JP5589463B2 - Silane compound, pressure-sensitive adhesive, method for producing resin composition for adhesive, and optical pressure-sensitive adhesive film - Google Patents

Description

  The present invention relates to a novel silane compound, a method for producing a resin composition for an adhesive containing a silane compound, and a pressure-sensitive adhesive and an optical pressure-sensitive type that are suitably used for optical applications including the resin composition for an adhesive. The present invention relates to an adhesive film.

Due to dramatic advances in electronics in recent years, various flat panel displays (FPD) such as liquid crystal displays (LCD), plasma displays (PDP), rear projection displays (RPJ), EL displays, light emitting diode displays, etc. As a device, it has come to be used in a wide range of fields. These FPDs are not only used fixed indoors, such as personal computer displays and liquid crystal televisions, but also mounted on vehicles such as car navigation displays and used in a moving state.
For such display devices, various films such as an antireflection film for preventing reflection from an external light source and a protective film (protection film) for preventing scratches on the surface of the display device are usually used. For example, in a liquid crystal cell member constituting an LCD, a polarizing film or a retardation film is laminated.
Further, the FPD is not only used as a display device, but may be used as an input device by providing a touch panel function on the surface thereof. This touch panel also uses an antireflection film, an ITO vapor-deposited resin film, and the like, and a protective film is stuck on the outermost surface to prevent damage in manufacturing, transportation, and the like. Such a film is used by being attached to an adherend through a pressure-sensitive adhesive. Since the pressure-sensitive adhesive is required to have excellent transparency, a pressure-sensitive adhesive mainly composed of a propenoic acid resin is generally used.

  By the way, among the various films described above, the polarizing film has a three-layer structure in which both sides of a polyhydroxyethene polarizer are sandwiched between cellulose triacetate or cycloolefin protective films. For this reason, in a polarizing film, the remarkable dimensional change by expansion / contraction accompanying the change of temperature or humidity arises according to the characteristic of the material which comprises each layer.

In addition, in the inspection process of a laminate with a polarizing film attached to the glass surface for a liquid crystal cell, the polarizing film etc. is peeled off and a new polarizing film etc. is attached to those that have air or dust trapped during lamination. Will be fixed. This re-pasting is also called “rework”.
However, since the laminated body is generally inspected after being stored at a high temperature for a certain period of time in order to improve adhesion, not only does the peel strength increase during that time, but it becomes difficult to peel off the polarizing film and the like. The glass member as the adherend is contaminated, such as adhesive residue and cloudiness, after re-peelability is reduced and peeled off.

  In addition, since the dimensional change due to shrinkage of the polyhydroxyethene film is severe under high temperature or high temperature and high humidity conditions, the laminate composed of the optical film / pressure-sensitive adhesive layer / adherent is If the dimensions of the polarizing film are changed under wet conditions, bubbles may be generated at the interface between the pressure-sensitive adhesive layer and the adherend (foaming phenomenon), or the optical film may be lifted from the adherend and peeled off ( Floating / peeling phenomenon). By adjusting the molecular weight of the main component of the pressure-sensitive adhesive and the degree of crosslinking of the pressure-sensitive adhesive and increasing the adhesive strength, it can foam, float and peel even under harsh environments against the dimensional change of the polarizing film. An attempt was made to prevent it from occurring.

  However, simply trying to resist the dimensional change of the optical film simply by increasing the adhesive force, the stress distribution due to the dimensional change of the polarizing film that occurs under high temperature or high temperature and high humidity conditions becomes non-uniform, and the stress becomes optical. It concentrates on the four corners and the peripheral edge of the film. As a result, in the display device using the polarizing film, there is a problem that light leaks from the peripheral end portion of the display device, that is, so-called white spots occur.

  As described above, the pressure-sensitive adhesive for laminating a polarizing film on a glass member for a liquid crystal cell has good optical properties (transparency), heat resistance and moist heat resistance, good stress relaxation properties, and removability. Etc. are required. Similar performance is also required for pressure sensitive adhesives for laminating retardation films and cover films for various displays.

Conventionally, various pressure-sensitive adhesives have been proposed for such various requirements.
For example, a pressure-sensitive adhesive obtained by mixing a polyether polyol with a propenoic acid-based pressure-sensitive adhesive containing a propenoic acid-based resin and a crosslinking agent is known (see Patent Document 1).

However, the optical pressure-sensitive adhesive film using the pressure-sensitive adhesive described in Patent Document 1 is optically bonded to an adherend and exposed to high temperatures or high temperature and high humidity conditions for a long time. Extremely small bubbles are generated in a streak-like state at the peripheral edge of the film. This phenomenon is called a “crack” because very small bubbles that appear as streaks look like a kind of crack.
In addition, about 10 bubbles of 10 μm or less, which cannot be confirmed unless using an electron microscope, are generated in the center part per 10 m ² .
Further, in a display device of 20 inches or more, the luminance of the light source must be set high from the viewpoint of easy viewing. In the pressure-sensitive adhesive optical film using the pressure-sensitive adhesive described in Patent Document 1, white spots were not regarded as a problem in a display device of less than 20 inches. However, there has also been a problem that white spots are conspicuous in a display device using a high-intensity light source used at 20 inches or more.

As pressure-sensitive adhesives for pressure-sensitive adhesive optical films, propenoic acid-based pressure-sensitive adhesives containing a propenoic acid-based resin, a crosslinking agent, and various silane coupling agents are disclosed in various documents.
However, even if a relatively low molecular weight silane coupling agent such as 3-glycidoxypropyltrimethoxysilane or 3-aminopropyltrimethoxysilane is contained, the demand for rework becomes more severe, which is more severe. The request has become unsatisfactory. In addition, there is a problem that cracking and foaming are likely to occur when the resin is stuck to an adherend and exposed to a high temperature or a high temperature and high humidity for a long period of time because of poor compatibility with the resin.

  Further, for example, Patent Document 2 discloses that the propenoic acid-based polymer contains a silane compound having a β-ketoester structure and an alkoxy group with respect to 100 parts by weight of the propenoic acid-based resin. A pressure-sensitive adhesive obtained by blending 0.001 to 5 parts by weight has been proposed. However, since the pressure-sensitive adhesive is not compatible with the propenoic acid polymer, there is a problem that durability with time is lowered due to liberation of the silane compound monomer (see Patent Document 2).

  In addition, for example, Patent Document 3 discloses that a propenoic acid oligomer-type silane coupling agent obtained by copolymerizing the propenoic acid polymer with a silane compound having a polymerizable double bond site and a reactive propenoic acid monomer. A pressure-sensitive adhesive obtained by polymerizing the silane compound in an amount of 0.05 to 5 parts by weight with respect to 100 parts by weight of the propenoic acid resin has been proposed. Even if the pressure-sensitive adhesive film described in Patent Document 3 is attached to an adherend and exposed to a high temperature or a high temperature and high humidity for a long period of time, cracks in the vicinity of the peripheral edge portion or microscopic deformation in the central portion are required. Bubbles were not generated, and no white spots were observed on a display device of less than 20 inches (see Patent Document 3).

However, in a pressure-sensitive adhesive composition containing a propenoic acid oligomer silane coupling agent obtained by copolymerizing a silane compound having a polymerizable double bond site and a reactive propenoic acid monomer, The oligomer type silane coupling agent has a problem in polymerization stability due to the influence of the reactive site such as an alkoxyl group different from the polymerizable double bond site. It is difficult to produce a ring agent, and the adhesiveness, which is a characteristic of a silane coupling agent, is significantly reduced. Furthermore, the pressure-sensitive adhesive optical film using this pressure-sensitive adhesive has a problem that the peelability from the peelable film is likely to be lowered as described in detail below.
The pressure-sensitive adhesive optical film is coated with a pressure-sensitive adhesive on the release-treated surface of a film-like substrate that has been subjected to a release treatment (hereinafter referred to as a peelable film), dried, and the optical film is applied to the surface of the pressure-sensitive adhesive layer. It can be obtained by laminating or applying a pressure-sensitive adhesive to an optical film, drying it, and laminating the release-treated surface of the peelable film on the surface of the pressure-sensitive adhesive layer. However, the pressure-sensitive adhesive optical film is not always attached to an adherend, that is, a liquid crystal cell member immediately after production. The obtained pressure-sensitive adhesive optical film is often used after being stored for a certain period. In such a case, when the peelable film was peeled off and the exposed pressure-sensitive adhesive layer was to be attached to a liquid crystal cell member such as glass, there was a problem that the peelable film was difficult to peel off.

  As described above, from the conventional propenoic acid pressure-sensitive adhesives using various silane coupling agents, the releasability of the peelable film and the removability from the adherend, which is called “reworkability”, the adherend It was impossible to obtain a pressure-sensitive adhesive optical film that satisfactorily satisfied the high durability after contamination and sticking.

JP-A-6-128539 JP-A-8-104855 JP 2008-101168 A

  The present invention is an optical adhesive film for providing a silane compound or for adhering to a glass member for a liquid crystal cell, having excellent peel stability of the peelable film, An object of the present invention is to provide a pressure-sensitive adhesive having a novel silane compound that can form an optical pressure-sensitive adhesive film excellent in adherend adherence and excellent in durability (heat resistance, moist heat resistance) after sticking. To do.

The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems.
That is, the present invention relates to a silane compound represented by the following general formula (1).

General formula (1)

[In General Formula (1), R1 to R3 are a hydrogen atom or an alkyl group having 1 to 30 carbon atoms, an alkenyl group, a cycloalkyl group, an aryl group, a hydroxyl group, an alkoxyl group, a mercapto group, an amino group, a glycidyl group, and Represents a halogen group. R4 represents a substituent in which a Si—C bond is formed on the α, β-unsaturated group of the α, β-unsaturated group-containing monomer (X) by a hydrosilylation reaction. ]

  In the present invention, the R4 is formed by forming an Si-C bond by hydrosilylation reaction on the α, β-unsaturated group of the copolymer (A) having a weight average molecular weight of 200 to 2,000,000. The present invention relates to a silane compound according to the invention, which is a substituent.

  The present invention also relates to an adhesive resin composition comprising a polymer (D) of an α, β-unsaturated group-containing monomer (X) and the silane compound of the invention.

In the present invention, the α, β-unsaturated group-containing monomer (X) is reacted with the compound (2) represented by the following general formula (2),
polymer (D) of α, β-unsaturated group-containing monomer (X);
Silane compound (1) which is a reaction product of α, β-unsaturated group-containing monomer (X) and compound (2);
It is related with the manufacturing method of the resin composition for adhesive agents characterized by obtaining the mixture of these.

