JPWO2008090813A1 - Adhesive composition and optical film with adhesive - Google Patents

Abstract

(A) Acrylic resin, (B) Crosslinker, (C) The following formula YaR1bSi (OCH3) c (OC2H5) d (OR2) e (OH) fO (4-abcdef) / 2 (Y is a mercapto group, epoxy group, An organic group having one or more selected from a (meth) acryloyloxy group, an alkenyl group, a haloalkyl group and an amino group; R1 is an unsubstituted monovalent hydrocarbon group having no one or more aliphatic unsaturated bonds; C 3 and / or 4 alkyl group or methoxypropyl group; 0.01 ≦ a ≦ 1, 0 ≦ b <2, 0 <c ≦ 2, 0 ≦ d ≦ 2, 0 <e ≦ 2, 0 ≦ A pressure-sensitive adhesive composition containing an organopolysiloxane of f ≦ 1 and 0.1 ≦ c + d + e ≦ 2.5 and 2 ≦ a + b + c + d + e + f ≦ 3). The composition of the present invention has a stable performance for a long time in a state in which it is adhered to an optical film to form an optical film with a pressure-sensitive adhesive. Also excellent.

Description

  The present invention relates to a pressure-sensitive adhesive composition and, in particular, an optical film with a pressure-sensitive adhesive that is used by being bonded to a glass cell for liquid crystal display.

  A liquid crystal cell generally used in a liquid crystal display device such as TN (Twisted Nematic) or STN (Super Twisted Nematic) has a structure in which a liquid crystal component is sandwiched between two glass substrates. And the optical film, such as a polarizing film and retardation film, is laminated | stacked on the surface of each glass substrate through the adhesive which has an acrylic resin as a main component. Therefore, the optical film is usually distributed in the form of an optical film with an adhesive having an adhesive layer formed on at least one side thereof, and in the stage of assembling the liquid crystal cell, the form in which the adhesive side is bonded to the glass substrate, Generally adopted.

  Since such an optical film with an adhesive has a large dimensional change due to expansion and contraction under heat or wet heat conditions, in the state of the optical laminate bonded to the glass substrate, foaming in the adhesive layer, There has been a problem that floating or peeling occurs between the glass substrate and the like. More recently, liquid crystal display devices are also used for in-car applications such as car navigation systems, but in-vehicle applications also require durability that does not cause foaming, floating, or peeling even under high temperature and high humidity conditions. It has become.

  In addition, when there is a deficiency when the optical film with pressure-sensitive adhesive is bonded to the glass cell for liquid crystal display, the optical film is peeled off and then re-attached. So-called reworkability is also required such that the layer is peeled off along with the optical film, the pressure-sensitive adhesive layer does not remain on the glass substrate, and no fogging occurs. Recently, with the increase in the size of optical films and the like, the area of optical films has become larger, and reworkability superior to that in the past has been demanded.

  In order to solve such a problem, various proposals have been made on pressure-sensitive adhesives mainly composed of acrylic resin. For example, Japanese Patent No. 3022993 (Patent Document 1) describes that an acrylic resin pressure-sensitive adhesive layer containing a silane compound having an epoxy group is provided on the surface of a polarizing film. Japanese Patent No. 3487940 (Patent Document 2) describes an adhesive composition in which a curing agent and a specific silicate oligomer are blended in an acrylic resin, and the adhesive composition is applied to an optical film such as a polarizing film. Application is also described.

Japanese Patent No. 3022993 (JP-A-4-223403) Japanese Patent No. 3487940 (JP-A-8-199130)

  However, when the present inventors examined, the optical film provided with the conventionally known adhesive was bonded to the glass substrate through the adhesive layer if it was about 3 months after the adhesive was applied. Although it is relatively good in terms of reworkability and adhesion durability after being applied, when it has passed for a long period of time, such as the second half of the coating or one year, the adhesive after being bonded to the glass substrate via the adhesive layer It has become clear that durability and reworkability may decrease.

  Therefore, the object of the present invention is that reworkability is good, and when bonded to a glass substrate, floating and peeling between the glass substrate and the pressure-sensitive adhesive layer, and foaming in the pressure-sensitive adhesive layer are suppressed. Even after a long period of time, such as half a year or a year after the application of the adhesive, such floating, peeling, foaming, fogging, etc. are unlikely to occur, and the durability and reworkability are excellent. It is providing the adhesive composition suitable as an adhesive of a film, and an optical film with an adhesive using the same.

As a result of diligent research to solve such problems, the inventors of the present invention required an organopolysiloxane containing a plurality of alkoxy groups having different numbers of carbon atoms in one molecule together with an organic functional group such as a mercapto group. It has been found that a pressure-sensitive adhesive as an ingredient is effective.
That is, silane compounds or organopolysiloxanes conventionally used in the field of pressure-sensitive adhesives have many methoxy groups and / or ethoxy groups in the molecule, but in this case, their hydrolyzability is sufficiently controlled. There was a problem in storage stability. In particular, since acrylic pressure-sensitive adhesive contains moisture, it has been difficult to stabilize the properties of the pressure-sensitive adhesive containing a silane compound for a long period of time. Therefore, by including in the same molecule a methoxy group or ethoxy group having high hydrolysis reactivity and an alkoxy group having 3 and / or 4 carbon atoms such as propoxy group or butoxy group having low hydrolysis reactivity, The present inventors have found an organopolysiloxane that can arbitrarily change the hydrolysis reactivity of a silane compound. Therefore, the pressure-sensitive adhesive composition in which such an organopolysiloxane is blended with an acrylic resin and a crosslinking agent has a stable performance because the amount of alkoxy groups to be hydrolyzed is kept constant over a long period of time.
In addition, the above organopolysiloxane has an effect as a silane coupling agent, and has a high affinity with glass and acrylic resin. Therefore, a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition to which it is distributed is provided. When an optical film with an adhesive is bonded to a glass substrate on the adhesive layer side, floating or peeling between the adhesive layer and the glass substrate is suppressed. Furthermore, since this organopolysiloxane also exhibits an effect as a silicone-based release agent, an optical film with an adhesive provided with an adhesive layer formed from an adhesive composition containing the organopolysiloxane is attached to a glass substrate. It has been found that the reworkability is excellent, and the present invention has been made.

Therefore, this invention provides the following adhesive composition and an optical film with an adhesive.
(1) (A) acrylic resin,
(B) Crosslinker, and (C) The following average composition formula (I)
Y _a R ¹ _b Si (OCH ₃ ) _c (OC ₂ H ₅ ) _d (OR ² ) _e (OH) _f O _{(4-abcdef) / 2}
... (I)
Wherein Y represents an organic group having at least one selected from a mercapto group, an epoxy group, a (meth) acryloyloxy group, an alkenyl group, a haloalkyl group and an amino group;
R ¹ represents an unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms which does not have at least one aliphatic unsaturated bond;
R ² represents an alkyl group having 3 and / or 4 carbon atoms or a methoxypropyl group;
a, b, c, d, e and f are 0.01 ≦ a ≦ 1, 0 ≦ b <2, 0 <c ≦ 2, 0 ≦ d ≦ 2, 0 <e ≦ 2, 0 ≦ f ≦ 1. And satisfying 0.1 ≦ c + d + e ≦ 2.5 and 2 ≦ a + b + c + d + e + f ≦ 3. )
A pressure-sensitive adhesive composition comprising an organopolysiloxane represented by the formula:
(2) The acrylic resin (A) contains an acrylic resin containing a structural unit derived from a (meth) acrylic acid-based compound having a polar functional group as a main component and derived from a (meth) acrylic acid alkyl ester. The pressure-sensitive adhesive composition according to (1).
(3) The pressure-sensitive adhesive composition according to (2), wherein the polar functional group is selected from a free carboxyl group, a hydroxyl group, an amino group, and an epoxy ring.
(4) The pressure-sensitive adhesive composition according to any one of (1) to (3), wherein the crosslinking agent (B) includes an isocyanate compound.
(5) The pressure-sensitive adhesive composition according to any one of (1) to (4), wherein in the average composition formula (I) representing the organopolysiloxane (C), Y is an organic group having a mercapto group or an epoxy group. .
(6) In the average composition formula (I) representing the organopolysiloxane (C), b is a positive number, R ¹ is a methyl group, and R ² is a propyl group or an isopropyl group (1) to (5) The pressure-sensitive adhesive composition according to any one of the above.
(7) In the said average composition formula (I) showing organopolysiloxane (C), d is a positive number, The adhesive composition in any one of (1)-(6).
(8) The pressure-sensitive adhesive composition according to any one of (1) to (7), wherein the organopolysiloxane (C) has an average degree of polymerization of 3 to 100.
(9) A pressure-sensitive adhesive optical, wherein a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition according to any one of (1) to (8) is provided on at least one surface of the optical film. the film.
(10) The optical film with an adhesive according to (9), wherein the optical film is selected from a polarizing film and a retardation film.
(11) The optical film includes a polarizing film in which a protective film made of an acetylcellulose-based resin or an amorphous cyclic polyolefin-based resin is attached to at least one surface of a polarizer. the film.

