ionic compound (B) may be an organic cation that is satisfied to be an ionic solid, and is not particularly limited. For example, an imidazolium cation, a pyridinium cation, an ammonium cation, a sulfonium cation, a phosphonium cation, etc. are mentioned, When used for the adhesive layer of a resin film, it is charged when peeling the peeling film formed on it. Pyridinium cation or imidazolium cation is preferable from the viewpoint of being unlikely.

On the other hand, in the ionic compound (B), the anion component that becomes a pair ion of the cationic component is not particularly limited as long as it is satisfied that it becomes an ionic solid, and may be an inorganic anion or an organic anion. For example, the following is mentioned.

Chloride anion [Cl ^-],

Bromide anion [Br ^-],

Iodide anion [I ^-],

Tetrachloro-aluminate anion [AlCl ₄ ^-],

Heptanoic Chlorodifluoromethane aluminate anion [Al ₂ Cl ₇ ^-],

Anion on tetrafluoroborate [BF ₄ ^-],

Phosphate anions hexafluorophosphate [PF ₆ ^-],

Perchlorate anion [ClO ₄ ^-],

Nitrate anions [NO ₃ ^-],

Acetate anion [CH ₃ COO ^-],

Trifluoroacetate anion [CF ₃ COO ⁻ ],

Methane sulfonate anion [CH ₃ SO ₃ ^-],

Methane sulfonate anion of trifluoroacetic [CF ₃ SO ₃ ^-],

p-toluenesulfonate anion [p-CH ₃ C ₆ H ₄ SO ₃ ⁻ ],

Bis (trifluoromethane sulfonyl) imide anion _{[(CF 3 SO 2) 2} N -],

Tris (trifluoromethane sulfonyl) bumetanide anion _{[(CF 3 SO 2) 3} C -],

Hexafluoro-acetoxy anion [AsF ₆ ^-],

Antimonate anion hexafluorophosphate [SbF ₆ ^-],

Hexafluoro niobate anions [NbF ₆ ^-],

Tantalum anion hexafluorophosphate [TaF ₆ ^-],

Dimethyl phosphinate anion ^{_{[(CH 3) 2 POO -}} ],

(Poly) hydrofluorofluoride anion [F (HF) _n ⁻ ] (n is about 1 to 3),

DC Ana imide anion ^{_{[(CN) 2 N -]}} ,

Thiocyanate anion [SCN ^-],

Perfluorobutanesulfonate anion [C ₄ F ₉ SO ₃ ⁻ ],

Bis (ethanesulfonyl pentafluorophenyl) 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, especially the anion component containing a fluorine atom is used preferably because it gives the ionic solid excellent in antistatic performance, and hexafluorophosphate anion is especially preferable.

The specific example of the ionic solid used for this invention can be suitably selected from the combination of the said cationic component and anionic component. As a compound which is a combination of a specific cationic component and an anion component, the following are mentioned.

N-hexylpyridinium hexafluorophosphate,

N-octylpyridinium hexafluorophosphate,

N-butyl-4-methylrupyridinium hexafluorophosphate,

N-butyl-N-methylpyrrolidinium hexafluorophosphate,

1-ethyl-3-methylimidazolium hexafluorophosphate,

1-ethyl-3-methylimidazolium p-toluenesulfonate,

1-butyl-3-methylimidazolium methanesulfonate,

Tetrabutylammonium hexafluorophosphate,

Tetrabutylammonium p-toluenesulfonate,

(2-hydroxyethyl) trimethylammonium dimethylphosphinate and the like.

These ionic solids can be used individually or in combination of 2 or more types, respectively. Examples of the ionic solids are not limited to the substances listed above.

As described above, the ionic compound (B) that is solid at room temperature is effective in imparting antistatic properties to the pressure-sensitive adhesive layer formed of the composition containing the acrylic resin (A) and maintaining various physical properties as the pressure-sensitive adhesive. In particular, the antistatic performance can be maintained for a long time compared with the case of using an ionic compound that is liquid at room temperature. From the viewpoint of such antistatic long-term stability, it is preferable that the ionic compound (B) has a melting point of 30 ° C. or higher and further 35 ° C. or higher. On the other hand, when the melting point is too high, the compatibility with the acrylic resin (A) is deteriorated, so it is preferable to have a melting point of 90 ° C. or lower, more preferably 80 ° C. or lower.