General formula (2)

[In General Formula (2), R1 to R3 are a hydrogen atom or an alkyl group having 1 to 30 carbon atoms, an alkenyl group, a cycloalkyl group, an aryl group, a hydroxyl group, an alkoxyl group, a mercapto group, an amino group, a glycidyl group, and Represents a halogen group. ]

The present invention also provides a first step of polymerizing the α, β-unsaturated group-containing monomer (X) until the reaction rate becomes 70 to 99.9%;
Subsequently, the compound (2) is added, and the α, β-unsaturation-containing monomer (X) remaining in the first step is reacted with the compound (2), whereby the monomer (X) and the compound (2) are reacted. A second step of obtaining a polymer (D) of the silane compound (1) and the α, β-unsaturated group-containing monomer (X), which is a reaction product with
It is related with the manufacturing method of the resin composition for adhesives of the said invention characterized by including this.

  Moreover, this invention relates to the resin composition for adhesive agents obtained by the manufacturing method of the said invention.

  Moreover, this invention relates to the pressure sensitive adhesive characterized by including the resin composition for adhesives of the said invention, and a crosslinking agent (G).

  The present invention also relates to an optical pressure-sensitive adhesive film, wherein a pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive of the invention is formed on a substrate (H).

  The present invention also relates to the optical pressure-sensitive adhesive film according to the invention, wherein the substrate (H) is an optical film.

  By using the novel silane compound of the present invention, it is an optical adhesive film for adhering to a glass member for a liquid crystal cell, excellent in peeling stability from the peelable film, It is now possible to provide a pressure-sensitive adhesive that can form an optical pressure-sensitive adhesive film that has excellent peelability and adherend contamination, and has excellent durability (heat resistance, heat and moisture resistance) after sticking. .

  The silane compound represented by the following general formula (1) used in the present invention (hereinafter referred to as silane compound (1)) is a compound in which substituents R1 to R4 are bonded to Si atoms.

General formula (1)

[In General Formula (1), R1 to R3 are a hydrogen atom or an alkyl group having 1 to 30 carbon atoms, an alkenyl group, a cycloalkyl group, an aryl group, a hydroxyl group, an alkoxyl group, a mercapto group, an amino group, a glycidyl group, and Represents a halogen group. R4 represents a substituent in which a Si—C bond is formed on the α, β-unsaturated group of the α, β-unsaturated group-containing monomer (X) by a hydrosilylation reaction. ]

  R1 to R3 may each independently have a substituent, a non-polar substituent such as a hydrogen atom or an alkyl group having 1 to 30 carbon atoms, an alkenyl group, a cycloalkyl group, an aryl group, a hydroxyl group, Polar substituents such as alkoxyl groups, mercapto groups, amino groups, glycidyl groups, and halogen groups are preferred. R4 is preferably a substituent in which a Si—C bond is formed on the α, β-unsaturated group of the α, β-unsaturated group-containing monomer (X) by a hydrosilylation reaction.

  Examples of nonpolar substituents such as an alkyl group having 1 to 30 carbon atoms, an alkenyl group, a cycloalkyl group, or an aryl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, Heptyl, octyl, nonyl, decyl, undecyl, dodecyl, octadecyl, isopropyl, isobutyl, sec-butyl, tert-butyl, 1-ethylpentyl, trifluoromethyl, 2- Alkyl groups such as ethylhexyl group;

  Ethenyl, 1-propenyl, 2-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-octenyl, 1-decenyl, 1-octadecenyl, 2-methylallyl Groups, acryloyl groups, methacryloyl groups, γ-methacryloxypropyl groups, 2-phenylethenyl groups, crotonoyl groups, isocrotonoyl groups, oleoyl groups and the like;

  Cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclooctadecyl group, 2-bornyl group, 2-isobornyl group, 1-adamantyl group;

  Phenyl group, biphenyl group, 1-naphthyl group, 2-naphthyl group, 9-anthryl group, 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 9-fluorenyl group Terphenyl group, quarterphenyl group, o-, m-, and p-tolyl group, xylyl group, o-, m-, and p-cumenyl group, mesityl group, pentarenyl group, binaphthalenyl group, turnaphthalenyl group, quarternaphthalene Renyl group, heptaenyl group, biphenylenyl group, indacenyl group, fluoranthenyl group, acenaphthylenyl group, aceanthrilenyl group, phenalenyl group, fluorenyl group, anthryl group, bianthracenyl group, teranthracenyl group, quarteranthracenyl group, Anthraquinolyl, phenanthryl, Phenylenyl group, pyrenyl group, chrycenyl group, naphthacenyl group, preadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, hexaphenyl group, hexacenyl group, rubicenyl group, coronenyl group, trinaphthylenyl group , Heptaphenyl group, heptacenyl group, pyrantrenyl group, overalenyl group, phenacyl group, 1-naphthoylmethyl group, 2-naphthoylmethyl group, 4-methylsulfanylphenacyl group, 4-phenylsulfanylphenacyl group, 4-dimethyl Aryl groups such as aminophenacyl group, 4-cyanophenacyl group, 4-methylphenacyl group, 2-methylphenacyl group, 3-fluorophenacyl group, 3-trifluoromethylphenacyl group, 3-nitrophenacyl group And the like.

  Examples of polar substituents such as hydroxyl group, alkoxyl group, mercapto group, amino group, glycidyl group and halogen group include hydroxyl group, methyl hydroxyl group, ethyl hydroxyl group, butyl hydroxyl group, hydroxycyclohexyl group, hydroxyphenyl group, etc. Hydroxyl groups of

  Methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, dodecyloxy, octadecyloxy, isopropoxy, isobutoxy, iso Pentyloxy group, sec-butoxy group, t-butoxy group, sec-pentyloxy group, t-pentyloxy group, tert-octyloxy group, neopentyloxy group, cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group Cyclohexyloxy group, adamantyloxy group, norbornyloxy group, boronyloxy group, 2-isobornyloxy group, 1-adamantyloxy group, 4-decylcyclohexyloxy group, 2-tetrahydrofuranyloxy group, 2-te Lahydrofuranyloxy group, phenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, 9-anthryloxy group, 9-phenanthryloxy group, 1-pyrenyloxy group, 5-naphthacenyloxy group, 1-indenyloxy group, 2-azurenyloxy group, 1-acenaphthyloxy group, 9-fluorenyloxy group, 2-furanyloxy group, 2-thienyloxy group, 2-indolyloxy group, 3-indolyloxy group Group, 2-benzofuryloxy group, 2-benzothienyloxy group, 2-carbazolyloxy group, 3-carbazolyloxy group, 4-carbazolyloxy group, 9-acridinyloxy group, acetoxy group , Propionyloxy group, butyryloxy group, isobutyryloxy group, valeryloxy group, isovaleryloxy group, pivaloyloxy Group, lauroyloxy group, myristoyloxy group, palmitoyloxy group, stearoyloxy group, cyclopentylcarbonyloxy group, cyclohexylcarbonyloxy group, acryloyloxy group, methacryloyloxy group, crotonoyloxy group, isocrotonoyloxy group, oleoyloxy Group, benzoyloxy group, 1-naphthoyloxy group, 2-naphthoyloxy group, cinnamoyloxy group, 3-furoyloxy group, 2-thenoyloxy group, nicotinoyloxy group, isonicotinoyloxy group, 9-anthroyl Oxy group, 5-naphthacenoyloxy group, ethoxycarbonylmethyl group, 2-ethylhexyloxycarbonylmethyloxy group, aminocarbonylmethyloxy group, N, N-dibutylaminocarbonylmethyloxy group, N-methylaminocarbonylmethyloxy group, N-ethylaminocarbonylmethyloxy group, N-octylaminocarbonylmethyloxy group, N-methyl-N-benzylaminocarbonylmethyloxy group, benzyloxy group, cyanomethyloxy group, etc. Alkoxyl groups;

  Mercapto group, methylthio group, ethylthio group, butylthio group, pentylthio group, hexylthio group, octylthio group, decylthio group, dodecylthio group, octadecylthio group, tert-butylthio group, phenylthio group, 2-methylphenylthio group, 4-tert- Mercapto groups such as butylphenylthio group, 1-naphthylthio group, 2-naphthylthio group, 9-anthrylthio group, 9-phenanthrylthio group;

  Amino, methylamino, ethylamino, propylamino, butylamino, pentylamino, hexylamino, heptylamino, octylamino, nonylamino, decylamino, dodecylamino, octadecylamino, isopropyl Amino group, isobutylamino group, isopentylamino group, sec-butylamino group, tert-butylamino group, sec-pentylamino group, tert-pentylamino group, tert-octylamino group, neopentylamino group, cyclopropylamino Group, cyclobutylamino group, cyclopentylamino group, cyclohexylamino group, cycloheptylamino group, cyclooctylamino group, cyclododecylamino group, 1-adamantamino group, 2-adamantamino group, dimethylamino group, Ethylamino group, dipropylamino group, dibutylamino group, dipentylamino group, dihexylamino group, diheptylamino group, dioctylamino group, dinonylamino group, didecylamino group, didodecylamino group, dioctadecylamino group, diisopropylamino group, Diisobutylamino group, diisopentylamino group, methylethylamino group, methylpropylamino group, methylbutylamino group, methylisobutylamino group, cyclopropylamino group, morpholino group, pyrrolidino group, piperidino group, piperazino group, 2H-pyrrolyl Group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H-indolyl group, 2-indolyl group, 3-indolyl group 1H-indazolyl group, purinyl group, 4H-quinolidinyl group, anilino group, 1-naphthylamino group, 2-naphthylamino group, o-toluidino group, m-toluidino group, p-toluidino group, 2-biphenylamino group, 3-biphenylamino group, 4-biphenylamino group, 1-fluoreneamino group, 2-fluoreneamino group, 2-thiazoleamino group, p-terphenylamino group, diphenylamino group, ditolylamino group, N-phenyl-1- Naphtylamino group, N-phenyl-2-naphthylamino group, N-methylanilino group, N-methyl-2-pyridino group, N-ethylanilino group, N-propylanilino group, N-butylanilino group, N-isopropyl, N -Pentylanilino group, N-ethylanilino group, N-methyl-1-naphthylamino group, etc. Amino groups;

  Ethene oxide group, propene oxide group, epichlorohydrin group, ethenylbenzene oxide group, epibromohydrin group, phenyl glycidyl ether group, cyclohexene oxide group, butene oxide group, butyl glycidyl ether group, cresyl glycidyl ether group, ethene oxide mono Glycidyl ether group, propene oxide monoglycidyl ether group, 1,2,3-trihydroxypropane monoglycidyl ether group, diglycerol monoglycidyl ether group, (2R, 3S, 4S, 5S) -hexane-1,2,3 4,5,6-hexol monoglycidyl ether group, alkylphenol glycidyl ether group, polyethene glycol monoglycidyl ether group, tripropene oxide monoglycidyl ether , Polypropene oxide monoglycidyl ether group, 3-methylbut-3-en-1-ol monoglycidyl ether group, 1,6-hexanediol monoglycidyl ether group, 2-methylpentane-2,4-diol monoglycidyl ether group Glycidyl groups such as aliphatic monoglycidyl ether group, tertiary aliphatic monoglycidyl ether group, spiroglycol monoglycidyl ether group;

And halogen groups such as fluorine, chlorine, bromine and iodine.
Furthermore, the hydrogen atom of the substituent preferably used for R1 to R3 may be further substituted with the other substituent described above.