  The pressure-sensitive adhesive composition of the present invention is a state in which the performance is stable for a long time in a state in which it is adhered to an optical film and made into an optical film with a pressure-sensitive adhesive, and reworkability is good even when the size is increased, Excellent durability. Therefore, this optical film with an adhesive is suitably used for a liquid crystal display device.

  Hereinafter, embodiments of the present invention will be described in detail. The pressure-sensitive adhesive composition of the present invention essentially contains (A) an acrylic resin, (B) a crosslinking agent, and (C) an organopolysiloxane represented by the average composition formula (I). First, these components will be described.

[acrylic resin]
Specifically, the acrylic resin used in the present invention is mainly composed of a structural unit derived from (meth) acrylic acid alkyl ester, and includes a free carboxyl group, a hydroxyl group, an amino group, a heterocyclic group including an epoxy ring, and the like. A monomer having a polar functional group, preferably an acrylic resin (A-1) containing a structural unit derived from a (meth) acrylic acid compound having a polar functional group is preferred. 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. Further, the alkyl group here does not include an alkyl group (cycloalkyl group) having an alicyclic structure.

  (Meth) acrylic acid esters include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, isooctyl acrylate, lauryl acrylate, stearyl acrylate Alkyl acrylates such as benzyl acrylate, methoxyethyl acrylate, ethoxymethyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, methacrylic acid Octyl acid, isooctyl methacrylate, lauryl methacrylate, stearyl methacrylate, benzyl methacrylate, methoxyethyl methacrylate, ethoxymethyl methacrylate Can, methacrylic acid alkyl esters. These (meth) acrylic acid alkyl esters can be used alone or in combination with a plurality of different ones.

  Examples of the monomer having a polar functional group include monomers having a free carboxyl group such as acrylic acid, methacrylic acid, and β-carboxyethyl acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxy (meth) acrylate Monomers having a hydroxyl group such as propyl, 2- or 3-chloro-2-hydroxypropyl (meth) acrylate, diethylene glycol mono (meth) acrylate; acryloylmorpholine, vinylcaprolactam, N-vinyl-2-pyrrolidone, tetrahydrofurfuryl Has a heterocyclic group such as (meth) acrylate, caprolactone-modified tetrahydrofurfuryl acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, glycidyl (meth) acrylate, 2,5-dihydrofuran That monomers; N, such as N- dimethylaminoethyl (meth) acrylate, and monomers having different amino group and heterocyclic. These monomers having polar functional groups can be used alone or in combination with a plurality of different monomers.

  In 100 parts by mass of the acrylic resin (A-1) in the pressure-sensitive adhesive composition, the structural unit derived from (meth) acrylic acid alkyl ester is usually 60-99.9 parts by mass, preferably 80-99. It is contained at a ratio of 6 parts by mass, and the structural unit derived from the monomer having a polar functional group is usually contained at a ratio of 0.1 to 20 parts by mass, preferably 0.4 to 10 parts by mass. Yes.

  The acrylic resin (A-1) used in the present invention may contain a structural unit derived from a monomer other than the (meth) acrylic acid alkyl ester described above and a monomer 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, and a plurality of structural units in the molecule. Examples include structural units derived from monomers having a (meth) acryloyl group.

  The alicyclic structure is usually a cycloparaffin structure having 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, and tert-butyl acrylate. Specific examples of methacrylic acid esters having an alicyclic structure include cyclohexyl, α-ethoxyacrylate cyclohexyl, cyclohexyl phenyl acrylate, etc. Specific examples of methacrylic acid esters having an alicyclic structure include isobornyl methacrylate, cyclohexyl methacrylate, dicyclopentanyl methacrylate, methacrylic acid. Cyclododecyl, methyl cyclohexyl methacrylate, trimethyl cyclohexyl methacrylate, tert-butyl cyclohexyl methacrylate, cyclohexyl methacrylate Eniru, and the like.

  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 styrene such as styrene, chlorostyrene, bromostyrene, dibromostyrene, iodostyrene; and nitrostyrene, acetylstyrene, methoxystyrene, divinylbenzene and the like.

  Examples of vinyl-based monomers include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl laurate such as vinyl esters; vinyl halides such as vinyl chloride and vinyl bromide; vinylidene chloride and the like. Examples thereof include vinylidene halides; nitrogen-containing aromatic vinyls such as vinyl pyridine, vinyl pyrrolidone and vinyl carbazole; 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, 1,9-nonanediol di ( 2 (meth) acryloyl groups 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 And a monomer having three (meth) acryloyl groups in the molecule, such as trimethylolpropane tri (meth) acrylate.

  Monomers other than (meth) acrylic acid esters and monomers having a polar functional group can be used alone or in combination of two or more. In the acrylic resin (A-1) constituting the pressure-sensitive adhesive composition, the structural unit derived from the monomer other than the (meth) acrylic acid ester and the monomer having a polar functional group is 100 parts by mass of the acrylic resin (A-1). The content is usually 0 to 20 parts by mass, preferably 0 to 10 parts by mass.

  The active ingredient of the pressure-sensitive adhesive composition includes an acrylic resin (A-1) containing a structural unit derived from a monomer having a polar functional group, the main component being a structural unit derived from (meth) acrylic acid alkyl ester as described above. ) May be included. Furthermore, the acrylic resin (A-1) has a structural unit derived from an acrylic resin (A-2) different from the acrylic resin (A-2), specifically (meth) acrylic acid alkyl ester, and includes a polar functional group. Acrylic resin (A-) containing a structural unit derived from a monomer having a polar functional group, the main component being a structural unit derived from alkylether (meth) acrylate. 1) is preferably 60 to 100% by mass, particularly 80 to 100% by mass, based on the total acrylic resin.

  The acrylic resin (A-1) containing a structural unit derived from a monomer having a polar functional group as a main component derived from a (meth) acrylic acid alkyl ester is a standard by gel permeation chromatography (GPC). The polystyrene-equivalent weight average molecular weight (Mw) is preferably in the range of 1,000,000 to 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 is improved, and there is a possibility that floating or peeling occurs between the glass substrate and the pressure-sensitive adhesive layer. This is preferable because it tends to be low and reworkability tends to improve. In addition, when the weight average molecular weight is 2,000,000 or less, even if the dimension of the optical film attached to the pressure-sensitive adhesive layer changes, the pressure-sensitive adhesive layer changes following the dimensional change. This is preferable because there is no difference between the brightness at the peripheral edge and the brightness at the center of the liquid crystal cell, 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 usually in the range of about 2 to 10.

  Acrylic resin (a mixture of both when two or more types are combined) is a solution prepared by dissolving it in ethyl acetate to a non-volatile content of 20% by mass at 25 ° C., 20 Pa · s or less, and further 0.1 to 7 Pa. -It is preferable to show the viscosity of s. If the viscosity at this time is 20 Pa · s or less, the adhesiveness under high temperature and high humidity is improved, and the possibility of floating or peeling between the glass substrate and the pressure-sensitive adhesive layer tends to be reduced. Moreover, it is preferable because reworkability tends to be improved. The viscosity can be measured by, for example, a Brookfield viscometer.

  The acrylic resin (A-1) constituting the pressure-sensitive adhesive composition 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. A polymerization initiator is used about 0.001-5 mass parts with respect to a total of 100 mass parts of all the monomers used for manufacture of an 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 Organic peroxides such as butyl peroxyneodecanoate, tert-butyl peroxypivalate, (3,5,5-trimethylhexanoyl) peroxide; inorganic peroxides such as potassium persulfate, ammonium persulfate, hydrogen peroxide An oxide etc. can be mentioned. A redox initiator or the like using a peroxide and a reducing agent in combination can also be used as the polymerization initiator.

  As a manufacturing method of an acrylic resin (A-1), 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 under a nitrogen atmosphere, and is about 40 to 90 ° C, preferably about 60 to 80 ° C. And a method of stirring for about 3 to 10 hours. 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 melt | dissolved in the organic solvent. Here, 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; methyl ethyl ketone and methyl isobutyl ketone. Ketones can be used.

[Crosslinking agent]
In the pressure-sensitive adhesive composition of the present invention, a crosslinking agent is further added to the acrylic resin as described above. The crosslinking agent is a compound having in the molecule at least two functional groups capable of crosslinking with polar functional groups, and specific examples include isocyanate compounds, epoxy compounds, metal chelate compounds, aziridine compounds and the like. be able to.

  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 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, etc., also serve as crosslinking agents for the pressure-sensitive adhesive composition. sell. Further, two or more kinds of 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 may 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 -1,6-bis (1-aziridinecarboxamide), trimethylolpropane-tri-β-aziridinylpropionate, tetramethylolmethane-tri-β-aziridinylpropionate, and the like.

  Among these crosslinking agents, isocyanate compounds are preferably used. It is also effective to use an isocyanate compound and an aziridine compound in combination.