The ionic compound (B) is contained at a ratio of 0.2 to 8 parts by weight relative to 100 parts by weight of the nonvolatile matter (total weight when using two or more types) of the acrylic resin (A). It is preferable to contain an ionic compound (B) 0.2 weight part or more with respect to 100 weight part of non volatile matters of an acrylic resin, since antistatic performance improves, and if the quantity is 8 weight part or less, durability will be improved. It is preferable because it is easy to maintain. The quantity of the ionic compound (B) with respect to 100 weight part of non volatile matters of an acrylic resin (A) may be in the range of 0.2-5 weight part, Preferably it is 0.5 weight part or more and 3 weight part or less.

[Other components constituting the adhesive]

Usually, a crosslinking agent (C) is further mix | blended with the above acrylic resin (A) and an ionic compound (B), and it is set as an adhesive composition. A crosslinking agent (C) is a compound which has at least two functional groups in a molecule | numerator which can bridge | crosslink with the structural unit derived from the polar functional group containing monomer especially in an acrylic resin (A), Specifically, an isocyanate type compound, an epoxy type compound, Metal chelate compounds, aziridine compounds and the like.

An isocyanate type compound is a compound which has at least 2 isocyanate group (-NCO) in a molecule | numerator, For example, tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate , Diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, etc. are mentioned. Moreover, the adduct body which made polyols, such as glycerol and a trimethylol propane, react with such an isocyanate compound, and also made the isocyanate compound into dimer, trimer, etc. can be a crosslinking agent used for an adhesive. You may use it in mixture of 2 or more types of isocyanate compounds.

An epoxy compound is a compound which has at least 2 epoxy groups in a molecule | numerator, For example, bisphenol-A epoxy resin, ethylene glycol diglycidyl ether, polyethyleneglycol diglycidyl ether, glycerine diglycidyl ether, Glycerine triglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, N, N- diglycidyl aniline, N, N, N ', N'-tetraglycidyl -m-xylenediamine, 1, 3-bis (N, N'- diglycidylaminomethyl) cyclohexane, etc. are mentioned. You may mix and use 2 or more types of epoxy compounds.

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

The aziridine-based compound is a compound having at least two three-membered ring skeletons containing one nitrogen atom and two carbon atoms, also called ethyleneimine, in the molecule. For example, diphenylmethane-4,4'-bis (1 -Aziridinecarboxamide), toluene-2,4-bis (1-aziridinecarboxamide), triethylenemelamine, isophthaloylbis-1- (2-methylaziridine), tris-1-aziridi Nylphosphine oxide, hexamethylene-1,6-bis (1-aziridinecarboxamide), trimethylolpropane-tri-β-aziridinylpropionate, tetramethylolmethane-tri-β-aziridinyl Propionate, and the like.

Among these crosslinking agents, an isocyanate compound, particularly an xylylene diisocyanate, tolylene diisocyanate or hexamethylene diisocyanate, or an adduct or an isocyanate compound obtained by reacting these isocyanate compounds with a polyol such as glycerol or trimethylolpropane , A mixture of trimers and the like, a mixture of these isocyanate compounds, and the like are preferably used. As a suitable isocyanate compound, an adduct formed by reacting tolylene diisocyanate, tolylene diisocyanate with a polyol, a dimer of tolylene diisocyanate and a trimer of tolylene diisocyanate, and hexamethylene diisocyanate and hexamethylene diisocyanate are reacted with a polyol. The adduct body, the dimer of hexamethylene diisocyanate, and the trimer of hexamethylene diisocyanate are mentioned.

A crosslinking agent (C) is mix | blended in the ratio of about 0.01-10 weight part normally, Preferably it is about 0.1-5 weight part with respect to 100 weight part (when using two or more types) of acrylic resin (A). . When the amount of the crosslinking agent (C) to 100 parts by weight of the acrylic resin (A) is 0.01 parts by weight or more, since the durability of the pressure-sensitive adhesive layer tends to be improved, the optical film with the pressure-sensitive adhesive is further provided. Since whitening at the time of applying to a liquid crystal display device becomes inconspicuous, it is preferable.

When the resin film with an adhesive of this invention is bonded to a glass substrate from the adhesive layer side, the adhesive for forming this adhesive layer is made to contain a silane type compound, in order to improve adhesiveness of an adhesive layer and a glass substrate. It is preferable that especially a silane type compound is contained in the acrylic resin before mix | blending a crosslinking agent.

As a silane type compound, vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, for example. , N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3- Mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, 3-glycidoxypropylethoxydimethyl Silane and the like. You may use 2 or more types of silane type compounds.

The silane compound may be a silicone oligomer type. When a silicone oligomer is represented by the form of a (monomer) oligomer, the following are mentioned, for example.