  R4 represents an α, β-unsaturated group-containing monomer (X) having at least one α, β-unsaturated double bond in the molecule, and a compound represented by the following general formula (2) [below , Also referred to as compound (2)] represents the remaining substituents produced by the Si—C bond obtained by the hydrosilylation reaction.

General formula (2)

[In Formula (2), R1-R3 is a hydrogen atom or a C1-C30 alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, a hydroxyl group, an alkoxyl group, a mercapto group, an amino group, a glycidyl group, and a halogen. Represents a group. ]

  The compound (2) is not particularly limited as long as it is a compound having an Si element, but a compound having a hydrosilyl group is preferable. For example, methylsilane, ethylsilane, dimethylsilane, diethylsilane, diethylmethylsilane, butyldimethylsilane, di-t-butylmethylsilane, triethylsilane, trihexylsilane, butyldimethylsilane, cyclohexyldimethylsilane, n-hexylsilane, n- Octylsilane, tri-n-octylsilane, tripropylsilane, triisopropylsilane, triisobutylsilane, trihexylsilane, n-octadecylsilane, phenylsilane, methylphenylsilane, dimethylphenylsilane, methylphenylvinylsilane, dimethylbenzylsilane, Diphenylsilane, triphenylsilane, (phenylethynyl) dimethylsilane, methyldichlorosilane, ethyldichlorosilane, dimethylchlorosilane, bis ( -Chloroethoxy) methylsilane, tris (2-chloroethoxy) silane, n-hexyldichlorosilane, diisopropylchlorosilane, dichlorosilane, di-t-butylchlorosilane, trichlorosilane, chloromethylsilane, methylphenylchlorosilane, phenyldichlorosilane, diphenyl Chlorosilane, chloroisopropylsilane, dichloromethylsilane, dichloroethylsilane, methyldimethoxysilane, dimethoxymethylsilane, methyldiethoxysilane, dimethylethoxysilane, diethoxysilane, trimethoxysilane, triethoxysilane, tripentyloxysilane, tris ( Trimethylsiloxy) silane, methylphenylethenylsilane, allyldimethylsilane, 1,1,2-trimethyldisilane, 1,1,2, -Tetraphenyldisilane, 1,1,3,3-tetramethyldisilazane, 1,4-bis (dimethylsilyl) benzene, methyltris (dimethylsiloxy) silane, tris (trimethylsiloxy) silane, phenyltris (dimethylsiloxy) silane , Tetrakis (dimethylsiloxy) silane, tetramethyldisilazane, dimethylsilyldimethylamine, bis (dimethylamino) methylsilane, tris (dimethylamino) silane, tris (dimethylsilyl) amine, N, N-dimethylaminomethylethoxysilane, di Acetoxymethylsilane, N, O-bis (dimethylsilyl) acetamide, 2- (dimethylsilyl) pyridine, tetrakis (dimethylsilyl) silane, allyldimethylsilane, mercaptodimethylsilane, cyclopropanesilane , Tris (trimethylsilyl) silane, 1,1,4,4-tetramethyldisilylethene, cyclohexanesilane, pentamethyldisiloxane, tetramethylcyclotetrasiloxane, 1,3-diphenyl-1,3-dimethyldisiloxane, penta Methyldisiloxane, 1,1,3,3-tetramethyldisiloxane, 1,1,3,3-tetraisopropyldisiloxane, 1,1,3,3-tetrakis (trimethylsiloxy) disiloxane, 1,1,3 3,3, -tetramethyldisilazane, 1,2-bis (dimethylsilyl) benzene, 1,1,3,3,5,5-hexamethyltrisiloxane, 1,1,3,3,5,5 7,7-octamethyltetrasiloxane, 1,1,1,3,5,5,5-heptamethyltrisiloxane, 1,1,3,3,5,5 Heptamethyltrisiloxane, 1,1,1,3,5,7,7,7-octamethyltetrasiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9- Pentamethylcyclopentasiloxane, 1,2,3,4,5,6-hexamethylcyclotrisilazane, α, ω-bis (hydrodiene) polydimethylsiloxane and long-chain dimethylsiloxane oligomer with oily hydroyl group Or a wax-like substance etc. are mentioned.

  As described above, the silane compound (1) of the present invention applies the α, β-unsaturated double bond of the α, β-unsaturated group-containing monomer (X) and the hydrosilylation reaction of the compound (2). It can be produced by solution reaction, solventless reaction, etc., but is not particularly limited in these reaction methods and operations.

  The hydrosilylation reaction described above preferably uses a catalyst. As the catalyst, a transition metal is preferable. Specific examples include transition metal complexes such as platinum, cobalt, iridium, indium, rhodium, palladium, copper and nickel, or halides thereof. Of these, chloroplatinic acid and palladium chloride are preferred in terms of safety, reaction efficiency, economy, and reaction conditions. The catalyst amount is preferably used in an amount of 1 part by weight or less based on 100 parts by weight of the total of the compound (2) and the α, β-unsaturated compound (X). If it exceeds 1 part by weight, not only catalyst precipitates may be produced in the product, but also there may be problems in terms of economy and hygiene.

  As the α, β-unsaturated group-containing monomer (X), propenoic acid, 2-methylpropenoic acid, propenoic acid derivatives, 2-methylpropenoic acid derivatives, and other alkenyl group-containing compounds are preferably used. Further, even a high molecular weight α, β-unsaturated compound having a α, β-unsaturated double bond consisting of a polymer portion having a weight average molecular weight (Mw) of 200 to 2,000,000, a so-called macromonomer. good.

  Examples of the propenoic acid derivative or 2-methylpropenoic acid derivative include, for example, methyl (2-methyl) propenoate [combination of methyl propenoate and methyl 2-methylpropenoate is referred to as “methyl (2-methyl) propenoate”. To do. The same applies below. ], (2-methyl) propenoic acid ethyl, (2-methyl) propenoic acid 1-propyl, (2-methyl) propenoic acid 2-propyl, (2-methyl) propenoic acid n-butyl, (2-methyl) propene Sec-butyl acid, iso-butyl (2-methyl) propenoate, tert-butyl (2-methyl) propenoate, n-amyl (2-methyl) propenoate, iso-amyl (2-methyl) propenoate, 2-methyl) propenoic acid n-hexyl, (2-methyl) propenoic acid 2-ethylhexyl, (2-methyl) propenoic acid n-octyl, (2-methyl) propenoic acid iso-octyl, (2-methyl) propenoic acid n-nonyl, iso-nonyl (2-methyl) propenoate, decyl (2-methyl) propenoate, dodecyl (2-methyl) propenoate, (2-methyl) propyl Pensan octadecyl, (2-methyl) propenoic acid lauryl, (2-methyl) (2-methyl) such as propenoic acid stearyl propenoic acid alkyl esters;

  For example, cyclohexyl (2-methyl) propenoate, benzyl (2-methyl) propenoate, iso-bonyl (2-methyl) propenoate, phenyl (2-methyl) propenoate, 2-phenoxy (2-methyl) propenoate (2-methyl) propenoic acid cyclic esters such as ethyl, 2-oxo-1,2-phenylethyl (2-methyl) propenoate, 2-oxo-1,2-diphenylethyl (2-methyl) propenoate;

  For example, 2-propenyl (2-methyl) propenoate, 1-methyl-2-propenyl (2-methyl) propenoate, 2-methyl-2-propenyl (2-methyl) propenoate, (2-methyl) propenoic acid 1-butenyl, 2-butenyl (2-methyl) propenoate, 3-butenyl (2-methyl) propenoate, 1,3-methyl-3-butenyl (2-methyl) propenoate, (2-methyl) propenoic acid 2-chloro-2-propenyl, (2-methyl) propenoic acid 3-chloro-2-propenyl, (2-methyl) propenoic acid-o-2-propenylphenyl, (2-methyl) propenoic acid 2- (2-propenyloxy) ) Ethyl, 2-propenyl lactyl (2-methyl) propenoate, 3,7-dimethyloct-6-en-1-yl (2-methyl) propenoate, (2-methyl) propyl Penic acid (E) -3,7-dimethylocta-2,6-dien-1-yl, rosinyl (2-methyl) propenoate, cinnamyl (2-methyl) propenoate, ethenyl (2-methyl) propenoate, etc. Further (2-methyl) propenoic acid esters containing an unsaturated group;

  For example, (2-methyl) propenoic acid perfluoromethyl, (2-methyl) propenoic acid perfluoroethyl, (2-methyl) propenoic acid perfluoropropyl, (2-methyl) propenoic acid perfluorobutyl, (2-methyl) ) Perfluorooctyl propenoate, trifluoromethyl methyl (2-methyl) propenoate, 2-trifluoromethyl ethyl (2-methyl) propenoate, diperfluoromethyl methyl (2-methyl) propenoate, (2-methyl) ) 2-perfluoroethylethyl acrylate, (2-methyl) propenoic acid 2-perfluoromethyl-2-perfluoroethylmethyl, (2-methyl) propenoic acid triperfluoromethylmethyl, (2-methyl) propenoic acid 2-perfluoroethyl-2-perfluorobutylethyl, (2-methyl) (2-methyl) propenoic acid perfluoroalkyl esters such as 2-perfluorohexylethyl lopenate, 2-perfluorodecylethyl (2-methyl) propenoate, 2-perfluorohexadecylethyl (2-methyl) propenoate Kind;

  For example, 2-hydroxyethyl (2-methyl) propenoate, 1-hydroxypropyl (2-methyl) propenoate, 2-hydroxypropyl (2-methyl) propenoate, 2-methoxyethyl (2-methyl) propenoate, Hydroxyl or alkoxysilyl group-containing (2-methyl) propenoic acid such as 2-ethoxyethyl (2-methyl) propenoate, 2-hydroxybutyl (2-methyl) propenoate, 4-hydroxybutyl (2-methyl) propenoate Esters;