[Organopolysiloxane]
In the present invention, an organopolysiloxane represented by the following average composition formula (I) containing a plurality of types of alkoxy groups having different organic functional groups and carbon atoms in one molecule is further blended.
Y _a R ¹ _b Si (OCH ₃ ) _c (OC ₂ H ₅ ) _d (OR ² ) _e (OH) _f O _{(4-abcdef) / 2}
... (I)

  In the formula (I), Y is an organic group having a functional group selected from a mercapto group, an epoxy group, a (meth) acryloyloxy group, an alkenyl group, a haloalkyl group, and an amino group. Among these functional groups, a mercapto group, an epoxy group, a (meth) acryloyloxy group, and an amino group are usually bonded to a silicon atom via a linking group. Examples of the linking group include an ether bond (—O—), Examples thereof include divalent hydrocarbon groups such as an alkylene group having 1 to 12 carbon atoms and an alkylene-arylene-alkylene group which may have a hetero atom such as an imino group (—NH—), for example, methylene, ethylene, Divalent hydrocarbon group having an aromatic ring including trimethylene, hexamethylene, decamethylene, etc., including methylphenylethyl, oxygen atoms including methoxymethyl, methoxyethyl, methoxypropyl, etc. Examples thereof include a divalent aliphatic group. The alkenyl group or haloalkyl group may be bonded to the silicon atom via the above linking group, or may be directly bonded to the silicon atom.

  Specific examples of the organic group having a functional group represented by Y (hereinafter, the group represented by Y may be referred to as “organic functional group”) are as follows. As an organic group having a mercapto group, a mercaptomethyl group , 3-mercaptopropyl group, 6-mercaptohexyl group, 10-mercaptodecyl group, 2- (4-mercaptomethylphenyl) ethyl group and the like, and the organic group having an epoxy group includes glycidoxymethyl group, 3 -Glycidoxypropyl group, 5,6-epoxyhexyl group, 9,10-epoxydecyl group, 2- (3,4-epoxycyclohexyl) ethyl group, 2- (3,4-epoxy-4-methylcyclohexyl) A propyl group is exemplified, and examples of the organic group having a (meth) acryloyloxy group include an acryloyloxymethyl group, a 3-acryloyloxypropyl group, 6 Examples include acryloyloxyhexyl group, 10-acryloyloxydecyl group, methacryloyloxymethyl group, 3-methacryloyloxypropyl group, 6-methacryloyloxyhexyl group, 10-methacryloyloxydecyl group, etc. Examples of the organic group having a vinyl group, an allyl group, a 5-hexenyl group, a 9-decenyl group, a 3-vinyloxypropyl group, a p-styryl group, a cyclohexenylethyl group, and the like, and an organic group having a haloalkyl group Chloromethyl group, 3-chloropropyl group, 6-chlorohexyl group, 10-chlorodecyl group, bromomethyl group, 3-bromopropyl group and the like, and as an organic group having an amino group, an aminomethyl group, 3-amino Propyl group, 6-aminohexyl group, N-methyl-3-aminopropyl group, , N-dimethyl-3-aminopropyl group, N-phenyl-3-aminopropyl group, N- (2-aminoethyl) -3-aminopropyl group, N- (6-aminohexyl) -3-aminopropyl group And N- (vinylbenzyl) -2-aminoethyl-3-aminopropyl group and the like.

  In the organopolysiloxane used in the present invention, among the above-described organic functional groups, when it is an organic group having a mercapto group, an epoxy group or a (meth) acryloyloxy group, it is preferable because of its high reactivity. An organic group having a mercapto group or an epoxy group is more preferable because it has a high effect of increasing the adhesive force between the glass and the optical film.

In the formula (I), R ¹ is an unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms that does not have at least one aliphatic unsaturated bond, specifically, methyl Group, ethyl group, propyl group, isopropyl group, 1-methylpropyl group, butyl group, isobutyl group, tert-butyl group, hexyl group, octyl group, phenyl group, tolyl group, benzyl group, phenylethyl group, etc. , Aryl groups and aralkyl groups are exemplified, and if desired, a plurality of groups can be introduced as R ¹ . Among these, from the viewpoint of the influence of steric hindrance on the reactivity of the organic functional group described above and the cost, it is particularly preferable that R ¹ is a methyl group.

In the formula (I), R ² is an alkyl group having 3 and / or 4 carbon atoms, specifically, a propyl group, an isopropyl group, a 1-methylpropyl group, a butyl group, an isobutyl group, or tert-butyl. Can be a group. A methoxypropyl group is also included in R ² as an equivalent effect. If desired, a plurality of groups can be introduced as R ² . Among these, R ² is particularly a propyl group or an isopropyl group from the viewpoint of moderately reducing the hydrolysis reactivity and the influence of the bulkiness of the alkyl group on the content (equivalent) of the organic functional group described above. It is preferable.

  Further, in the above formula (I), a, b, c, d, e and f are 0.01 ≦ a ≦ 1, 0 ≦ b <2, 0 <c ≦ 2, 0 ≦ d ≦ 2, 0 <e. ≦ 2, 0 ≦ f ≦ 1, and 0.1 ≦ c + d + e ≦ 2.5 and 2 ≦ a + b + c + d + e + f ≦ 3.

  Here, the coefficient a is a numerical value representing the degree of substitution of the organic functional group with respect to the silicon atom, and if it is too small, the characteristic due to the reactivity of the organic functional group that should be originally not exhibited when the organopolysiloxane is used. It is necessary to have at least one organic functional group in one molecule. On the other hand, it is difficult to make the degree of substitution of the organic functional group greater than 1 from the viewpoint of synthesis and cost. The range is 01 ≦ a ≦ 1. The range is preferably 0.1 ≦ a ≦ 1, more preferably 0.1 ≦ a ≦ 0.8.

  The coefficient b is a numerical value that represents the degree of substitution of an unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms that does not have an aliphatic unsaturated bond to a silicon atom, and is 0 or close to 0. In some cases, the content of alkoxy groups is relatively increased, and the contribution rate to the hydrolysis reaction or silylation reaction is increased. In some cases, the affinity of organopolysiloxane for water is improved. On the other hand, if this value is large, depending on the type of monovalent hydrocarbon group, it imparts hydrophobicity to the organopolysiloxane (alkyl group, etc.), improves compatibility with acrylic resin (phenyl group, etc.), pressure-sensitive adhesive There are effects such as imparting flexibility and releasability to the cured product of (methyl group), but since the content of alkoxy groups is relatively reduced when b is increased, the reactivity of alkoxysilyl groups is utilized. It becomes unsuitable for an adhesive use. Therefore, the range of 0 ≦ b <2 is set according to the purpose of use. The range is preferably 0 ≦ b ≦ 1, more preferably the range 0 ≦ b ≦ 0.8.

  The coefficients c, d, and e are numerical values representing the degree of substitution of a plurality of types of alkoxy groups having different carbon atoms relative to the silicon atom, c is the degree of substitution of the methoxy group, d is the degree of substitution of the ethoxy group, and e is the carbon atom The degree of substitution of the alkoxy group of the formula 3 and / or 4 is shown. C and d representing the content of methoxy group and ethoxy group having high hydrolysis reactivity, and the content of alkoxy group having 3 and / or 4 carbon atoms such as propoxy group and butoxy group having low hydrolysis reactivity e can be appropriately set according to the purpose of use and the desired degree of hydrolysis reactivity, but a plurality of types of alkoxy groups having different hydrolysis reactivity are present in the same molecule. From the purpose, the range of 0 <c ≦ 2, 0 ≦ d ≦ 2, 0 <e ≦ 2, and c + d + e representing the total substitution degree of the alkoxy group is 0.1 ≦ c + d + e ≦ 2.5 Range. Preferably, 0 <c ≦ 1.8 and 0 <d ≦ 1.8, and at least one of c and d is 0.1 or more, 0.1 ≦ e ≦ 1.8, 0.2 ≦ c + d + e ≦ 2. 35, more preferably 0.1 ≦ c ≦ 1.8, 0.1 ≦ d ≦ 1.8, 0.1 ≦ e ≦ 1.8, 0.5 ≦ c + d + e ≦ 2.35. It is a range. An organopolysiloxane containing both a methoxy group and an ethoxy group and further containing an alkoxy group having 3 and / or 4 carbon atoms is preferable because the hydrolysis reactivity can be controlled appropriately.

  The coefficient f is a numerical value representing the degree of substitution of the hydroxyl group with respect to the silicon atom, that is, the silanol group content. This silanol group can be subjected to a silylation reaction or a condensation reaction, and imparts hydrophilicity to the organopolysiloxane. However, from the viewpoint of securing the storage stability of the organopolysiloxane, it is preferable to reduce it as much as possible. Therefore, the range is 0 ≦ f ≦ 1. The range is preferably 0 ≦ f ≦ 0.5, and more preferably 0 ≦ f ≦ 0.2.

  The total a + b + c + d + e + f of each coefficient described above is a numerical value that determines [4- (a + b + c + d + e + f)] / 2 indicating the degree of condensation of the organopolysiloxane, and is in the range of 2 ≦ a + b + c + d + e + f ≦ 3. The degree of polymerization of the organopolysiloxane can range from a dimer having 2 silicon atoms to a polymer having about several hundred silicon atoms. When the average degree of polymerization is 2, monomers in the produced organopolysiloxane If the content increases, the intended purpose of the silicone alkoxy oligomer is impaired, and if the average degree of polymerization is too large, it becomes a high-viscosity product, paste or solid, making it difficult to handle. The range is preferably 3 to 100, and more preferably 3 to 50. From this point of view, the above-mentioned a + b + c + d + e + f is also preferably in the range of 2 ≦ a + b + c + d + e + f ≦ 2.67, more preferably in the range of 2 <a + b + c + d + e + f ≦ 2.67.