3-mercaptopropyltrimethoxysilane-tetramethoxysilane copolymer,

3-mercaptopropyltrimethoxysilane-tetraethoxysilane copolymer,

3-mercaptopropyltriethoxysilane-tetramethoxysilane copolymer,

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

Mercaptomethyltrimethoxysilane-tetramethoxysilane copolymer,

Mercaptomethyltrimethoxysilane-tetraethoxysilane copolymer,

Mercaptomethyltriethoxysilane-tetramethoxysilane copolymer,

Copolymers containing mercaptomethyl groups, such as 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 group such as 3-methacryloyloxypropylmethyldiethoxysilane-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,

Copolymers 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,

Vinyl group-containing copolymers 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,

Copolymers containing amino groups such as 3-aminopropylmethyldiethoxysilane-tetraethoxysilane copolymer and the like.

These silane compounds are in most cases liquid. The compounding quantity of a silane type compound in an adhesive is about 0.01-10 weight part normally with respect to 100 weight part (non-volatile components, the total weight when using two or more types) of acrylic resin (A), Preferably it is 0.05-5 Used in parts by weight. Since the adhesiveness of an adhesive layer and a glass substrate improves that the quantity of a silane type compound with respect to 100 weight part of non volatile matters of an acrylic resin improves, it is preferable. Moreover, since the quantity tends to be suppressed that bleeding out a silane type compound from an adhesive layer is 10 weight part or less, it is preferable.

You may further mix | blend a crosslinking catalyst, a weathering stabilizer, a tackifier, a plasticizer, a softener, a dye, a pigment, an inorganic filler, resin other than an acrylic resin (A), to the adhesive demonstrated above. Moreover, it is also useful to mix | blend an ultraviolet curable compound with an adhesive, to irradiate and harden an ultraviolet-ray after adhesive layer formation, and to set it as a harder adhesive layer. Especially, when a crosslinking catalyst is mix | blended with a crosslinking agent to an adhesive, an adhesive layer can be prepared by aging of a short time, and in the resin film with an adhesive obtained, the lifting and peeling generate | occur | produce between a resin film and an adhesive layer, or an adhesive layer Foaming can be suppressed from occurring, and reworkability may be further improved. As a crosslinking catalyst, for example, hexamethylenediamine, ethylenediamine, polyethyleneimine, hexamethylenetetraamine, diethylenetriamine, triethylenetetraamine, isophoronediamine, trimethylenediamine, polyamino resin, melamine resin An amine compound etc. are mentioned. When mix | blending an amine compound as a crosslinking catalyst with an adhesive, an isocyanate type compound is suitable as a crosslinking agent.

Each component which comprises an adhesive becomes an adhesive composition in the state melt | dissolved in the solvent, is apply | coated on a suitable base material, it is dried, and becomes an adhesive layer.

In the resin film with an adhesive of this invention, it is preferable for an adhesive layer to make the gel fraction into the range of 50 to 99 weight%. The gel fraction is a value measured according to the following (I)-(IV) here.

(I) A pressure-sensitive adhesive layer having an area of about 8 cm x about 8 cm, and a metal mesh made of SUS304 of about 10 cm x about 10 cm (the weight of which is Wm) are joined.

(II) The weight of the joined product obtained in the above (I) is weighed, and the weight thereof is Ws. Next, it is folded four times so as to surround the pressure-sensitive adhesive layer, fixed with a stapler (stapler), and weighed, and the weight thereof is Wb.

(III) The mesh fixed by the stapler in the above (II) was put into a glass container, and 60 ml of ethyl acetate was added and immersed, and this 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 the weight thereof is Wa, and the gel fraction is calculated based on the following equation.

Gel fraction (wt%) = [{Wa- (Wb-Ws) -Wm} / (Ws-Wm)] × 100

If the gel fraction of the pressure-sensitive adhesive layer is 50% by weight or more, the durability of the pressure-sensitive adhesive layer tends to be improved, and if the gel fraction is 99% by weight or less, it is preferable because it is easy to manufacture.

In order to adjust the gel fraction of the pressure-sensitive adhesive layer to 50 to 99% by weight, the amount of the crosslinking agent is increased even if the amount of the crosslinking agent is increased. You can adjust the fraction. Specifically, the blending amount of the crosslinking agent with respect to 100 parts by weight of the nonvolatile content of the acrylic resin constituting the pressure-sensitive adhesive layer (when using two or more types thereof) is adjusted in the range of about 0.01 to 10 parts by weight to the type of acrylic resin. This is a good choice. The gel fraction of the pressure-sensitive adhesive layer is more preferably 65% by weight or more, further 75% by weight or more, and 95% by weight or less.