  For example, N-methylaminoethyl (2-methyl) propenoate, N-tributylaminoethyl (2-methyl) propenoate, N, N-dimethylaminoethyl (2-methyl) propenoate, (2-methyl) propenoic acid Amino group-containing (2-methyl) propenoates such as N, N-diethylaminoethyl, pentamethylpiperidinyl (2-methyl) propenoate, tetramethylpiperidinyl (2-methyl) propenoate;

  For example, glycidyl (2-methyl) propenoate, (2-methyl) propenoate (3,4-epoxycyclohexyl) methyl, (2-methyl) propenoate (3-methyl-3-oxetanyl) methyl, (2-methyl) ) Oxygen atom-containing heterocycle-containing (2-methyl) propenoates such as tetrahydrofurfuryl propenoate;

  For example, 3- (2-methylpropane-2-enoyloxypropyl) trimethoxysilane, 3- (2-methylpropane-2-enoyloxypropyl) triethoxysilane, 3- (2-methylpropan-2- Enoyloxypropyl) triisopropoxysilane, 3- (2-methylpropane-2-enoyloxypropyl) methyldimethoxysilane, 3- (2-methylpropane-2-enoyloxypropyl) methyldiethoxysilane, 3 -(2-methyl) propenoic acid esters containing alkoxysilyl groups such as (propane-2-enoyloxypropyl) trimethoxysilane;

  For example, 2- (2′-hydroxy-5 ′-(2-methyl) propane-2-enoyloxyethylphenyl) -2H-benzotriazole, 2- (2′-hydroxy-5 ′-(2-methyl) Propane-2-enoyloxyethylphenyl) -5-chloro-2H-benzotriazole, 2- (2'-hydroxy-5 '-(2-methyl) propan-2-enoyloxypropylphenyl) -2H-benzo Triazole, 2- (2′-hydroxy-5 ′-(2-methyl) propane-2-enoyloxypropylphenyl) -5-chloro-2H-benzotriazole, 2- (2′-hydroxy-3′-tert) -Butyl-5 ′-(2-methyl) propane-2-enoyloxyethylphenyl) -2H-benzotriazole, 2- (2′-hydroxy-3) -tert- butyl-5 '- (2-methyl) propan-2-enoyl oxyethyl phenyl) -5-chloro -2H- benzotriazole of benzotriazole (2-methyl) propenoic acid derivatives;

  For example, 2-hydroxy-4- {2- (2-methyl) propane-2-enoyloxy} ethoxydiphenylmethanone, 2-hydroxy-4- {2-((2-methyl) propane-2-enoyloxy} butoxydiphenyl Methanone, 2,2′-dihydroxy-4- {2- (2-methyl) propane-2-enoyloxy} ethoxydiphenylmethanone, 2-hydroxy-4- {2- (2-methyl) propan-2-enoyloxy } Diphenylmethanone-based (2-methyl) propenoic acid derivatives such as ethoxy-4 ′-(2-hydroxyethoxy) diphenylmethanone;

  For example, 2,4-diphenyl-6- [2-hydroxy-4- (2- (2-methyl) propane-2-enoyloxyethoxy)]-S-triazine, 2,4-bis (2-methylphenyl) ) -6- [2-hydroxy-4- (2- (2-methyl) propane-2-enoyloxyethoxy)]-S-triazine, 2,4-bis (2-methoxyphenyl) -6- [ 2-hydroxy-4- (2- (2-methyl) propane-2-enoyloxyethoxy)]-S-triazine, 2,4-bis (2-ethylphenyl) -6- [2-hydroxy-4- (2- (2-Methyl) propane-2-enoyloxyethoxy)]-S-triazine, 2,4-bis (2-ethoxyphenyl) -6- [2-hydroxy-4- (2- (2- Methyl) propane-2-enoyloxyethoxy)] -S-triazine, 2,4-bis (2,4-dimethoxyphenyl) -6- [2-hydroxy-4- (2- (2-methyl) propane-2-enoyloxyethoxy)] -S-triazine 2,4-bis (2,4-dimethylphenyl) -6- [2-hydroxy-4- (2- (2-methyl) propane-2-enoyloxyethoxy)]-S-triazine, 2,4 -Bis (2,4-diethoxylphenyl) -6- [2-hydroxy-4- (2- (2-methyl) propane-2-enoyloxyethoxy)]-S-triazine, 2,4-bis ( 2,4-diethylphenyl) -6- [2-hydroxy-4- (2- (2-methyl) propane-2-enoyloxyethoxy)]-S-triazine, 2,4-diamino-6-2- Methylprop-2-enoyloxyethyl-s Triazine (2-methyl) propenoic acid derivatives such as triazine;

  For example, alkene oxide-containing (2-methyl) propenoic acid derivatives such as an oxirane adduct of (2-methyl) propenoic acid;

  For example, sulfomethyl (2-methyl) propenoate [sulfomethyl propenoate and sulfomethyl 2-methylpropenoate are collectively referred to as “(2-methyl) propenoate sulfomethyl”. The same applies below. ], 2-sulfoethyl (2-methyl) propenoate, 2-sulfopropyl (2-methyl) propenoate, 3-sulfopropyl (2-methyl) propenoate, 2-sulfobutyl (2-methyl) propenoate, (2 -Methyl) propenoate 4-sulfobutyl, (2-methyl) propenoate 2-sulfobutyl, (2-methyl) propenoate 6-sulfohexyl, (2-methyl) propenoate sulfooctyl, (2-methyl) propenoate sulfodecyl Sulfonyl group-containing (2-methyl) propenoic acid alkyl esters such as (2-methyl) propenoic acid sulfolauryl, (2-methyl) propenoic acid sulfostearyl, (2-methyl) propenoic acid sulfophenoxyethyl, (2 (2-Methyl) propenoic acid containing a sulfonyl group such as -methyl) propenoic acid sulfocyclohexyl Jo esters;

  Further, metal salts and ammonium salts of the sulfonyl group-containing (2-methyl) propenoic acid alkyl esters, (2-methyl) propenoyloxydimethylethylammonium ethyl sulfate, (2-methyl) propenoylaminopropyltrimethylammonium Metal salts and ammonium salts of sulfonyl group-containing (2-methyl) propenoic acid alkyl esters such as sulfate and (2-methyl) propenoylaminopropyltriethylammonium sulfate, and sulfonyl group-containing (2-methyl) propenoic acid cyclic esters Metal salts and ammonium salts, (2-methyl) propenoic acid sulfobenzyl, (2-methyl) propenoyloxyethyldimethylbenzylammonium-p-toluenesulfonate, (2-methyl) propenoyloxy Tilt trimethyl ammonium -p- toluenesulfonate, (2-methyl) metal salts or ammonium salts of propenoyl-aminopropyl trimethylammonium -p- toluenesulfonate, etc. sulfonyl group-containing (2-methyl) propenoic acid cyclic ester;

  For example, as a bifunctional monomer, di (2-methyl) propenoic acid ethene oxide, di (2-methyl) propenoic acid triethene oxide, di (2-methyl) propenoic acid tetraethene oxide, di (2-methyl) ) Propenoic acid polyethene oxide, di (2-methyl) propenoic acid propene oxide, di (2-methyl) propenoic acid dipropene oxide, di (2-methyl) propenoic acid tripropene oxide, di (2-methyl) propenoic acid Polypropene oxide, di (2-methyl) propenoic acid butene oxide, di (2-methyl) propenoic acid pentenoxide, di (2-methyl) propenoic acid 2,2-dimethylpropyl, di (2-methyl) propenoic acid hydroxy Pivalylhydroxypivalate (common name: Manda), di (2-methyl) propenoic acid hydride Xipivalyl hydroxypivalate dicaprolactonate, 1,6-hexanediol di (2-methyl) propenoate, 1,2-hexanediol di (2-methyl) propenoate, di (2-methyl) propenoic acid 1 , 5-hexanediol di, di (2-methyl) propenoic acid 2,5-hexanediol, di (2-methyl) propenoic acid 1,7-heptanediol, di (2-methyl) propenoic acid 1,8-octane Diol, di (2-methyl) propenoic acid 1,2-octanediol, di (2-methyl) propenoic acid 1,9-nonanediol di, di (2-methyl) propenoic acid 1,2-decanediol, di ( 2-methyl) propenoic acid 1,10-decanediol, di (2-methyl) propenoic acid 1,2-decanediol, di (2-methyl) propenoic acid 1,12-dode Diol, di (2-methyl) propenoic acid 1,2-dodecanediol, di (2-methyl) propenoic acid 1,14-tetradecanediol, di (2-methyl) propenoic acid 1,2-tetradecanediol, di (2 -Methyl) propenoic acid 1,16-hexadecanediol, di (2-methyl) propenoic acid 1,2-hexadecanediol, di (2-methyl) propenoic acid 2-methyl-2,4-pentanediol, di (2- Methyl) propenoate 3-methyl-1,5-pentanediol, di (2-methyl) propenoate 2-methyl-2-propyl-1,3-propanediol, di (2-methyl) propenoate 2,4- Dimethyl-2,4-pentanediol, di (2-methyl) propenoic acid 2,2-diethyl-1,3-propanediol, di (2-methyl) propenoic acid 2 2,4-trimethyl-1,3-pentanediol, dimethyloloctane di (2-methyl) propenoate, 2-ethyl-1,3-hexanediol di (2-methyl) propenoate, di (2-methyl) 2,5-dimethyl-2,5-hexanediol propenoate, 2-methyl-1,8-octanediol di (2-methyl) propenoate, 2-butyl-2-ethyl di (2-methyl) propenoate 1,3-propanediol, di (2-methyl) propenoic acid 2,4-diethyl-1,5-pentanediol, di (2-methyl) propenoic acid 1,2-hexanediol, di (2-methyl) propene Acid 1,5-hexanediol, di (2-methyl) propenoic acid 2,5-hexanediol, di (2-methyl) propenoic acid 1,7-heptanediol, di (2-methyl) propenoic acid 1 , 8-octanediol, 1,2-octanediol di (2-methyl) propenoate, 1,9-nonanediol di (2-methyl) propenoate, 1,2-decanediol di (2-methyl) propenoate Di (2-methyl) propenoic acid 1,10-decanediol, di (2-methyl) propenoic acid 1,2-decanediol, di (2-methyl) propenoic acid 1,12-dodecanediol, di (2- Methyl) propenoic acid 1,2-dodecanediol, di (2-methyl) propenoic acid 1,14-tetradecanediol, di (2-methyl) propenoic acid 1,2-tetradecanediol, di (2-methyl) propenoic acid 1 , 16-hexadecanediol, di (2-methyl) propenoic acid 1,2-hexadecanediol, di (2-methyl) propenoic acid 2-methyl-2,4-pentane Di (2-methyl) propenoic acid 3-methyl-1,5-pentanediol, di (2-methyl) propenoic acid 2-methyl-2-propyl-1,3-propanediol, di (2-methyl) propenoic acid 2,4-dimethyl-2,4-pentanediol, 2,2-diethyl-1,3-propanediol di (2-methyl) propenoate, 2,2,4-trimethyl-di (2-methyl) propenoate 1,3-pentanediol, di (2-methyl) propenoic acid dimethyloloctane, di (2-methyl) propenoic acid 2-ethyl-1,3-hexanediol, di (2-methyl) propenoic acid 2,5- Dimethyl-2,5-hexanediol, di (2-methyl) propenoate 2-butyl-2-ethyl-1,3-propanediol, di (2-methyl) propenoate 2,4-diethyl-1,5- Ntandiol, di (2-methyl) propenoic acid 1,1,1-trishydroxymethylethane, di (2-methyl) propenoic acid tricyclodecane dihydroxymethyl, di (2-methyl) propenoic acid tricyclodecane dihydroxymethyl dica Prolactonate, tetraethene oxide adduct of di (2-methyl) -2,2-bis (hydroxyphenyl) propane, tetraethene oxide of 2,2-bis (hydroxyphenyl) methane di (2-methyl) propenoate Adduct, tetraethene oxide adduct of di (2-methyl) propenoic acid-4,4′-sulfonyldiphenol, di (2-methyl) propenoic acid-water-added 2,2-bis (hydroxyphenyl) propane tetra Ethene oxide adduct, di (2-methyl) propenoic acid-water added 2,2-bis (hydro (Ciphenyl) methane tetraethene oxide adduct, di (2-methyl) propenoic acid-water-added 2,2-bis (hydroxyphenyl) propane, di (2-methyl) propenoic acid-water-added 2,2-bis (hydroxy Phenyl) methane, di (2-methyl) propenoic acid-2,2-bis (hydroxyphenyl) propane tetraethylene oxide adduct-dicaprolactonate, di (2-methyl) propenoic acid-2,2-bis ( (2-methyl) propenoic acid-based bifunctional derivatives such as hydroxyphenyl) methane tetraethene oxide adduct-dicaprolactonate;