  The organopolysiloxane containing an organic functional group and a plurality of types of alkoxy groups having different numbers of carbon atoms in one molecule is represented by the average composition formula (I), and a to f satisfy the above ranges. It suffices to have a linear, branched, or cyclic structure, or a combination thereof.

[Method for producing organopolysiloxane]
Organopolysiloxane containing an organic functional group and a plurality of types of alkoxy groups having different numbers of carbon atoms in one molecule can be produced by various conventionally known formulations. As a general means, for example, Can be mentioned.

(1) A method of partially hydrolyzing and polycondensing an alkoxysilane containing a plurality of types of alkoxy groups having different carbon atoms from the organic functional group described above,
(2) A method of partially cohydrolyzing and polycondensing an alkoxysilane containing an organic functional group and an alkoxysilane containing an alkoxy group having a different number of carbon atoms from that, and not containing an organic functional group,
(3) Transesterification of an organopolysiloxane containing an organic functional group and a methoxy group and / or ethoxy group obtained by the same partial hydrolysis / polycondensation operation with an alcohol having 3 and / or 4 carbon atoms A method of introducing an alkoxy group having 3 and / or 4 carbon atoms by reaction.

  In the present invention, at least one organic functional group represented by the following general formula (II) is contained on the basis of the above formula (2) from the viewpoint of freedom of structural design of organopolysiloxane and easy availability of raw materials. A mixture of an alkoxysilane and / or a partial hydrolyzate thereof and at least one alkoxy group-containing silane compound represented by the following general formula (III) and / or a partial hydrolyzate thereof and / or a condensate thereof, It is preferable to co-hydrolyze and polycondensate into an organopolysiloxane.

YR ¹ _m Si (OCH ₃ ) _n (OC ₂ H ₅ ) _3-mn (II)
R ¹ _p Si (OCH ₃ ) _q (OC ₂ H ₅ ) _r (OR ² ) _4-pqr (III)

Here, Y, R ¹ and R ² each represent the same meaning as in the formula (I), m is an integer of 0 to 2, n is an integer of 0 to 3, but m + n is 3 or less. And p is an integer of 0 to 2, q is an integer of 0 to 4, and r is an integer of 0 to 4, but p + q + r is 4 or less, provided that n in the general formula (II) and / or the general formula At least one component having an OCH ₃ group is used as q in (III), and at least one component having an OR ² group is used as the alkoxy group-containing silane compound of the general formula (III).

As a modification method, an organopolysiloxane can be obtained by the following method. That is, first, an organic functional group-containing alkoxysilane represented by the general formula (II) and at least one alkoxy group-containing silane compound represented by the general formula (III) are partially cohydrolyzed in advance. Next, this partial cohydrolyzed product is represented by the above general formula (III) and is different from the alkoxy group-containing silane compound and / or partial hydrolyzate thereof and / or different from that used in the partial cohydrolysis. The condensate is mixed, partially hydrolyzed and polycondensed to obtain organopolysiloxane. Also in this method, at least one component having an OR ² group is used as the alkoxy group-containing silane compound represented by the general formula (III).

  Specific examples of the organic functional group-containing alkoxysilane represented by the general formula (II) include, as organic functional groups, mercaptomethyl group, 3-mercaptopropyl group, 6-mercaptohexyl group, 10-mercaptodecyl group, 2- (4-mercaptomethylphenyl) ethyl group, glycidoxymethyl group, 3-glycidoxypropyl group, 5,6-epoxyhexyl group, 9,10-epoxydecyl group, 2- (3,4-epoxy (Cyclohexyl) ethyl group, 2- (3,4-epoxy-4-methylcyclohexyl) propyl group, acryloyloxymethyl group, 3-acryloyloxypropyl group, 6-acryloyloxyhexyl group, 10-acryloyloxydecyl Group, methacryloxymethyl group, 3-methacryloyloxypropyl group, 6-methacryloyloxyhexyl 10-methacryloyloxydecyl group, vinyl group, allyl group, 5-hexenyl group, 9-decenyl group, 3-vinyloxypropyl group, p-styryl group, cyclohexenylethyl group, chloromethyl group, 3-chloropropyl Group, 6-chlorohexyl group, 10-chlorodecyl group, bromomethyl group, 3-bromopropyl group, aminomethyl group, 3-aminopropyl group, 6-aminopropyl group, N-methyl-3-aminopropyl group, N, N-dimethyl-3-aminopropyl group, N-phenyl-3-aminopropyl group, N- (2-aminoethyl) -3-aminopropyl group, N- (6-aminohexyl) -3-aminopropyl group, Trimethoxysilane compounds having N- (vinylbenzyl) -2-aminoethyl-3-aminopropyl group, etc., triethoxysilane Compound, methyldimethoxysilane compound, methyldiethoxysilane compound, ethyldimethoxysilane compound, ethyldiethoxysilane compound, propyldimethoxysilane compound, propyldiethoxysilane compound, dimethylmethoxysilane compound, dimethylethoxysilane compound, ethoxydimethoxysilane compound And methoxydiethoxysilane compounds.

  Next, specific examples of the alkoxy group-containing silane compound represented by the general formula (III) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, p = 0 alkoxysilane, Tetrabutoxysilane, tetraisobutoxysilane, etc. are p = 1 alkoxysilanes such as methyl, ethyl, propyl, isopropyl, 1-methylpropyl, butyl, isobutyl, tert-butyl, hexyl , Octyl group, phenyl group, tolyl group, benzyl group, phenylethyl group, etc., trimethoxysilane, triethoxysilane, tripropoxysilane, triisopropoxysilane, tributoxysilane, triisobutoxysilane, etc., p = 2 As an alkoxysilane of Dimethoxysilane, dimethyl diethoxy silane, dimethyl dipropoxy silane, dimethyl dibutoxy silane, methyl ethyl dimethoxy silane, diphenyl dimethoxy silane, diphenyl diethoxy silane, etc., are respectively illustrated.

From the viewpoint of easy availability of raw materials and cost, m in the general formula (II) is 0 and n is 3 or 0, that is, trimethoxysilane, triethoxysilane and / or organic functional group-containing ones. Or a partial hydrolyzate thereof, wherein R ¹ in the above general formula (III) is a methyl group and p is 1 and / or 0, that is, methyltrialkoxysilane, tetraalkoxysilane and / or a partial hydrolyzate thereof. And / or a condensate thereof, and further, an alkoxy group-containing silane compound in which q and r in the general formula (III) are both 0 and / or a partial hydrolyzate thereof and / or a condensation thereof. More preferably, the product is an essential component.

  In particular, as the organofunctional group-containing alkoxysilane represented by the general formula (II), 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxy At least one selected from propyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, and the above general formula (III) As the alkoxy group-containing silane compound represented by the formula, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, methyltributoxysilane, methyltriisobutoxysilane, tetramethoxysilane, At least one selected from laethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, tetraisobutoxysilane (provided that at least one silane compound having a propoxy group, isopropoxy group, butoxy group or isobutoxy group is used) It is particularly preferable to use an essential component).

  These organic functional group-containing alkoxysilanes and / or partial hydrolysates thereof, and alkoxy group-containing silane compounds and / or partial hydrolysates thereof and / or condensates thereof can each be used in combination of a plurality of types. When using 2 or more types of organic functional group containing alkoxysilane and / or its partial hydrolyzate represented by the said general formula (II), it is preferable to have the same organic functional group. Further, in order to arbitrarily design the ratio of methoxy group, ethoxy group, alkoxy group having 3 and / or 4 carbon atoms in organopolysiloxane, an alkoxy group-containing silane compound represented by the above general formula (III) And as the partial hydrolyzate and / or condensate thereof, it is preferable to use two or more different types of alkoxy groups in combination.

  The organic functional group-containing alkoxysilane represented by the general formula (II) and / or a partial hydrolyzate thereof, the alkoxy group-containing silane compound represented by the general formula (III) and / or a partial hydrolyzate thereof, and Although the blending ratio with the condensate thereof is not particularly limited, if the former blending ratio is too small, the characteristics based on the reactivity of the organic functional group that should be originally used when the obtained organopolysiloxane is not sufficiently exhibited. Since it is necessary to have at least one organic functional group in one molecule, the molar ratio of both components is preferably in the range of 1:99 to 99: 1, and more preferably 10: More preferably, it is in the range of 90-80: 20.

  Further, the blending order and mixing method of these various raw materials, and the method of performing partial cohydrolysis and polycondensation are not particularly limited, and are based on conventionally known methods, for example, the above-described organic functional group-containing alkoxysilane and / or its In a mixture of the partial hydrolyzate and the alkoxy group-containing silane compound and / or the partial hydrolyzate and / or the condensate thereof, water is added in the presence of a hydrolysis / condensation reaction catalyst to perform partial cohydrolysis and It can be obtained by conducting a polycondensation reaction, and at this time, an appropriate organic solvent can be used as necessary.