[Resin Film with Adhesive]

The resin film with an adhesive of this invention forms the adhesive layer formed from the above-mentioned adhesive composition on at least one surface of a resin film. The resin film used here is a surface protection film etc. which are bonded to the optical film containing the film chosen from a polarizing film and retardation film, the optical film which is a to-be-protected body, etc., and are used for the purpose of protecting the surface from damage, contamination, etc. Can be mentioned.

A polarizing film is an optical film which has a function which emits 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, reflects linearly polarized light having a property of transmitting linearly polarized light having a vibrating surface orthogonal thereto, and linearly polarized light having a vibrating surface in a certain direction, and is perpendicular to the There exists a polarization separation film which has the property which permeate | transmits linearly polarized light which has an oscillation surface, and the elliptical polarizing film which laminated | stacked the polarizing film and the retardation film mentioned later. As a suitable specific example of a polarizing film, especially a linearly polarizing film (sometimes called a polarizer or a polarizer film), the dichroic dye, such as iodine and a dichroic dye, adsorb | sucked to the uniaxially stretched polyvinyl alcohol-type resin film Can be mentioned.

Retardation film is an optical film which shows optical anisotropy, for example, polyvinyl alcohol, polycarbonate, polyester, polyarylate, polyimide, polyolefin, cyclic polyolefin, polystyrene, polysulfone, polyether sulfone, polyvinylidene Stretched films obtained by stretching a polymer film containing fluoride / polymethyl methacrylate, liquid crystalline polyester, acetyl cellulose, ethylene-vinyl acetate copolymer saponification, polyvinyl chloride, and the like in about 1.01 to 6 times . Especially, the polymer film which uniaxially stretched or biaxially stretched the polycarbonate film and the cyclic polyolefin type film is preferable. Although there exist some called a uniaxial retardation film, a wide viewing angle retardation film, a low photoelastic-rate retardation film, etc., it is applicable to all these.

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 layer type compound can also be used as retardation film. In such a retardation film, a film having a twist-oriented rod-like liquid crystal, which is referred to as a temperature-compensated retardation film and sold under the brand name "LC film" by Nippon Oil Co., Ltd., Nippon Petroleum Co., Ltd. Film with tilted rod-shaped liquid crystal sold under the trade name "NH Film" in Fujifilm Co., Ltd. film with tilted alignment of disc-shaped liquid crystal sold under the trade name "WV film" from Fujifilm Co., Ltd., Sumitomo Chemical Co., Ltd. The biaxially oriented film sold under the brand name "VAC film", and the biaxially oriented film sold under the brand name "new VAC film" by Sumitomo Chemical Co., Ltd. are mentioned.

Moreover, what bonded the protective film to these optical films can also be used as an optical film. A transparent resin film is used as a protective film, As this transparent resin, For example, acetyl cellulose type resin represented by triacetyl cellulose or diacetyl cellulose, methacryl resin represented by polymethyl methacrylate, polyester Resin, polyolefin resin, polycarbonate resin, polyether ether ketone resin, polysulfone resin and the like. Ultraviolet absorbers, such as a salicylic acid ester compound, a benzophenone type compound, a benzotriazole type compound, a triazine type compound, a cyanoacrylate type compound, and a nickel complex salt type compound, may be mix | blended with resin which comprises a protective film. As a protective film, acetyl cellulose type resin films, such as a triacetyl cellulose film, are used suitably.

Among the optical films described above, a linear polarizing film is often used in a state in which a protective film is adhered to one or both surfaces of a polarizer constituting the polarizer, for example, a polyvinyl alcohol-based resin. Moreover, although the above-mentioned elliptical polarizing film laminated | stacked the linear polarizing film and retardation film, the polarizing film also has the state which the protective film adhered to one side or both sides of a polarizer film in many cases. When forming the adhesive layer by this invention in such an elliptical polarizing film, an adhesive layer is normally formed in the retardation film side.