  Tri (2-methyl) propenoic acid 1,2,3-propanetriol, tri (2-methyl) propenoic acid 2-methylpentane-2,4-diol, tri (2-methyl) propene as trifunctional monomers Acid 2-methylpentane-2,4-diol tricaprolactonate, tri (2-methyl) propenoic acid 2,2-dimethylpropane-1,3-diol, tri (2-methyl) propenoic acid trimethylolhexane, tri (2-methyl) propenoic acid trimethyloloctane, tri (2-methyl) propenoic acid 2,2-bis (hydroxymethyl) 1,3-propanediol, tri (2-methyl) propenoic acid 1,1,1-tris Trifunctional (2-methyl) propene such as hydroxymethylethane, tri (2-methyl) propenoic acid 1,1,1-trishydroxymethylpropane Esters;

  Tetra (2-methyl) propenoic acid 2,2-bis (hydroxymethyl) 1,3-propanediol, tetra (2-methyl) propenoic acid 2,2-bis (hydroxymethyl) 1,3-propanediol tetracaprolactonate, tetra (2-methyl) propenoic acid di1,2,3-propanetriol, tetra (2-methyl) propenoic acid di-2-methylpentane-2,4-diol, Tetra (2-methyl) propenoic acid di-2-methylpentane-2,4-diol tetracaprolactonate, tetra (2-methyl) propenoic acid di-2,2-dimethylpropane-1,3-diol, tetra (2 -Methyl) ditrimethylolbutane propenoate, ditrimethylolhexane tetra (2-methyl) propenoate, tetra (2-methyl) propene Acid ditrimethyloloctane, tetra (2-methyl) propenoate di-2,2-bis (hydroxymethyl) 1,3-propanediol, hexa (2-methyl) propenoate di-2,2-bis (hydroxymethyl) 1, 3-propanediol, hexa (2-methyl) propenoate tri-2,2-bis (hydroxymethyl) 1,3-propanediol, hepta (2-methyl) propenoate tri-2,2-bis (hydroxymethyl) 1, 3-propanediol, tri (2-methyl) propenoate tri-2,2-bis (hydroxymethyl) 1,3-propanediol, hepta (2-methyl) propenoate di-2,2-bis (hydroxymethyl) 1, Polyfunctional (2-methyl) propenoic acid esters such as 3-propanediol polyalkene oxide;

  For example, di (2-methyl) propenoic acid ethane 1,2-diol, di (2-methyl) propenoic acid, 2,2′-oxyethane-1-ol, di (2-methyl) propenoic acid 3,6-di Oxaoctane-1,8-diol, di (2-methyl) propenoic acid 3,6,9-trioxaundecane-1,11-diol, di (2-methyl) propenoic acid 3,6,9,12-tetra Oxatetradecane-1,14-diol, 2-ethyl-2- (hydroxymethyl) propane-1,3-diol tri (2-methyl) propenoate, 2,2-bis (hydroxy) tri (2-methyl) propenoate Methyl) propane-1,3-diol, 1,1,1-trishydroxymethylethane di (2-methyl) propenoate, 1,1,1-trishydroxy tri (2-methyl) propenoate Chiruetan, tri (2-methyl) polyfunctional (2-methyl) propenoic acid esters such as propenoic acid 1,1,1-tris hydroxymethyl propane.

  Examples of the alkenyl group-containing compound include ethenylbenzene, α-isopropenylbenzene, β-isopropenylbenzene, 1-methylethenylbenzene, 2-methylethenylbenzene, 3-methylethenylbenzene, 1-butylethenyl. Aromatic ethenyl monomers such as tenenylbenzene and 1-chloro-4-isopropenylbenzene;

  For example, ethenyl phenyl pentyl ether, ethenyl phenyl hexyl ether, ethenyl phenyl heptyl ether, ethenyl phenyl octyl ether, ethenyl phenyl nonyl ether, ethenyl phenyl decyl ether, ethenyl phenyl undecyl ether, ethenyl phenyl dodecyl ether Ethenyl phenyl tridecyl ether, ethenyl phenyl tetradecyl ether, ethenyl phenyl pentadecyl ether, ethenyl phenyl hexadecyl ether, ethenyl phenyl heptadecyl ether, ethenyl phenyl octadecyl ether, ethenyl phenyl nonadecyl ether, Tenenylphenyl eicosyl ether, ethenylphenyl henecosyl ether, ethenylphenyl docosyl ether, ethenylphenyl Butyl butyl ether, ethenyl phenyl methyl pentyl ether, ethenyl phenyl methyl hexyl ether, ethenyl phenyl methyl heptyl ether, ethenyl phenyl methyl octyl ether, ethenyl phenyl methyl nonyl ether, ethenyl phenyl methyl decyl ether, ethenyl phenyl methyl ether Decyl ether, ethenyl phenyl methyl dodecyl ether, ethenyl phenyl methyl tridecyl ether, ethenyl phenyl methyl tetradecyl ether, ethenyl phenyl methyl pentadecyl ether, ethenyl phenyl methyl hexadecyl ether, ethenyl phenyl methyl heptadecyl ether, Ethenyl phenyl methyl octadecyl ether, ethenyl phenyl methyl nonadecyl ether, ethenyl phenyl methyl Lee waist ether, ethenyl phenylmethyl hen eicosyl ether, aromatic ethenyl ether monomer having a long-chain alkyl groups such as ethenyl phenylmethyl docosyl ether;

  For example, isopropenyl phenylmethyl butyl ether, isopropenyl phenyl methyl pentyl ether, isopropenyl phenyl methyl hexyl ether, isopropenyl phenyl methyl heptyl ether, isopropenyl phenyl methyl octyl ether, isopropenyl phenyl methyl nonyl ether, isopropenyl phenyl methyl decyl ether, Isopropenyl phenylmethyl undecyl ether, isopropenyl phenyl methyl dodecyl ether, isopropenyl phenyl methyl tridecyl ether, isopropenyl phenyl methyl tetradecyl ether, isopropenyl phenyl methyl pentadecyl ether, isopropenyl phenyl methyl hexadecyl ether, isopropenyl phenyl Methyl heptadecyl ether, Isopropenyl phenyl having a long chain alkyl group such as isopropenyl phenyl methyl octadecyl ether, isopropenyl phenyl methyl nonadecyl ether, isopropenyl phenyl methyl eicosyl ether, isopropenyl phenyl methyl heneicosyl ether, isopropenyl phenyl methyl docosyl ether System monomers;

  Hexyl 4-ethenylbenzenecarboxylate, octyl 4-ethenylbenzenecarboxylate, nonyl 4-ethenylbenzenecarboxylate, decyl 4-ethenylbenzenecarboxylate, dodecyl 4-ethenylbenzenecarboxylate, 4-ethenylbenzene Tetradecyl carboxylate, hexadecyl 4-ethenylbenzenecarboxylate, octadecyl 4-ethenylbenzenecarboxylate, eicosyl 4-ethenylbenzenecarboxylate, docosyl 4-ethenylbenzenecarboxylate, hexyl 4-isopropenylbenzenecarboxylate, 4 -Octyl isopropenylbenzenecarboxylate, nonyl 4-isopropenylbenzenecarboxylate, decyl 4-isopropenylbenzenecarboxylate, dodecyl 4-isopropenylbenzenecarboxylate, 4-isopropenylbenzenecarboxyl Ethenylbenzene having a long-chain alkyl group such as tetradecyl acid, hexadecyl 4-isopropenylbenzenecarboxylate, octadecyl 4-isopropenylbenzenecarboxylate, eicosyl 4-isopropenylbenzenecarboxylate, docosyl 4-isopropenylbenzenecarboxylate Carboxylate ester or isopropenylbenzene carboxylate monomers;