  As the hydrolysis / condensation reaction catalyst in this reaction, various conventionally known catalysts can be used. Specific examples include organic acids such as acetic acid, trifluoroacetic acid, butyric acid, oxalic acid, maleic acid, citric acid, methanesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, etc. Inorganic acids, basic compounds such as sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate, sodium acetate, potassium acetate, ammonia, ammonium hydroxide, triethylamine, and fluorine-containing compounds such as potassium fluoride and ammonium fluoride Examples thereof include organometallic compounds such as compounds, tetraisopropyl titanate, tetrabutyl titanate, dioctyl tin dilaurate, and aluminum chelates. The above catalyst may be used alone or in combination of two or more kinds, but the amount of the catalyst used is 0.0001 to 10 mol% with respect to the number of moles of Si atoms present in the whole raw material. Preferably, it is more preferable to set it as the range of 0.001-3 mol%.

  As described above, the degree of polymerization of the organopolysiloxane may be from a dimer having 2 silicon atoms to a polymer having about several hundred silicon atoms, but the average degree of polymerization depends on the amount of water used for partial hydrolysis and polycondensation. Determined. If water is added excessively, the alkoxy group is hydrolyzed to form a resin having a lot of branched structures, and the desired silicone alkoxy oligomer cannot be obtained. Therefore, the amount of water used for hydrolysis is strictly determined. There is a need. For example, when the alkoxysilane raw material used is a monomer having one silicon atom, in order to prepare an organopolysiloxane having an average polymerization degree of Z, (Z-1) What is necessary is just to perform partial hydrolysis and polycondensation using water.

  At this time, an organic solvent such as alcohols, ethers, esters, and ketones may be used as necessary. Specific examples of these organic solvents include alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol and propylene glycol monomethyl ether, ethers such as diethyl ether and dipropyl ether, methyl acetate, ethyl acetate and acetoacetic acid. Examples include esters such as ethyl, and ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. Moreover, you may use together nonpolar solvents, such as hexane, toluene, and xylene, with the above polar solvents. In particular, it is preferable to use alcohols such as methanol, ethanol and isopropyl alcohol.

  The amount of the organic solvent used may be in the range of 0 to 1000 parts by mass with respect to 100 parts by mass in total of the alkoxysilane and / or its partial hydrolyzate and / or its condensate as raw materials. If the amount is too small, the reaction system at the start of hydrolysis may not be uniform, and if it is too much, not only the addition effect is seen, but also the pot yield is lowered and economically disadvantageous. The range is preferably 500 parts by mass, and more preferably 20 to 200 parts by mass.

  As an actual operation in the partial (co) hydrolysis and polycondensation reaction, a predetermined amount of water or a mixture of water / organic solvent is dropped into a mixed system composed of an alkoxysilane raw material, a catalyst and an organic solvent, or alkoxysilane. It is preferable to drop a predetermined amount of a mixed solution of water / catalyst or a mixed solution of water / catalyst / organic solvent into a mixed system composed of a raw material and an organic solvent. In this case, an alkoxysilane raw material having a methoxy group or an ethoxy group having a high hydrolysis reactivity and an alkoxysilane raw material having an alkoxy group having 3 and / or 4 carbon atoms such as a propoxy group or a butoxy group having a low hydrolysis reactivity It is also possible to carry out the polycondensation reaction after separately hydrolyzing and separately mixing the two components and optionally further carrying out partial cohydrolysis. Each reaction may be carried out in a temperature range of 0 to 150 ° C., but in general, the reaction proceeds slowly at a temperature lower than room temperature, which is not practical, and even when the temperature is too high, a mercapto group, an epoxy group It is preferable that the temperature be in the range of 20 to 130 ° C., since adverse effects on the organic functional group such as thermal decomposition such as thermal polymerization and thermal polymerization of acryloyloxy groups occur. After the reaction, the removal of the used catalyst by neutralization, adsorption, filtration, etc., and the purification process by distilling off the used organic solvent and by-produced alcohol and low-boiling substances, etc. are performed to obtain the desired organopolysiloxane. be able to. The organopolysiloxane thus obtained is often a liquid.

[Adhesive composition]
In the present invention, the acrylic resin as described above is blended with the crosslinking agent and organopolysiloxane as described above to obtain a pressure-sensitive adhesive composition. The crosslinking agent is usually about 0.1 to 10 parts by mass, preferably 0.1 to 7 parts by mass with respect to 100 parts by mass of the acrylic resin constituting the pressure-sensitive adhesive composition (when two or more types are used, the total amount) More preferably, it is blended at a ratio of about 0.2 to 3 parts by mass. The amount of the crosslinking agent with respect to 100 parts by mass of the acrylic resin is preferably 0.1 parts by mass or more because the durability of the pressure-sensitive adhesive layer tends to be improved. Moreover, when the amount is 10 parts by mass or less, so-called white spots are not noticeable when the optical film with an adhesive is applied to a liquid crystal display device.

  The organopolysiloxane is usually about 0.0001 to 10 parts by mass, preferably 0.01 to 5 parts per 100 parts by mass of acrylic resin constituting the pressure-sensitive adhesive composition (when two or more types are used, the total amount). About 1 part by mass, more preferably about 1 to 1 part by mass is used. It is preferable that the amount of the organopolysiloxane with respect to 100 parts by mass of the acrylic resin is 0.0001 parts by mass or more because adhesion between the pressure-sensitive adhesive layer and the glass substrate is improved. Moreover, when the amount is 10 parts by mass or less, it is preferable because organopolysiloxane tends to be suppressed from bleeding out from the pressure-sensitive adhesive layer.

  The pressure-sensitive adhesive composition described above may further contain a crosslinking catalyst, a weather stabilizer, a tackifier, a plasticizer, a softener, a dye, a pigment, an inorganic filler, and the like. Among them, when a crosslinking catalyst is blended with a crosslinking agent in the pressure-sensitive adhesive, the pressure-sensitive adhesive layer can be prepared by aging in a short time, and when the resulting optical film with pressure-sensitive adhesive is bonded to a liquid crystal cell glass, the pressure-sensitive adhesive layer Occurrence of floating or peeling between the optical film and the optical film 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.

  The pressure-sensitive adhesive composition is usually prepared in a state where the above components are dissolved in an organic solvent. The organic solvent used for this purpose is not limited as long as it dissolves each of the above-mentioned components. For example, aromatic hydrocarbons such as toluene and xylene, esters such as ethyl acetate and butyl acetate, acetone, methyl ethyl ketone, and methyl isobutyl. Ketones such as ketones are used.

[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 film and a retardation film.

  A polarizing film is an optical film having a function of emitting polarized light with respect to incident light such as natural light. The polarizing film absorbs linearly polarized light having a vibration surface in a certain direction and reflects linearly polarized film having a property of transmitting linearly polarized light having a vibration surface orthogonal to the vibration surface, and reflects linearly polarized light having a vibration 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 film, an elliptically polarizing film in which a polarizing film and a retardation film described later are laminated. As a suitable specific example of a polarizing film, particularly a linear polarizing film (sometimes called a polarizer or a polarizer film), a dichroic dye such as iodine or a dichroic dye is 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 them, 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 any of them.

  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 Shin Nippon Oil Co., Ltd., 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 product name “new VAC film” by Sumitomo Chemical Co., Ltd. A biaxially oriented film.

  Furthermore, those in which a protective film is attached to these optical films can also be used as the optical film. As the protective film, a transparent resin film is used. As the transparent resin, for example, an acetylcellulose-based resin typified by triacetylcellulose or diacetylcellulose, or an amorphous cyclic polyolefin-based resin typified by norbornene-based resin is used. And methacrylic resin represented by polymethyl methacrylate, polyester resin, 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 acetylcellulose-based resin film such as a triacetylcellulose film or an amorphous cyclic polyolefin-based resin film such as a norbornene-based resin film is preferably used. Commercially available amorphous cyclic polyolefin resin films include, for example, “Arton Film” sold by JSR Corporation, “Zeonor Film” sold by Optes Corporation, etc. (all trade names) There is. Moreover, the above-mentioned retardation film can also be directly used as a protective film.

  Among the optical films described above, the linearly polarizing film 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. Moreover, although the above-mentioned elliptically polarizing film is a laminate of a linearly polarizing film and a retardation film, the linearly polarizing film is also in a state where a protective film is attached to one side or both sides of the polarizer film. There are many. When the pressure-sensitive adhesive layer according to the present invention is formed on such an elliptically polarizing film, the pressure-sensitive adhesive layer is usually formed on the retardation film side. Preferred examples of the optical film provided with the pressure-sensitive adhesive layer according to the present invention include a polarizing film in which a protective film made of an acetylcellulose-based resin or an amorphous cyclic polyolefin-based resin is attached to at least one surface of a polarizer. Things can be mentioned.