A surface protection film is a film used for the purpose of protecting the surface, such as an optical film which is a to-be-protected body from a wound and a contamination, For example, the polarizing film, retardation film, light-diffusion sheet, and reflection used for production of a liquid crystal display device Various optical films, such as a sheet, distribute | circulate in the state which bonded the surface protection film to the surface (surface on the opposite side to the adhesive layer, when it has an adhesive layer on one surface), and after bonding to a liquid crystal cell etc., the surface It is common to peel off a protective film. As a base material of a surface protection film, For example, polyolefin resin like polyethylene, polypropylene, polymethyl pentene, fluorinated polyolefin resin, such as polyvinyl fluoride, polyvinylidene fluoride, poly ethylene fluoride, polyethylene, Polyester resins such as phthalate, polyethylene terephthalate, polybutylene terephthalate, polyethylene terephthalate / isophthalate copolymer, polyamide such as nylon 6, nylon 6, 6, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer , Ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polyvinyl alcohol, vinyl polymer such as vinylon, cellulose triacetate, cellulose diacetate, cellulose resin such as cellophane, polymethyl methacrylate, polymethacrylic acid Such as ethyl, ethyl polyacrylate, butyl polyacrylate Methacrylic based resin, and the number of the outside polystyrene, polycarbonate, polyarylate, polyimide and the like.

In the resin film with an adhesive of this invention, it is preferable to adhere | attach a peeling film on the adhesive layer surface, and to temporarily attach and protect until use. The release film used here is based on the film containing various resins, such as a polyethylene terephthalate, a polybutylene terephthalate, a polycarbonate, and a polyarylate, for example, to the bonding surface with the adhesive layer of this base material, And a release treatment such as silicon treatment may be performed.

The resin film with an adhesive adheres to the above-mentioned peeling film, for example, forms the adhesive layer by forming the adhesive layer, and further laminates a resin film on the obtained adhesive layer, and an adhesive composition on a resin film. It can apply | coat and form an adhesive layer, bond a peeling film to the adhesive surface, and protect it, and can manufacture by the method etc. which make it the resin film with an adhesive.

Although the thickness of an adhesive layer is not specifically limited, Usually, it is preferable that it is 30 micrometers or less, Moreover, it is preferable that it is 10 micrometers or more, More preferably, it is 10-20 micrometers. When the thickness of an adhesive layer is 30 micrometers or less, since adhesiveness under high temperature, high humidity improves, there exists a tendency for the possibility of lifting and peeling between a glass substrate and an adhesion layer to become low, and reworkability tends to improve. If the thickness is 10 µm or more, and the thickness of the optical film bonded thereto is changed, the adhesion layer fluctuates according to the change of the dimension, so that the brightness between the brightness of the periphery of the liquid crystal cell and the brightness of the central part is varied. It is preferable because there is a tendency that there is no difference and whitening and color unevenness are suppressed. Generally, although the thickness of the adhesive layer adhere | attached on liquid crystal cell glass was 25 micrometers as a standard, in this invention, even if the thickness is 20 micrometers or less, sufficient performance is exhibited as an adhesive layer.

When the resin film with an adhesive of this invention adheres to a glass substrate and makes it an optical laminated body, when there exists a problem and peels the resin film from a glass substrate, an adhesive layer peels according to a resin film, and an adhesive layer Since cloudiness, debris, etc. hardly generate | occur | produce on the surface of the glass substrate which contacted, it is easy to rebond | attach the resin film with an adhesive on the glass substrate after peeling. That is, it is excellent in what is called rework property.

[Optical laminate]

The resin film with an adhesive of this invention comprises a resin film with an optical film, can be laminated | stacked on a glass substrate in the adhesive layer, and can be set as an optical laminated body. In order to laminate | stack the optical film with an adhesive on a glass substrate, and to make an optical laminated body, the peeling film is peeled off from the resin film with an adhesive obtained as mentioned above, for example, and the exposed adhesive layer is made to the surface of a glass substrate. It is good to join. Here, as a glass substrate, the glass substrate of a liquid crystal cell, the glass for glare-proof, the glass for sunglass, etc. are mentioned, for example. Especially, the optical film (upper polarizing film) with an adhesive was laminated | stacked on the glass substrate of the front side (viewing side) of a liquid crystal cell, and another optical film (low polarization light) with an adhesive was attached to the glass substrate of the back side of a liquid crystal cell. Since the optical laminated body formed by laminating | stacking a film) can be used as a liquid crystal display device, it is preferable. As a material of a glass substrate, soda lime glass, low alkali glass, an alkali free glass, etc. are mentioned, for example.

The optical laminated body of this invention can be used as a liquid crystal cell of a liquid crystal display device. The liquid crystal display device formed from the optical laminated body of this invention is a liquid crystal display for personal computers containing a notebook type | mold, a desktop type, PDA (Personal Digital Assistance), etc., a television, a vehicle display, an electronic dictionary, a digital camera, It can be used for digital video cameras, electronic desk calculators and watches.