  For example, tetra (ethene oxide) ethenylphenyl ether, methyltetra (etheneoxide) ethenylphenylether, ethyltetra (etheneoxide) ethenylphenylether, propyltetra (etheneoxide) ethenylphenylether, n-butyltetra (etheneoxide) ) Ethenyl phenyl ether, n-pentyltetra (ethene oxide) ethenyl phenyl ether, tetra (propene oxide) ethenyl phenyl ether, methyl tetra (propene oxide) ethenyl phenyl ether, ethyl tetra (propene oxide) ethenyl phenyl ether, Propoxytetra (propene oxide) ethenyl phenyl ether, n-butyltetra (propene oxide) ethenyl phenyl ether, n Pentaxytetra (propene oxide) ethenyl phenyl ether, poly (ethene oxide) ethenyl phenyl ether, methyl poly (ethene oxide) ethenyl phenyl ether, ethyl poly (ethene oxide) ethenyl phenyl ether, poly (propene oxide) ethenyl phenyl Ether, methyl poly (propene oxide) ethenyl phenyl ether, ethyl poly (propene oxide) ethenyl phenyl ether, poly (ethene oxide) ethenyl benzyl ether, methyl poly (ethene oxide) ethenyl benzyl ether, ethyl poly (ethene oxide) ethenyl benzyl Ether, poly (propene oxide) ethenyl benzyl ether, methyl poly (propene oxide) ethenyl benzyl ether Ethyl poly (propene oxide) ethenyl benzyl ether, poly (ethene oxide) ethenyl phenyl ethyl ether, methyl poly (ethene oxide) ethenyl phenyl ethyl ether, ethyl poly (ethene oxide) ethenyl phenyl ethyl ether, poly (oxypropylene) vinyl phenyl An ethenylbenzene monomer having a long-chain polyalkene oxide moiety such as ethyl ether, methyl poly (propene oxide) ethenylphenyl ethyl ether, ethyl poly (propene oxide) ethenylphenyl ethyl ether;

  For example, poly (ethene oxide) isopropenyl phenyl ether, methyl poly (ethene oxide) isopropenyl phenyl ether, ethyl poly (ethene oxide) isopropenyl phenyl ether, poly (propene oxide) isopropenyl phenyl ether, methyl poly (propene oxide) isopropenyl phenyl Ether, ethyl poly (propene oxide) isopropenyl phenyl ether, poly (ethene oxide) isopropenyl benzyl ether, methyl poly (ethene oxide) isopropenyl benzyl ether, ethyl poly (ethene oxide) isopropenyl benzyl ether, poly (propene oxide) isopropenyl benzyl ether Ether, methylpoly (propene oxide) isopropenylbenzyl Isopropenyl monomer having a polyalkene oxide moiety, such as ether;

  For example, mono long chain alkyl ester of dicarboxylic acid such as ethenylphenylnonyl butanedioate, ethenylphenylmethyldecyl hexahydrobenzene-1,2-dicarboxylate, ethenylphenylethyldodecyl benzene-1,4-dicarboxylate Monomer;

  For example, butanedioic acid ethenyl phenyl poly (ethene oxide), hexahydrobenzene-1,2-dicarboxylic acid ethenyl phenyl methyl poly (ethene oxide), benzene-1,4-dicarboxylic acid ethenyl phenyl ethyl poly (ethene oxide) ) Monocarboxylic acid esters of dicarboxylic acids such as 4-ethenylbenzenecarboxylate methyl poly (ethene oxide), 4-ethenylbenzenecarboxylate ethyl poly (ethene oxide), 4-isopropenylbenzenecarboxylate methyl poly (propene oxide), 4-Ethenylbenzenecarboxylic acid ester or polypropenebenzenecarboxylic acid ester having a polyalkene oxide moiety such as ethyl 4- (isopropenylbenzenecarboxylate) poly (propene oxide) Monomer;

  For example, fluorine-containing ethenyl monomers such as perfluoroethene, perfluoropropene, perfluoro (propyl ethenyl ether), ethenylidene fluoride;

  For example, triethyloxysilyl group-containing ethenyl monomers such as ethenyltrimethoxysilane and ethenyltriethoxysilane;

  For example, cis-butenedioic acid di-2-propenyl, 2-methylidenebutanedioic acid diallyl, (E) -but-2-enoic acid ethenyl, (Z) -octadec-9-enoic acid ethenyl, (9Z, 12Z, 15Z) -Ethenyl ester monomers further containing an unsaturated bond such as octadeca-9,12,15-trienoic acid ethenyl;

  For example, nitrile group-containing ethenyl monomers such as 2-propenenitrile, 2-methyl-2-propenenitrile, 2-cyanoethyl (2-methyl) propenoate;

  For example, 2-propenamide, 2-methylprop-2-enoylamine, N, N-dimethyl-2-propenamide, N, N-diethyl-2-propenamide, N-methoxymethyl-2-propenamide, N-ethoxy Methyl (2-methyl) propenamide, N- (n-, iso-) butoxymethyl (2-methyl) propenamide, N-methoxyethyl (2-methyl) propenamide, N-ethoxyethyl (2-methyl) propene Amide, N- (n-, iso-) butoxyethyl (2-methyl) propenamide, N- [3- (N ′, N′-dimethylamino) propyl] -2-propenamide, N-isopropyl-2- Aliphatic amide group-containing ethenyl monomers such as propeneamide, N-ethenylmethanamide, N-ethenylacetamide;

  For example, cyclic amide group-containing ethenyl monomers such as 4-propenoylmorpholine, N-ethenyl-2-pyrrolidone, N-ethenyl-2-azehan-2-one;

  For example, nitrogen atom content such as 2-ethenylpyridine, 4-ethenylpyridine, 2-ethenylpiperazine, N-ethenylimidazole, 4-ethenylpiperazine, 2,4-diamino-6-ethenyl-s-triazine Heterocyclic ethenyl monomers;

  For example, ethenyl esters such as ethenyl ethanoate, ethenyl propanoate, ethenyl pivalate, ethenyl benzenecarboxylate, ethenyl 3-phenyl-2-propenoate;

  For example, ethenylbenzenesulfonic acid, ethenylsulfonic acid, 2-propenylsulfonic acid, 2-propenyloxybenzenesulfonic acid, 2-methyl-2-propenylsulfonic acid, 2-methyl-2-propenyloxybenzenesulfonic acid, ethenyl Alkenyl group-containing sulfonic acid compounds such as sulfuric acid, ammonium ethenylbenzenesulfonate, monomethylammonium ethenylbenzenesulfonate, dimethylammonium ethenylbenzenesulfonate, trimethylammonium ethenylbenzenesulfonate, tetramethylammonium ethenylbenzenesulfonate Ethenylammonium ethenylbenzenesulfonate, diethylammonium ethenylbenzenesulfonate, triethylammonium ethenylbenzenesulfonate, ethenylbenzenesulfate Tetraethylammonium nitrate, propylammonium ethenylbenzenesulfonate, dipropylammonium ethenylbenzenesulfonate, tripropylammonium ethenylbenzenesulfonate, butylammonium ethenylbenzenesulfonate, pentylammonium ethenylbenzenesulfonate or ethenylbenzene Alkenyl salts containing alkenyl groups such as hexylammonium sulfonate, sodium ethenylbenzenesulfonate, potassium ethenylbenzenesulfonate, lithium ethenylbenzenesulfonate, magnesium ethenylbenzenesulfonate, ethenylbenzenesulfone Alkenyl group-containing ethenylbenzene sulfonic acid metal salts such as zinc acid and iron ethenylbenzene sulfonate Metal salts and ammonium salts of alkenyl groups containing alkenyl groups such as ammonium sulfonate, sodium ethenyl sulfonate, potassium ethenyl sulfonate, etc., containing ammonium ethenyl sulfonate, sodium ethenyl sulfonate, potassium ethenyl sulfonate alkenyl group 2 -Metal salts such as propenyl sulfonic acid, sodium ethenyl alkyl sulfosuccinate and ammonium salts, ammonium ethenyloxybenzene sulfonate, sodium ethenyloxybenzene sulfonate, potassium ethenyloxybenzene sulfonate alkenyl group-containing ethenyloxybenzene Metal salts and ammonium salts of sulfonic acid, ammonium 2-methyl-2-propenylsulfonate, sodium 2-methyl-2-propenylsulfonate, 2-methyl-2 -Metal salts and ammonium salts of 2-methyl-2-propenylsulfonic acid containing alkenyl group such as potassium propenylsulfonate, ammonium 2-methyl-2-propenyloxybenzenesulfonate, 2-methyl-2-propenyloxybenzenesulfonic acid Sodium, 2-methyl-2-propenyloxybenzenesulfonic acid potassium alkenyl group-containing 2-methyl-2-propenyloxybenzenesulfonic acid metal salt and ammonium salt, (2-methyl) 2-propenamidesulfonic acid [2-propene Amidosulfonic acid and 2-methyl-2-propenamidesulfonic acid are collectively referred to as “(2-methyl) 2-propenamidesulfonic acid”. The same applies below. ], Tert-butyl- (2-methyl) 2-propenamidesulfonic acid, alkenyl group-containing sulfonic acids such as (2-methyl) 2-propenamide-2-methyl-1-propanesulfonic acid

  For example, 2-carboxyethyl propenoate, 2-methylidenebutanedioic acid, cis-butenedioic acid, trans-butenedioic acid, penta-2-enedioic acid, 2-methyl (E) -2-butenedioic acid, etc. Saturated carboxylic acids;

  For example, unsaturated carboxylic acid anhydrides such as 2,5-dihydrofuran-2,5-dione, 3-methylidenetetrahydrofuran-2,5-dione, 3-methyl-2,5-dihydrofuran-2,5-dione, etc. Things;

  For example, monoalkyl esters and dialkyl esters of the above unsaturated carboxylic acids;

  For example, glycidyl group-containing ethenyl esters such as glycidyl cinnamate, 2-propenyl glycidyl ether, ethenyl cyclohexene monooxirane, 1,3-butadiene monooxirane;

  Examples include chloroethylene, 1,1-dichloroethylene, 2-propenyl chloride, 2-propenyl alcohol and the like, but are not particularly limited thereto. These may use only 1 type or may use multiple types together.

  Moreover, in obtaining the silane compound (1) used for this invention, the compound which has (alpha), (beta)-unsaturated double bond other than these can also be used as needed, and the example of such a compound Examples of maleimide derivatives such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide;

  For example, ethene, propene, 1-butene, 2-butene, 2-methylpropene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene 1-docosene, 1-tetracocene, 1-hexacocene, 1-octacocene, 1-triacontene, 1-dotriacontene, 1-tetratoacontene, 1-hexatriacontene, 1-octatriacontene, 1-tetraconten And alkenes such as polybutene-1, polypentene-1, poly-4-methylpentene-1, etc .;

  Examples thereof include dienes such as allene, 1,2-butadiene, 1,3-butadiene, 2-methyl-1,3-butadiene, and 2-chloro-1,3-butadiene.

  Further, for example, an α, β-unsaturated compound having a copolymerizable α, β-unsaturated double bond obtained by reacting the above-mentioned glycidyl group-containing ethenyl ester with a fatty acid, the above-mentioned halogenation Copolymerizable α obtained by reacting alkylethenylbenzenes with at least one alcoholic hydroxyl group-containing compound selected from long-chain alcohols, poly (ethene oxide), and / or poly (ethene oxide) monoalkyl ethers , Β-unsaturated compounds having a β-unsaturated double bond are also included in the α, β-unsaturated group-containing monomer (X).