  An optical film with an adhesive is, for example, a method of applying the adhesive composition described above on a release film to form an adhesive layer, and further laminating the optical film on the obtained adhesive layer, optical A pressure-sensitive adhesive composition is formed on a film to form a pressure-sensitive adhesive layer, and a release film is bonded to the surface of the pressure-sensitive adhesive to protect it, thereby producing an optical film with a pressure-sensitive adhesive. Here, as the release film, for example, a film made of various resins such as polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyarylate and the like is used as a base material, and the bonding surface with the adhesive layer of the base material is treated with silicone. The thing etc. which the mold release process was given are mentioned. The pressure-sensitive adhesive layer can be formed by a method in which the pressure-sensitive adhesive composition that is an organic solvent solution as described above is applied onto the release film or the optical film and dried. Various known coaters can be used for coating. After coating, it is usually aged for about 3 to 14 days at a temperature of about 0 to 50 ° C. and a relative humidity of about 20 to 80%. Preferred conditions for aging are a temperature of about 20-30 ° C., a relative humidity of about 55-75%, and a period of about 5-7 days. By this aging, the crosslinking reaction of the adhesive proceeds. When the pressure-sensitive adhesive layer is provided on the release film, the aging may be performed in a state where the pressure-sensitive adhesive layer is formed on the release film, or the pressure-sensitive adhesive layer on the release film is laminated on the optical film. It may be done later.

  Although the thickness of an adhesive layer is not specifically limited, Usually, it is preferable that it is 30 micrometers or less, and it is preferable that it is 10 micrometers or more. 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. Moreover, it is preferable because reworkability tends to be improved, and if the thickness is 10 μm or more, the adhesive layer follows the change in dimensions even if the dimensions of the optical film bonded thereto change. Therefore, there is no difference between the brightness at the peripheral edge of the liquid crystal cell and the brightness at the center, which is preferable because white spots and color unevenness tend to be suppressed.

  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. 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 film) is laminated on the glass substrate on the front side (viewing side) of the liquid crystal cell, and another optical film with adhesive (lower polarizing film) on the glass substrate on the rear side of the liquid crystal cell. The optical layered body formed by laminating can be used as a liquid crystal display device. Examples of the material for the glass substrate include soda lime glass, low alkali glass, non-alkali glass, and the like. 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.

  The optical film with the 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 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.

  The liquid crystal display device formed by bonding the optical film with an adhesive of the present invention to at least one surface of the liquid crystal cell glass is, for example, a personal computer including a notebook type, a desktop type, a PDA (Personal Digital Assistance), etc. It can be used for liquid crystal displays, televisions, in-vehicle displays, electronic dictionaries, digital cameras, 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, the parts and% representing the amount used or the content are based on mass unless otherwise specified.

In the following examples, the nonvolatile content of the acrylic resin 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 mass, and the residual nonvolatile mass after drying at 115 ° C. for 2 hours in an explosion-proof oven was expressed as a percentage of the mass of the solution first measured. It is. The weight average molecular weight of the acrylic resin was determined by placing two “TSK gel GMH _HR- H (S)” manufactured by Tosoh Corporation as a column in series in a GPC apparatus, and using tetrahydrofuran as an eluent. This is a value measured in terms of standard polystyrene under conditions of a concentration of 5 mg / ml, a sample introduction amount of 100 μl, a temperature of 40 ° C., and a flow rate of 1 ml / min.

  Moreover, the analysis of the organopolysiloxane obtained in each example was performed by the method shown below.

(1) Average molecular weight and average degree of polymerization of organopolysiloxane By gel permeation chromatography (GPC) analysis, the weight average molecular weight was determined based on a calibration curve prepared from a polystyrene standard sample, and the average degree of polymerization was further calculated therefrom.

(2) Alkoxy group content in organopolysiloxane Alkali group content was determined by alkali cracking-GC (GC) analysis method (see Silicone Handbook, pages 792-793 (1990, published by Nikkan Kogyo Shimbun)). Measurements were made to determine the coefficients c, d and e in the average composition formula (I).

(3) Structural analysis of organopolysiloxane Conducted by silicon nuclear magnetic resonance spectrum ( ²⁹ Si-NMR) analysis and proton nuclear magnetic resonance spectrum ( ¹ H-NMR) analysis. From the measurement results, the coefficient a in the average composition formula (I) , B and f were determined.

(4) Mercapto group equivalent of organopolysiloxane Acetic acid / potassium iodide / potassium iodate added-sodium thiosulfate solution titration method [Analytical Chemistry Handbook, 2nd revised edition, pages 432-433 (1976, issued by Maruzen Co., Ltd.)] ] And was measured according to.

(5) Viscosity of organopolysiloxane The viscosity at 25 ° C. was measured by a method according to JIS K 8803.

First, the example which manufactured the acrylic resin used by this invention is shown.
[Polymerization Example 1]
A reactor equipped with a cooling pipe, a nitrogen introducing pipe, a thermometer and a stirrer was charged with a mixed solution of 81.8 parts of ethyl acetate, 98.9 parts of butyl acrylate and 1.1 parts of acrylic acid, and the apparatus was equipped with nitrogen gas The internal temperature was raised to 55 ° C. while substituting the inside air to make it oxygen-free. 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, while adding ethyl acetate continuously to the reactor at an addition rate of 17.3 parts / hr so that the concentration of the acrylic resin excluding the monomer was 35%, the internal temperature was 54 to 56 ° C. The temperature was kept 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 polystyrene-reduced weight average molecular weight Mw of 1,670,000 and Mw / Mn of 4.4 by GPC. This is designated as acrylic resin A1.

[Polymerization Example 2]
An acrylic resin solution was obtained in the same manner as in Polymerization Example 1 except that the monomer composition was changed to 98.8 parts of butyl acrylate, 1.0 part of 2-hydroxyethyl acrylate, and 0.2 part of acrylic acid. The obtained acrylic resin had a polystyrene-reduced weight average molecular weight Mw of 1,470,000 and Mw / Mn of 4.2 by GPC. This is designated as acrylic resin A2.

Next, an example in which an organopolysiloxane used in the present invention is synthesized will be shown.
[Organopolysiloxane Synthesis Example 1]
In a 1 L flask equipped with a stirrer, cooling condenser, thermometer and dropping funnel, 62.5 g (0.3 mol) of tetraethoxysilane, 52.9 g (0.2 mol) of tetrapropoxysilane, 62.5 g of ethanol And 52.9 g of isopropyl alcohol were added and heated in an oil bath with stirring and mixing to raise the internal temperature to 50 ° C. While stirring the flask, a mixed solution of 7.2 g of 0.1N hydrochloric acid aqueous solution (water: 0.4 mol, hydrogen chloride: 7.2 × 10 ⁻⁴ mol) and ethanol 7.2 g was added dropwise over 10 minutes. The mixture was further heated and aged for 2 hours under reflux to obtain a prehydrolysis reaction liquid C11.

Separately, in a mixed solution of 39.3 g (0.2 mol) of 3-mercaptopropyltrimethoxysilane, 40.9 g (0.3 mol) of methyltrimethoxysilane and 80.2 g of methanol, an internal temperature of 20 to A mixed solution of 7.2 g of 0.1N hydrochloric acid (water: 0.4 mol, hydrogen chloride: 7.2 × 10 ⁻⁴ mol) and 7.2 g of methanol was added dropwise at 30 ° C. over 10 minutes. A pre-hydrolysis reaction liquid C12 was obtained by aging at a temperature of 20 to 30 ° C. for 30 minutes.

After adding the prehydrolysis reaction liquid C12 to the prehydrolysis reaction liquid C11 and stirring and mixing, 1.8 g of 0.1N hydrochloric acid aqueous solution (water: 0.1 mol, chloride) at an internal temperature of 20-30 ° C. Hydrogen: 1.8 × 10 ⁻⁴ mol) and 1.8 g of ethanol were added, and the mixture was heated in an oil bath and aged for 2 hours under reflux. Next, 9.4 g of a 1% ethanol solution of potassium fluoride (KF: 1.62 × 10 ⁻³ mol) was added, and further aged for 2 hours under reflux to carry out partial cohydrolysis and polycondensation reaction. .
Subsequently, the alcohol component was distilled off while raising the internal temperature to 80 ° C. under normal pressure, and the internal temperature was raised to 100 ° C. under a reduced pressure of 30 Torr (about 4 kPa) to reduce the residual alcohol component and the low boiling point. After distilling off the components, filtration was performed to obtain a colorless and transparent liquid organopolysiloxane C1 (yield: 127.5 g, yield: 92%).

This organopolysiloxane C1 has the above-mentioned average composition formula (I), wherein Y is a 3-mercaptopropyl group, R ¹ is a methyl group, and R ² is a propyl group, and the molar ratio of each raw material (other than the organic solvent) used. The weight average molecular weight, average polymerization degree, average composition formula corresponding to the formula (I), mercapto group equivalent, and viscosity were as follows.