Although an Example is given to the following and this invention is demonstrated to it further more concretely, this invention is not limited by these examples. In the examples, "parts" and "%" indicating the amount to content of use are based on weight unless otherwise specified.

In the following example, a non volatile matter is the value measured by the method according to JISK5407. Specifically, the pressure-sensitive adhesive solution was added to the chalet at any weight, and the residual non-volatile content weight after drying for 2 hours at 115 ° C. in an explosion-proof oven was initially measured and expressed as a percentage of the less solution weight. In addition, the measurement of a weight average molecular weight is carried out by GPC apparatus and arrange | positioned two "TSK gel GMHHR-H (S)" by Toso Corporation in series as a column, and sample concentration using tetrahydrofuran as an eluent. It carried out by standard polystyrene conversion on the conditions of 5 mg / mL, 100 microliters of sample introduction amounts, the temperature of 40 degreeC, and the flow rate of 1 mL / min.

First, the manufacture example of an acrylic resin is shown.

[Polymerization Example 1]

A mixed solution of 81.8 parts of ethyl acetate, 98.6 parts of butyl acrylate, 1.0 part of 2-hydroxyethyl acrylate, and 0.4 part of acrylic acid was placed in a reaction vessel equipped with a cooling tube, a nitrogen inlet tube, a thermometer, and a stirrer, and the air in the apparatus with nitrogen gas. The internal temperature was raised to 55 ° C while replacing with oxygen. Then, the whole amount of the solution which melt | dissolved 0.14 parts of azobisisobutyronitrile (polymerization initiator) in 10 parts of ethyl acetate was added. After 1 hour of initiator addition, ethyl acetate was continuously added to the reaction vessel at an addition rate of 17.3 parts / hr so that the concentration of the acrylic resin except for the monomer was 35%. Ethyl acetate was added to adjust the concentration of the acrylic resin to 20%. As for the obtained acrylic resin, the weight average molecular weight Mw of polystyrene conversion by GPC was 1,230,000, and Mw / Mn was 3.9. Let this be acrylic resin A1. The structural unit derived from 2-hydroxyethyl acrylate which is a hydroxyl group containing monomer in acrylic resin A1 is 1%, and the structural unit derived from acrylic acid which is a carboxyl group containing monomer is 0.4%.

[Polymerization Example 2]

An acrylic resin was produced in the same manner as in Polymerization Example 1 except that the monomer composition was changed to 81.8 parts of ethyl acetate, 78.6 parts of butyl acrylate, 20.0 parts of methyl acrylate, 1.0 part of 2-hydroxyethyl acrylate, and 0.4 part of acrylic acid. As for the obtained acrylic resin, 1,648,000 and Mw / Mn of the weight average molecular weight Mw of polystyrene conversion by GPC were 4.1. Let this be acrylic resin A2. Also in acrylic resin A2, the ratio of the structural unit derived from 2-hydroxyethyl acrylate which is a hydroxyl-containing monomer is 1%, and the ratio of the structural unit derived from acrylic acid which is a carboxyl group-containing monomer is 0.4%.

Next, the adhesive is prepared using the acrylic resin manufactured above, and the Example and comparative example applied to the optical film are shown. In the following examples, the following were used as the ionic compound. The symbol of each compound is attached for future reference, The compound called ionic solid 1-ionic solid 5 is solid at room temperature of 25 degreeC, and the compound called ionic liquid 1 is at room temperature of 25 degreeC. It was a liquid.

Ionic solid 1: N-butyl-4-methylpyridinium hexafluorophosphate (has the structure of the following formula, melting point 48 degreeC)

Ionic solids 2: N-hexylpyridinium hexafluorophosphate (has the structure of the following formula, melting point 45 ℃)

Ionic solids 3: N-octyl-4-methylpyridinium hexafluorophosphate (having the structure of the following formula, melting point 44 ℃)

Ionic solid 4: 1-methyl-3-ethylimidazolium hexafluorophosphate (has the structure of the following formula, melting point 62 degreeC)

Ionic solid 5: tetrabutylammonium hexafluorophosphate (has the structure of the following formula, melting point 78 ℃)

Ionic liquid 1: N-hexyl-4-methylpyridinium hexafluorophosphate (has the structure of following formula, melting point 18 degreeC)

Moreover, the following were used as a crosslinking agent and a silane type compound (all are brand names).

<Bridge school>

Takeate D160N: Obtained from the ethyl acetate solution (solid content concentration 75%) of the trimethylolpropane adduct of hexamethylene diisocyanate, and Mitsui Chemical Polyurethanes.