In addition, as R4, the polymer (A) that forms a Si—C bond by a hydrosilylation reaction has a weight average molecular weight (Mw) of 200 to 2,000,000 and an α, β-unsaturated double bond. It is necessary.
The polymer (A) is preferably a polymer of an α, β-unsaturated group-containing monomer (X) or the like, and is a polymer of at least two types of α, β-unsaturated group-containing monomers (X). Preferably there is. It may be a so-called macromonomer. The polymerization method is preferably bulk polymerization. For example, when bulk polymerization is performed on the α, β-unsaturated group-containing monomer (X) at 200 ° C. or higher, a high molecular weight type in which an α, β-unsaturated double bond is selectively generated at the polymer terminal. A polymer (A) is produced. In addition, by subjecting a polymer produced by general copolymerization to a thermal decomposition reaction, an α, β-unsaturated double bond is produced at the polymer terminal by the cleavage reaction of the main chain by heat, and the polymer (A ) Is generated.

  As described above, when R4 is a site excluding the α, β-unsaturated double bond of the α, β-unsaturated compound, the compatibility with the polymer (D) described later is improved. After application to an adherend such as a glass plate when a pressure sensitive adhesive using a resin composition for an adhesive containing the silane compound (1) and the polymer (D) is applied to an optical film, etc. When exposed to a high temperature or high temperature and high humidity for a long period of time, the compatibility is good, the coating film is not whitened, and cracks and foaming are less likely to occur. Moreover, since the compatibility is good, the problem of deterioration in durability over time due to the liberation of the silane compound (1) hardly occurs, which is preferable. Moreover, when R4 containing silane compound (1) in the present invention is formed from a polymer site, the weight average molecular weight (Mw) is preferably from 200 to 2,000,000, more preferably from 500 to 100,000. . When the polymer part has a weight average molecular weight (Mw) of 200 or less, the silane compound (1) is a part of the part excluding the α, β-unsaturated double bond of the α, β-unsaturated compound (X). Since the compatibility is good, the characteristics of the polymer site cannot be obtained, which is not preferable. On the other hand, in the case of 2,000,000 or more, the compatibility is poor, and the coating film is whitened or the content of Si element is lowered, so that the expected effect cannot be obtained, which is not preferable.

Next, the polymer (D) will be described.
The polymer (D) of the present invention is a polymer of an α, β-unsaturated group-containing monomer (X), and is a polymer of at least two types of α, β-unsaturated group-containing monomers (X). It is preferably a coalescence. Moreover, you may superpose | polymerize by adding the macromonomer mentioned above. As the α, β-unsaturated group-containing monomer (X), the above-described monomers can be used.
The polymer (D) used in the present invention does not contain the active hydrogen group-containing α, β-unsaturated monomer and the active hydrogen group from the α, β-unsaturated group-containing monomer (X). It can be obtained by appropriately selecting and polymerizing an α, β-unsaturated monomer. The active hydrogen group-containing α, β-unsaturated monomer is an α, β-unsaturated compound having various functional groups such as hydroxyl group, carboxyl group, amino group, amide group and maleimide group in its structure. . Considering the reactivity with the cross-linking agent (G) described later, a homogeneous cross-linking structure or IPN structure [interpenetrating polymer network (intermutating polymer network) that does not clearly express a sparse / dense distribution with the cross-linking agent (G) described later. In order to form an intrusion polymer network)], a carboxyl group or a hydroxyl group is more preferable as the functional group. When the reactivity of the functional group in the polymer (D) that reacts with the crosslinking agent (G) described later to form a crosslinked structure or an IPN structure is slow, it takes a long time to complete the formation of the crosslinked structure. However, since it is not allowed for such a long time industrially, a uniform cross-linked state or IPN structure cannot be exhibited, and the pressure-sensitive adhesive layer has a sparse part and a dense part. Since the pressure-sensitive adhesive layer having such a coarse and dense distribution has a small cohesive force, after applying the optical pressure-sensitive adhesive film to the adherend and exposing it to a harsh environment under high temperature or high temperature and high humidity, Since stress concentrates on a portion having a low crosslinking density, and foaming, floating and peeling are likely to occur, this is not preferable. Accordingly, the functional group in the polymer (D) preferably has at least one of a carboxyl group and a hydroxyl group rich in reactivity.
A carboxyl group and a hydroxyl group are located in the side chain of the polymer (D), and these functional groups react with a crosslinking agent (G) described later to form a pressure-sensitive adhesive layer.
The carboxyl group is preferably introduced into the polymer (D) using propenoic acid or 2-methylpropenoic acid in the copolymerization.
Moreover, it is preferable to introduce into the polymer (D) a hydroxyl group using a propenoic acid derivative having a hydroxyl group or a 2-methylpropenoic acid derivative having a hydroxyl group during the polymerization.

Compound having a carboxyl group that can react with the crosslinking agent (G) when the total amount of the α, β-unsaturated group-containing monomer (X) used as a raw material for the polymer (D) is 100% by weight. The total amount of the compounds having a hydroxyl group is preferably 0.01 to 80% by weight. If it is less than 0.01% by weight, a sufficient cross-linked structure cannot be obtained. Therefore, the cohesive strength of the pressure-sensitive adhesive layer is low, and the stability and durability during repeated use are inferior.
Moreover, when it exceeds 80 weight%, since the cohesion force of a pressure sensitive adhesive layer becomes high too much, As a result, between glass and a pressure sensitive adhesive layer becomes easy to peel, it is unpreferable. In particular, when placed in an environment where the temperature and humidity vary, the glass and the pressure-sensitive adhesive layer are more easily peeled off.

When the polymer (D) is used as a pressure-sensitive adhesive, the glass transition point (Tg) is −80 to 10 so that it can exhibit well-balanced adhesive properties (particularly, both tack and cohesive force). It is preferable to select the α, β-unsaturated group-containing monomer (X) so as to form a polymer at ° C, more preferably from -60 to 0 ° C.
When the glass transition point of the copolymer is lower than −80 ° C., the cohesive force of the pressure-sensitive adhesive layer obtained by using the polymer is lowered, and it is likely to be lifted off. On the other hand, when the glass transition point exceeds 10 ° C., a pressure-sensitive adhesive layer having sufficient tack cannot be obtained.

If the Tg of the homopolymer that can be formed from each α, β-unsaturated group-containing monomer (X) that is a constituent of the polymer (D) is known, the Tg of each homopolymer and each α, Based on the composition ratio of the β-unsaturated group-containing monomer (X), the Tg of the polymer (D) can be theoretically determined.
By the way, in the case of a pressure sensitive adhesive, it is common to mix | blend a small amount of below-mentioned crosslinking agent (G) with respect to the polymer (D) which is a main component. Since the adhesive layer formed from such a pressure-sensitive adhesive is loosely crosslinked (in other words, sparse), the Tg of the adhesive layer is different from that of a cured coating film that is densely crosslinked. It is approximately equal to the Tg of the combined (D). Accordingly, the types of various α, β-unsaturated group-containing monomers (X) so that the Tg of the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive is 10 ° C. or lower, preferably 0 ° C. or lower, Just select the amount. On the other hand, the pressure sensitive adhesive layer having a so-called IPN structure in which a large amount of a crosslinking agent (G) described later is blended with the polymer (D) has a Tg after crosslinking that is significantly different from that before crosslinking. It is preferable to obtain by (differential scanning calorimetry) or dynamic viscoelasticity measurement.

  The polymer (D) in the present invention is 0.001 to 5 parts by weight of the polymerization initiator based on 100 parts by weight of the total of various α, β-unsaturated group-containing monomers (X) as described above. Is synthesized by a method such as bulk polymerization, solution polymerization, emulsion polymerization or suspension polymerization. Preferably, it is synthesized by solution polymerization.

  Examples of the polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane 1-carbonitrile) and 2 , 2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile) and dimethyl 2,2'-azobis (2-methylpropionate) 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2-hydroxymethylpropionitrile), 2,2′-azobis [2- (2-imidazolin-2-yl) An azo compound such as propane].

  Also, benzoyl peroxide, tert-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di (2-ethoxyethyl) peroxydicarbonate, tert-butyl peroxy Organic such as 2-ethylhexanoate, tert-butylperoxyneodecanoate, tert-butylperoxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, diacetyl peroxide A peroxide is mentioned.

  In the synthesis, mercaptans such as lauryl mercaptan and n-dodecyl mercaptan, chain transfer agents such as α-methylethenylbenzene dimer and limonene may be used.

  The weight average molecular weight (Mw) of the polymer (D) is preferably 50,000 to 2,000,000 from the viewpoint of adhesiveness, and more preferably in the range of 200,000 to 1,500,000. . When Mw exceeds 2,000,000, the fluidity of the polymer becomes poor, so that the coating property of the pressure-sensitive adhesive deteriorates and it is difficult to produce the pressure-sensitive adhesive layer itself on the peelable film. It becomes. On the other hand, when Mw is less than 50,000, cohesive failure of the pressure-sensitive adhesive layer is likely to occur after the optical pressure-sensitive adhesive film is attached to a liquid crystal cell member such as glass, which is not preferable.

  It is preferable that the resin composition for adhesives of this invention contains 0.01-30 weight part of silane compounds (1) with respect to 100 weight part of polymers (D), and contains 0.1-20 weight part More preferably. If it is less than 0.01 part by weight, the effect of suppressing cracks and the effect of improving removability cannot be expected. On the other hand, if it exceeds 30 parts by weight, the cohesive force is insufficient, foaming is likely to occur in the durability test, and the optical properties are deteriorated, which is not preferable.

As described above, the silane compound (1) of the present invention has an organic functional group having affinity and reactivity for the polymer (D) in one molecule, and affinity and reaction for inorganic and metallic materials. A silane compound having a silyl group having an adhesive property and a polymer (D), and an adhesion improver showing adhesion improvement appropriateness such as improved adhesion at the interface between the polymer (D) and an inorganic or glass or metal material; can do.
That is, when a pressure-sensitive adhesive containing a resin composition for an adhesive containing a silane compound (1) is used, there is an adhesion improvement suitability. Therefore, a laminate in which a polarizing film or the like is attached to a glass surface for a liquid crystal cell is used. Even if it is exposed to high temperature or high temperature and high humidity for a long time, the polarizing film does not come off and cracks in the vicinity of the peripheral edge and microbubbles in the center do not occur. Since white spots do not occur, it is preferable.

  Next, a manufacturing method will be described.