Raw material molar ratio, average composition formula and physical property value raw material molar ratio of “organopolysiloxane C1”:
HS (CH ₂ ) ₃ Si (OCH ₃ ) ₃ / CH ₃ Si (OCH ₃ ) ₃ /
Si (OC ₂ H ₅ ) ₄ / Si (OC ₃ H ₇ ) ₄ = 0.2 / 0.3 / 0.3 / 0.2
Catalyst: HCl / KF / water = 0.00162 / 0.00162 / 0.9
Weight average molecular weight: 1,400
Average degree of polymerization: 10.1
Average composition formula:
[HS (CH ₂ ) ₃ ] _0.2 (CH ₃ ) _0.3 Si (OCH ₃ ) _0.52 (OC ₂ H ₅ ) _0.71
(OC ₃ H ₇ ) _0.49 O _0.89
Mercapto group equivalent: measured value 696 g / mol, theoretical value 693 g / mol viscosity: 21.0 mm ² / s

[Organopolysiloxane Synthesis Example 2]
In a 1 L flask equipped with a stirrer, cooling condenser, thermometer and dropping funnel, 41.7 g (0.2 mol) of tetraethoxysilane, 79.3 g (0.3 mol) of tetrapropoxysilane, and 41.7 g of ethanol. And 79.3 g of isopropyl alcohol were added and heated in an oil bath with stirring and mixing to raise the internal temperature to 50 ° C. While stirring the flask, a mixed solution of 7.2 g of 0.5N hydrochloric acid aqueous solution (water: 0.4 mol, hydrogen chloride: 3.6 × 10 ⁻³ mol) and ethanol 7.2 g was added dropwise over 10 minutes. The mixture was further heated and aged for 2 hours under reflux to obtain a preliminary hydrolysis reaction liquid C21.

Separately, in a mixed solution of 47.7 g (0.2 mol) of 3-mercaptopropyltriethoxysilane, 40.9 g (0.3 mol) of methyltrimethoxysilane, 40.9 g of methanol and 47.7 g of ethanol. A mixed solution of 7.2 g of 0.5N hydrochloric acid (water: 0.4 mol, hydrogen chloride: 3.6 × 10 ⁻³ mol) and 7.2 g of methanol at an internal temperature of 20-30 ° C. over 10 minutes. The solution was added dropwise and further aged at an internal temperature of 20 to 30 ° C. for 30 minutes to obtain a preliminary hydrolysis reaction liquid C22.

Preliminary hydrolysis reaction liquid C22 is added to the above preliminary hydrolysis reaction liquid C21 and mixed with stirring. Then, 1.8 g of 0.5N hydrochloric acid aqueous solution (water: 0.1 mol, chloride) at an internal temperature of 20-30 ° C. Hydrogen: 9 × 10 ⁻⁴ mol) and 1.8 g of ethanol were added, and then the mixture was heated in an oil bath and aged for 2 hours under reflux. Next, 9.4 g of a 5% ethanol solution of potassium fluoride (KF: 8.1 × 10 ⁻³ mol) was added, and the mixture was further aged for 2 hours under reflux to perform partial cohydrolysis and polycondensation reaction. .
Subsequently, the alcohol component was distilled off while raising the internal temperature to 80 ° C. under normal pressure, and the internal temperature was raised to 100 ° C. under a reduced pressure of 30 Torr (about 4 kPa) to reduce the residual alcohol component and the low boiling point. After the components were distilled off, filtration was performed to obtain colorless and transparent liquid organopolysiloxane C2 (yield: 136.7 g, yield: 94%).

This organopolysiloxane C2 has a molar ratio of each raw material (other than an organic solvent) used in which Y is a 3-mercaptopropyl group, R ¹ is a methyl group, and R ² is a propyl group in the average composition formula (I). The weight average molecular weight, average polymerization degree, average composition formula corresponding to the formula (I), mercapto group equivalent, and viscosity were as follows.

Raw material molar ratio, average composition formula and physical property value raw material molar ratio of “organopolysiloxane C2”:
HS (CH ₂ ) ₃ Si (OC ₂ H ₅ ) ₃ / CH ₃ Si (OCH ₃ ) ₃ /
Si (OC ₂ H ₅ ) ₄ / Si (OC ₃ H ₇ ) ₄ = 0.2 / 0.3 / 0.2 / 0.3
Catalyst: HCl / KF / water = 0.0081 / 0.0081 / 0.9
Weight average molecular weight: 1,460
Average degree of polymerization: 10.0
Average composition formula:
[HS (CH ₂ ) ₃ ] _0.2 (CH ₃ ) _0.3 Si (OCH ₃ ) _0.3 (OC ₂ H ₅ ) _0.63
(OC ₃ H ₇ ) _0.78 O _0.895
Mercapto group equivalent: measured value 741 g / mole, theoretical value 728 g / mole viscosity: 22.5 mm ² / s

[Organopolysiloxane Synthesis Example 3: Comparison]
In a 1 L flask equipped with a stirrer, cooling condenser, thermometer and dropping funnel, 39.3 g (0.2 mol) of 3-mercaptopropyltrimethoxysilane and 40.9 g (0.3 mol) of methyltrimethoxysilane , 104.2 g (0.5 mol) of tetraethoxysilane, 80.2 g of methanol and 104.2 g of ethanol were added, and the inside of the flask was stirred at an internal temperature of 20-30 ° C. : 0.9 mol, hydrogen chloride: 1.62 × 10 ⁻³ mol) and 16.2 g of methanol were added dropwise over 30 minutes, and the mixture was further heated and aged for 2 hours under reflux.

Next, 9.4 g of a 1% ethanol solution of potassium fluoride (KF: 1.62 × 10 ⁻³ mol) was added, and further aged for 2 hours under reflux to carry out partial cohydrolysis and polycondensation reaction. . Subsequently, the alcohol component was distilled off while raising the internal temperature to 80 ° C. under normal pressure, and the internal temperature was raised to 100 ° C. under a reduced pressure of 30 Torr (about 4 kPa) to reduce the residual alcohol component and the low boiling point. After distilling off the components, filtration was carried out to obtain colorless and transparent liquid organopolysiloxane C3 (yield: 117.0 g, yield: 90%).

This organopolysiloxane C3 is composed of Y (3-mercaptopropyl group), R ¹ (methyl group), no OR ² (e = 0) in the average composition formula (I), and each of the raw materials used (other than the organic solvent). The molar ratio, the weight average molecular weight determined from the above analysis results, the average degree of polymerization, the average composition formula corresponding to the formula (I), the mercapto group equivalent, and the viscosity were as follows.

Raw material molar ratio, average composition formula and physical property value raw material molar ratio of “organopolysiloxane C3”:
HS (CH ₂ ) ₃ Si (OCH ₃ ) ₃ / CH ₃ Si (OCH ₃ ) ₃ / Si (OC ₂ H ₅ ) ₄
= 0.2 / 0.3 / 0.5
Catalyst: HCl / KF / water = 0.00162 / 0.00162 / 0.9
Weight average molecular weight: 1,380
Average degree of polymerization: 10.6
Average composition formula:
[HS (CH ₂ ) ₃ ] _0.2 (CH ₃ ) _0.3 Si (OCH ₃ ) _0.61 (OC ₂ H ₅ ) _1.08 O _0.905
Mercapto group equivalent: measured value 638 g / mol, theoretical value 651 g / mol viscosity: 20.5 mm ² / s

[Organopolysiloxane Synthesis Example 4: Comparison]
A 1 L flask equipped with a stirrer, cooling condenser, thermometer and dropping funnel was charged with 132.2 g (0.5 mol) of tetrapropoxysilane and 132.2 g of isopropyl alcohol and heated in an oil bath while stirring and mixing. The internal temperature was raised to 50 ° C. While stirring the flask, a mixed solution of 7.2 g of 1N aqueous hydrochloric acid (water: 0.4 mol, hydrogen chloride: 7.2 × 10 ⁻³ mol) and 7.2 g of isopropyl alcohol was added dropwise over 10 minutes. The mixture was further heated and aged for 2 hours under reflux to obtain a prehydrolysis reaction liquid C41.

Apart from this, 4-mercaptopropyltriethoxysilane 47.7 g (0.2 mol), methyltriethoxysilane 17.8 g (0.1 mol), methyltriisopropoxysilane 44.1 g (0.2 mol) In a mixed solution of 65.5 g of ethanol and 44.1 g of isopropyl alcohol, 7.2 g of 1N hydrochloric acid aqueous solution at an internal temperature of 20 to 30 ° C. (water: 0.4 mol, hydrogen chloride: 7.2 × 10 ⁻³ mol) A mixed solution of isopropyl alcohol and 7.2 g was added dropwise over 10 minutes, and further aged at an internal temperature of 20 to 30 ° C. for 30 minutes to obtain a prehydrolysis reaction liquid C42.

Preliminary hydrolysis reaction liquid C42 is added to the above preliminary hydrolysis reaction liquid C41 and mixed with stirring. Then, 1.8 g of 1N hydrochloric acid aqueous solution (water: 0.1 mol, hydrogen chloride: 1.8 × 10 ⁻³ mol) and 1.8 g of isopropyl alcohol were added, and then the mixture was heated in an oil bath and aged for 2 hours under reflux. Next, 0.94 g of potassium fluoride (KF: 1.62 × 10 ⁻² mol) was added, and the mixture was further aged for 2 hours under reflux to perform partial cohydrolysis and polycondensation reaction.
Subsequently, the alcohol component was distilled off while raising the internal temperature to 80 ° C. under normal pressure, and the internal temperature was raised to 100 ° C. under a reduced pressure of 30 Torr (about 4 kPa) to reduce the residual alcohol component and the low boiling point. After distilling off the components, filtration was performed to obtain colorless and transparent liquid organopolysiloxane C4 (yield: 140.8 g, yield: 90%).