Colonate L: Obtained from the ethyl acetate solution (solid content concentration 75%) of the trimethylolpropane adduct of tolylene diisocyanate, and the Japanese Polyurethane Co., Ltd. (Silane-based compound)

KBE-402: Glycidoxypropyl diethoxy methyl silane (liquid) obtained from Shin-Etsu Chemical Co., Ltd.

KBM-403: Glycidoxypropyl trimethoxysilane (liquid) obtained from Shin-Etsu Chemical Co., Ltd.

[Examples 1-5 and Comparative Examples 1-3]

(a) Preparation of pressure-sensitive adhesive

About 100 parts of solid content of acrylic resin A1 obtained by the polymerization example 1, 0.8 part of crosslinking agent "Takenate D160N" as solid content, 0.5 part of silane type compound "KBE-402", and the ionic compound shown in Table 1 were put therein, respectively. It mixed by the quantity shown, and further added ethyl acetate so that solid content concentration might be 13%, and it was set as the adhesive composition.

(b) Preparation of Resin Film with Adhesive

Each said adhesive composition is apply | coated so that the thickness after drying using an applicator may be applied to the mold release process surface of the release-processed polyethylene terephthalate film (brand name "PET 3811", available from Lintec Co., Ltd .; separator). And it dried at 90 degreeC for 1 minute, and obtained the sheet-like adhesive. Next, the surface (adhesive side) on the opposite side to the separator of the sheet-like adhesive obtained above on one side of the polarizing film of the three-layered structure which pinched both surfaces of the polyvinyl alcohol polarizer with iodine adsorption-aligned between the protective films containing triacetylcellulose. After laminating | stacking with a laminator, it cured for 7 days on condition of the temperature of 23 degreeC, and 65% of a relative humidity, and obtained the polarizing film with an adhesive. About the pressure-sensitive adhesive layer after curing, the gel fraction was measured by the method described above, and the results are shown in Table 2.

(c) Evaluation of antistatic property of resin film with adhesive

When peeling the separator of the obtained adhesive polarizing film, the surface resistance value of an adhesive was measured by the surface specific resistance measuring apparatus ["Hirest-up MCP-HT450" (brand name) by Mitsubishi Chemical Corporation], and antistatic property was performed. Evaluated. If the surface resistance value is 10 ¹¹ Ω / □ orders or less, good antistatic property can be obtained. Evaluation of antistatic property was performed immediately after the curing of the polarizing film with an adhesive was completed. Moreover, since it shows a change with time at the time of long-term preservation, after the polarizing film with a cured adhesive was stored for 6 days in oven with the temperature of 60 degreeC, and 70% of a relative humidity, the separator was carried out similarly to the above. It peeled and measured the surface resistance of an adhesive. Here, storage for 6 days at a temperature of 60 ° C. and a relative humidity of 70% can obtain an effect almost equivalent to storage for 6 months at room temperature. The results are summarized in Table 2.

(d) Fabrication and Evaluation of Optical Laminates

After peeling a separator from the polarizing film with an adhesive produced in the said (b), the adhesive surface was adhere | attached on one side of the glass substrate for liquid crystal cells ("1737" (brand name) by a Corning company), and the optical laminated body was produced. . About this optical laminated body, when it carried out the heat resistance test stored for 300 hours under the dry condition of temperature 80 degreeC, and the moisture proof heat test stored for 300 hours at the temperature of 60 degreeC and 90% of a relative humidity, and it heated at 70 degreeC The optical laminated body after a test was carried out with respect to the case where the heat shock test in which the temperature was lowered to −30 ° C. in one state and then the temperature was increased to 70 ° C. was 1 cycle (1 hour) was repeated 100 cycles. Observed visually. The results were classified according to the following criteria and summarized in Table 2.

<Evaluation Criteria for Heat, Moist Heat, and Heat Shock (Listed as "HS" in Table 2)>

(Double-circle): No external appearance changes, such as lifting, peeling, and foaming, are seen.

(Circle): Almost no external appearance change, such as lifting, peeling, and foaming, is seen.

(Triangle | delta): Appearance changes, such as lifting, peeling, and foaming, are slightly outstanding.

X: Appearance changes, such as lifting, peeling, foaming, are remarkable.

Example 6

About 100 parts of solid content of acrylic resin A2 obtained by the polymerization example 2, 0.5 part of crosslinking agents "colonate L" as solid content, 0.5 part of silane type compound "KBM-403", and 7.5 parts of ionic solid 3 are mixed, and solid content Ethyl acetate was further added so that a density | concentration might be 13%, and it was set as the adhesive composition. It evaluated like Example 1-5 using this adhesive composition, and summarized the result in Table 2.

As can be seen from Table 1 and Table 2, 7.5 parts of Examples 1 to 5 and an ionic solid in which 1 part of an ionic solid defined in the present invention was blended to form an adhesive, and 100 parts of an acrylic resin were blended to form an adhesive. Compared with Comparative Example 1 in which the ionic liquid was formulated, Example 6 constituted of the product exhibits the same antistatic properties at the initial stage of production, and the antistatic property hardly changes even after long-term use, and the heat resistance, heat and moisture resistance, and heat shock resistance. Almost satisfactory results have been obtained in the castle.

On the other hand, Comparative Example 1 in which the pressure-sensitive adhesive was formed by blending N-hexyl-4-methylpyridinium hexafluorophosphate (ionic liquid 1) as a liquid at 25 ° C shows good antistatic properties at the beginning of production, When stored for 6 days at a temperature of 60 ° C. and a relative humidity of 70%, which is an accelerated test, the surface resistance value after peeling the separator became 10 times or more compared with the initial value, and the antistatic property tended to be weakened by long-term storage. On the other hand, in the result of Example 3, Comparative Example 2, and Comparative Example 3 in which the same ionic solid 3 was blended, the amount of the ionic solid with respect to 100 parts of the acrylic resin was 0.1 part, so that it was antistatic. When the effect of imparting was insufficient and the amount was 10 parts, the durability was insufficient.

The resin film with an adhesive of this invention can suppress the charging of an optical member effectively. Moreover, even if it is stored for a long time after manufacture, it is possible to maintain the initial antistatic performance.

The resin film with this adhesive consists of an optical film, for example, and laminates it on the glass substrate of a liquid crystal cell, and provides the optical laminated body for liquid crystal displays. Since the pressure-sensitive adhesive layer absorbs and relaxes the stress caused by the dimensional change of the optical film and the glass substrate under moist heat conditions, this optical laminated body reduces local stress concentration and lifts or peels off the pressure-sensitive adhesive layer on the glass substrate. Etc. are suppressed. Moreover, since optical defects resulting from nonuniform stress distribution are prevented, whitening is suppressed. Moreover, after laminating | stacking a resin film with an adhesive once on a glass substrate, when there exists a problem, even if the resin film is peeled from a glass substrate with an adhesive, debris and cloudiness generate | occur | produce on the surface of the glass substrate after peeling. There are few cases, and it can use again as a glass substrate, and it becomes the thing excellent in rework property.

Moreover, this resin film with an adhesive can also be bonded to the surface of an optical film, and can also be set as the surface protection film which protects the surface until use. Also in this case, the outstanding antistatic effect is provided, for example, when an optical film is bonded to a liquid crystal cell through the adhesive layer on the opposite side to a surface protection film, the static electricity generate | occur | produces when peeling off the surface protection film. Can be less.

The resin film with an adhesive of this invention is provided with high antistatic property, the antistatic property is maintained for a long time, and it is excellent also in durability. The resin film with this adhesive consists of an optical film, and is used suitably for a liquid crystal display device. Moreover, the resin film with this adhesive is used suitably also as a surface protection film which protects the surface of an optical film.

Claims (6)

A pressure-sensitive adhesive resin film having a pressure-sensitive adhesive layer formed on at least one side of a resin film, wherein the pressure-sensitive adhesive layer is
(A) the following formula (I)

(In formula, R <_1> represents a hydrogen atom or a methyl group, and R <_2> represents the C1-C14 alkyl group or aralkyl group which may respectively be substituted by the C1-C10 alkoxy group.)
100 parts by weight of an acrylic resin containing a structural unit derived from (meth) acrylic acid ester represented by
(B) The resin film with an adhesive which has an organic cation and is formed from the composition containing 0.2-8 weight part of ionic compounds which are solid at room temperature. The resin film with an adhesive of Claim 1 which an ionic compound (B) exists in the ratio of 0.2-3 weight part with respect to 100 weight part of acrylic resin (A). The resin film with an adhesive of Claim 1 or 2 which is an optical film containing the film chosen from a polarizing film and retardation film. The resin film with an adhesive of Claim 1 or 2 which is a surface protection film. The resin film with an adhesive of Claim 1 with which the peeling film is adhere | attached on the surface of an adhesive layer. The resin film with an adhesive of Claim 3 is laminated | stacked on the glass substrate at the adhesive layer side, The optical laminated body characterized by the above-mentioned.