This organopolysiloxane C4 has the above average composition formula (I), wherein Y is a 3-mercaptopropyl group, R ¹ is a methyl group, OCH ₃ is not present (c = 0), and R ² is a propyl group and an isopropyl group. The molar ratio of each raw material used (other than the organic solvent), the weight average molecular weight determined from the above analysis results, the average degree of polymerization, the average composition formula corresponding to the formula (I), the mercapto group equivalent, and the viscosity are as follows: It was as follows.

Raw material molar ratio, average composition formula and physical property value raw material molar ratio of “organopolysiloxane C4”:
HS (CH ₂ ) ₃ Si (OC ₂ H ₅ ) ₃ / CH ₃ Si (OC ₂ H ₅ ) ₃ /
CH ₃ Si (OC ₃ H ₇ ) ₃ / Si (OC ₃ H ₇ ) ₄ = 0.2 / 0.1 / 0.2 / 0.5
Catalyst: HCl / KF / water = 0.0162 / 0.0162 / 0.9
Weight average molecular weight: 1,620
Average degree of polymerization: 10.3
Average composition formula:
[HS (CH ₂ ) ₃ ] _0.2 (CH ₃ ) _0.3 Si (OC ₂ H ₅ ) _0.39 (OC ₃ H ₇ ) _1.31 O _0.9
Mercapto group equivalent: measured value 803 g / mol, theoretical value 785 g / mol viscosity: 33.6 mm ² / s

Next, Examples and Comparative Examples in which pressure-sensitive adhesives were prepared using the acrylic resin and organopolysiloxane produced above and applied to an optical film are shown. Here, the following were used as a crosslinking agent.
“Coronate L”: Ethyl acetate solution of trimethylolpropane adduct of tolylene diisocyanate (solid content concentration 75%), trade name “TAZM”: Trimethylolpropane tri-β-aziridinylpro manufactured by Nippon Polyurethane Industry Co., Ltd. Pionate (liquid), trade name manufactured by Mutual Yako Co., Ltd.

Moreover, the following were each used as the silane compound of a comparative example.
“KBM-803”: 3-mercaptopropyltrimethoxysilane (liquid), trade name “KBM-303” manufactured by Shin-Etsu Chemical Co., Ltd .: 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (liquid), Product name manufactured by Shin-Etsu Chemical Co., Ltd.

[Examples 1 to 3 and Comparative Examples 1 to 6]
(A) Production of pressure-sensitive adhesive The ethyl acetate solution of acrylic resin A1 obtained in Polymerization Example 1 or the ethyl acetate solution of acrylic resin A2 obtained in Polymerization Example 2 was used in a non-volatile content of 100 parts, respectively. Coronate L ”or“ Coronate L ”and“ TAZM ”are mixed in the amounts shown in Table 1, and the organopolysiloxane or silane compound shown in Table 1 in amounts shown in Table 1 to prepare an adhesive composition. did. However, in Table 1, the blending amount (part) of the crosslinking agent “Coronate L” is the amount of solids.

(B) Production of optical film with pressure-sensitive adhesive The release-treated surface of each of the above-mentioned pressure-sensitive adhesive compositions was subjected to a release-treated polyethylene terephthalate film ("PET 3811", product name manufactured by Lintec Corporation; called a separator). Then, it was applied using an applicator so that the thickness after drying was 15 μm, and dried at 90 ° C. for 1 minute to obtain a sheet-like pressure-sensitive adhesive. Next, on one side of a polarizing film 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 aged for 7 days under conditions of a temperature of 23 ° C. and a relative humidity of 65% to obtain a polarizing film with a pressure-sensitive adhesive. Moreover, these polarizing films with an adhesive were sealed with a pack with an aluminum foil, and further aged for 6 days at a temperature of 60 ° C., thereby accelerating changes with time.

(C) Production of optical layered product (polarized film glass-attached product) Polarized film with pressure-sensitive adhesive produced in (b) above (23 ° C. × 65% RH × 7 days aged, and then further 60 ° C. × 6 The product was aged for 2 days, and was adhered on both sides of the glass substrate for liquid crystal cell (“1737”, product name manufactured by Corning) so as to be crossed Nicol, respectively, thereby producing an optical laminate.

(D) Evaluation of heat resistance and heat-and-moisture resistance of the optical layered body The optical layered body obtained in (c) above was subjected to a heat resistance test that was stored for 300 hours under dry conditions at a temperature of 80 ° C. A moisture and heat resistance test was performed for storage for 300 hours at a humidity of 90%. Each optical laminate after the test was visually observed and evaluated in the following four stages. The results are summarized in Table 2.
<Evaluation criteria for heat resistance and moist heat resistance>
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, a polarizing plate with an adhesive produced in (b) (23 ° C. × 65% RH × 7 days aged and then 60 ° C. × 6 days aged), each having a size of 25 mm × 150 mm test piece Cut to. Next, this test piece was attached to the glass substrate for a liquid crystal cell on the pressure-sensitive adhesive layer side using a sticking device (“Lami Packer”, a product name manufactured by Fuji Plastic Co., Ltd.), and 50 ° C., 5 kgf / cm ² (490). .3 kPa) for 20 minutes. Next, two types of samples, a sample stored for 24 hours in an atmosphere at a temperature of 23 ° C. and a relative humidity of 50%, and a sample stored for 48 hours in an oven at 50 ° C. were prepared. In a% atmosphere, the polarizing film was peeled off from this sticking test piece at a rate of 300 mm / min in the 180 ° direction, and the state of each glass substrate surface was observed and evaluated according to the following criteria. The results are also shown in Table 2.
<Reworkability evaluation criteria>
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 3 in which the organopolysiloxane as defined in the present invention was blended with the acrylic resin and the crosslinking agent were good in any of heat resistance, moist heat resistance and reworkability. Moreover, even after aging these optical films with pressure-sensitive adhesives at 60 ° C. for 6 days, almost satisfactory results were obtained in heat resistance, moist heat resistance and reworkability.

  On the other hand, Comparative Examples 1-6 which mix | blended another organopolysiloxane or a silane compound were inadequate results in any of heat resistance, heat-and-moisture resistance, and rework property.

Claims (11)

(A) acrylic resin,
(B) Crosslinker, and (C) The following average composition formula (I)
Y _a R ¹ _b Si (OCH ₃ ) _c (OC ₂ H ₅ ) _d (OR ² ) _e (OH) _f O _{(4-abcdef) / 2}
... (I)
Wherein Y represents an organic group having at least one selected from a mercapto group, an epoxy group, a (meth) acryloyloxy group, an alkenyl group, a haloalkyl group and an amino group;
R ¹ represents an unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms which does not have at least one aliphatic unsaturated bond;
R ² represents an alkyl group having 3 and / or 4 carbon atoms or a methoxypropyl group;
a, b, c, d, e and f are 0.01 ≦ a ≦ 1, 0 ≦ b <2, 0 <c ≦ 2, 0 ≦ d ≦ 2, 0 <e ≦ 2, 0 ≦ f ≦ 1. And satisfying 0.1 ≦ c + d + e ≦ 2.5 and 2 ≦ a + b + c + d + e + f ≦ 3. )
A pressure-sensitive adhesive composition comprising an organopolysiloxane represented by the formula:   The acrylic resin (A) contains an acrylic resin containing a structural unit derived from a (meth) acrylic acid compound having a polar functional group, the main component being a structural unit derived from a (meth) acrylic acid alkyl ester. 2. The pressure-sensitive adhesive composition according to 1.   The pressure-sensitive adhesive composition according to claim 2, wherein the polar functional group is selected from a free carboxyl group, a hydroxyl group, an amino group, and an epoxy ring.   The pressure-sensitive adhesive composition according to any one of claims 1 to 3, wherein the crosslinking agent (B) contains an isocyanate compound.   In the said average composition formula (I) showing organopolysiloxane (C), Y is an organic group which has a mercapto group or an epoxy group, The adhesive composition in any one of Claims 1-4. The average composition formula (I) representing the organopolysiloxane (C), wherein b is a positive number, R ¹ is a methyl group, and R ² is a propyl group or an isopropyl group. The pressure-sensitive adhesive composition described.   The pressure-sensitive adhesive composition according to claim 1, wherein d is a positive number in the average composition formula (I) representing the organopolysiloxane (C).   The pressure-sensitive adhesive composition according to any one of claims 1 to 7, wherein the organopolysiloxane (C) has an average degree of polymerization of 3 to 100.   An optical film with an adhesive, wherein an adhesive layer formed from the adhesive composition according to any one of claims 1 to 8 is provided on at least one surface of the optical film.   The optical film with an adhesive according to claim 9, wherein the optical film is selected from a polarizing film and a retardation film.   The optical film with an adhesive according to claim 10, wherein the optical film includes a polarizing film in which a protective film made of an acetylcellulose-based resin or an amorphous cyclic polyolefin-based resin is attached to at least one surface of a polarizer.