The manufacturing method of the resin composition for adhesives of this invention can be implemented with the following two methods.
(Production Method I) A silane compound (1) is prepared in advance by hydrosilylation reaction of an α, β-unsaturated group-containing monomer (X) and a compound (2), and the polymer (D) Adjustment process to mix.
The method for synthesizing the silane compound (1) is as described above.

(Production Method II) During the process of polymerizing the α, β-unsaturated group-containing monomer (X) to produce the polymer (D), at any time, adding the compound (2) any number of times, A resin composition for an adhesive containing the silane compound (1) can be produced by a hydrosilylation reaction.
And preferably, a first step of polymerizing the α, β-unsaturated group-containing monomer (X) to react the polymer (D) to a reaction rate of 70 to 99.9%;
Next, the compound (2) is added, and the unpolymerized α, β-unsaturated group-containing monomer (X) remaining in the first step and the compound (2) are subjected to a hydrosilylation reaction, and the monomer ( A second step of obtaining a silane compound (1), which is a reaction product of X) and the compound (2), and a polymer (D);
It can manufacture by the process including. In addition to the monomer (X), a macromonomer may be used.

(Manufacturing method II) is demonstrated in detail.
In the production method II, after the α, β-unsaturated group-containing monomer (X) is polymerized to a reaction rate of 70 to 99.9% (the first step), the compound (2) is added and the remaining α , Β-unsaturated group-containing monomer (X) and an oligomer having an α, β-unsaturated double bond are preferably subjected to a hydrosilylation reaction (second step). It is more preferable to carry out the hydrosilylation reaction after reacting to a reaction rate of 80 to 99%. When the reaction rate is 70% or less, the content of the silane compound (1) to be produced is 30% or more, the cohesive force is insufficient, foaming is likely to occur in the durability test, and the optical characteristics are deteriorated. It is not preferable. A reaction rate of 99.9% or more is not preferable because a crack suppressing effect and a removability improving effect cannot be expected. In addition, the application of the production method of production method II can reduce the amount of unpolymerized α, β-unsaturated group-containing monomer (X) not involved in the polymerization in the polymer (D). When used as an adhesive, it not only suppresses foaming and fumes during coating due to the residual α, β-unsaturated group-containing monomer (X), but also as an optical adhesive film on glass, etc. Adhesion is preferred because foaming and floating of the adhesive layer during heating or heat of humidification are suppressed. Furthermore, since scattering of the α, β-unsaturated group-containing monomer (X) is eliminated, it is particularly preferable in terms of environment and hygiene.

  Thus, after reacting the α, β-unsaturated compound (X) to a reaction rate of 70 to 99.9% (first step), the compound (2) is added to the remaining α, β-unsaturated. Resin composition for adhesives by production method II including a two-stage process of hydrosilylation reaction with a group-containing monomer (X) and an oligomer having an α, β-unsaturated double bond (second process) Can be manufactured.

Further, these two production methods are advantageous in adjusting the reaction conditions because changes in the infrared absorption spectrum 2190 cm ⁻¹ of the silyl group before and after production methods I and II can be confirmed.
Furthermore, the resin composition for adhesives can also be produced by using production methods I and II in combination.

Thus, among the silane compounds (1) contained in the resin compositions for adhesives obtained by the production methods I and II, the active hydrogen group-containing α, β-unsaturated monomer and the compound (2) The silane compound (1) obtained by the addition reaction has an R4 (active hydrogen group-containing α, β-unsaturated monomer α, β-unsaturated double bond in the structure of the hydrosilyl group of the compound (2). It is a compound having various functional groups such as a hydroxyl group, a carboxyl group, an amino group, an amide group, and a maleimide group derived from the active hydrogen group-containing α, β-unsaturated monomer (B) at the added site. Having these functional groups allows reaction with the crosslinking agent (G) described later, delocalizes the polymer, and allows it to be firmly fixed, so that it adheres to glass plates and the like. Is improved and preferable.
On the other hand, the silane compound (1) obtained by the addition reaction between an α, β-unsaturated monomer not containing an active hydrogen group and the compound (2) has a polymer (D) described later on R4 in the structure. Since it has a chain | strand which becomes compatibility improvement with, it is preferable.

Next, the crosslinking agent (G) will be described.
In this invention, a pressure-sensitive adhesive is obtained by containing a crosslinking agent (G) in the resin composition for adhesives which has the silane compound (1) in the polymer (D).
As described above, the crosslinking agent (G) of the present invention is used to form a crosslinked structure with the polymer (D) and further to form an IPN structure in addition to the crosslinked structure.
When the functional group in the polymer (D) is a carboxyl group, examples of the functional group of the crosslinking agent (G) include an isocyanate group, an oxirane group, an amino group, an aziridyl group, an oxazoline group, and a metal chelate group. When the functional group in D) is a hydroxyl group, the functional group of the crosslinking agent (G) includes an isocyanate group and an N-hydroxymethyl group.
In particular, a polyisocyanate compound having an isocyanate group is preferably used because it is excellent in the adhesion of the pressure-sensitive adhesive after the crosslinking reaction and the adhesion to the coating layer.

  For example, examples of the polyisocyanate compound having an isocyanate group include aromatic polyisocyanate, aliphatic polyisocyanate, araliphatic polyisocyanate, and alicyclic polyisocyanate.

  Aromatic polyisocyanates include 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-triisocyanate. Range isocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4 ', 4 " -Triphenylmethane triisocyanate etc. can be mentioned.

  Aliphatic polyisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate. 2,4,4-trimethylhexamethylene diisocyanate and the like.

  Examples of the araliphatic polyisocyanate include ω, ω′-diisocyanate-1,3-dimethylbenzene, ω, ω′-diisocyanate-1,4-dimethylbenzene, ω, ω′-diisocyanate-1,4-diethylbenzene, , 4-tetramethylxylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate, and the like.

  Examples of alicyclic polyisocyanates include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl- Examples include 2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4′-methylene bis (cyclohexyl isocyanate), 1,4-bis (isocyanate methyl) cyclohexane and the like.

  Moreover, 2-methylpentane-2,4-diol adduct of the above polyisocyanate, trimer having an isocyanurate ring, etc. can be used together. Polyphenylmethane polyisocyanate (PAPI), naphthylene diisocyanate, and these polyisocyanate modified products can be used. As the polyisocyanate-modified product, a carbodiimide group, a uretdione group, a uretoimine group, a burette group reacted with water, a group of isocyanurate groups, or a modified product having two or more of these groups can be used. A reaction product of a polyol and a diisocyanate can also be used as a polyisocyanate.

  These polyisocyanate compounds include 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), xylylene diisocyanate, 4,4′-methylenebis. From the viewpoint of weather resistance, it is particularly preferable to use a non-yellowing or hardly yellowing polyisocyanate compound such as (cyclohexyl isocyanate) (hydrogenated MDI).

  When using a polyisocyanate compound as a crosslinking agent (G), a well-known catalyst can be used as needed for reaction promotion. For example, a tertiary amine compound, an organometallic compound, etc. are mentioned, and it is possible to use a single compound or plural compounds.

  Examples of the tertiary amine compound include triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, diazabicycloundecene (DBU) and the like, and depending on the case, they can be used alone or in combination. .

Examples of organometallic compounds having a metal chelate group include tin compounds and non-tin compounds.
Examples of tin compounds include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (DBTDL), dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, tributyltin acetate , Triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate, tin 2-ethylhexanoate and the like.
Examples of non-tin compounds include titanium compounds such as dibutyltitanium dichloride, tetrabutyltitanate and butoxytitanium trichloride, lead compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate and lead naphthenate, 2- Iron such as iron ethylhexanoate and iron 2,4-pentadionate, cobalt such as cobalt benzenecarboxylate and cobalt 2-ethylhexanoate, zinc such as zinc naphthenate and zinc 2-ethylhexanoate, naphthene Examples thereof include zirconium acid.
Among the above catalysts, dibutyltin dilaurate (DBTDL), tin 2-ethylhexanoate and the like are preferable in terms of reactivity and hygiene.

Examples of oxirane compounds having an oxirane group include 2,2-bis (hydroxyphenyl) propane / 2-chloromethyloxirane type oxirane resins, 2,2-bis (hydroxyphenyl) methane type, 2,2 -Bis (4-hydroxyphenyl) ethane type, 2,2-bis (4-hydroxyphenyl) butane type, 4,4'-sulfonyldiphenol type, 1,1-dichloro-2,2-bis (4-hydroxy) Phenyl) ethene type, 1,3-bis [2- (4-hydroxyphenyl) -2-propyl] benzene type, 2,2-bis (4-hydroxy-3-methylphenyl) propane type, 2,2-bis (4-hydroxy-3-methylphenyl) methane type, 2,2-bis (4-hydroxy-3-methylphenyl) hexafluoropropane type, 2,2-bis ( 4-hydroxy-3,5-dimethylphenyl) propane type, 2,2-bis (4-hydroxycyclohexyl) propane type, 2,2-bis (2-hydroxy-5-biphenylyl) propane type, and combinations thereof Polymerization type oxirane resin, phenol novolak type, orthocresol novolak type, paratertiary butylphenol novolak type, paraoctylphenol novolak type, nonylphenol novolak type and co-condensation type oxirane resins, ethene oxide diglycidyl ether, polyethene oxide Diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, diglycidyl ether Phosphorus, N, N, N ', N'-tetraglycidyl -m- xylylenediamine, 1,3-bis (N, N'-diglycidyl aminomethyl) cyclohexane.
Etc.

An example of an amine compound having an amino group is preferably a polyamine having two or more primary amino groups, and has two or more primary amino groups not directly bonded to an aromatic ring from the viewpoint of excellent crosslinking speed. An aliphatic polyamine (which may contain an aromatic ring in its skeleton) which is a polyamine is preferred.
Aliphatic polyamines include 2,5-dimethyl-2,5-hexamethylenediamine, mensendiamine, 1,4-bis (2-amino-2-methylpropyl) piperazine, and propylene branched carbon at both ends of the molecule. Polypropene oxide (propene skeleton diamine such as “Jeffamine D230” and “Jephamine D400” manufactured by Sun Techno Chemical Co., Ltd., etc.), propene oxide skeleton triamine such as “Jeffamine T403”, etc. Ethenediamine, propenediamine, butenediamine, diethenetriamine, triethenetetramine, tetraethenepentamine, pentaethenehexamine, hexamethylenediamine, trimethylhexamethylenediamine, N-aminoethylpiperazine, 1,2-diaminopropa , Iminobispropylamine, methyl _{iminobispropylamine, H 2 N (CH 2 CH} 2 O) 2 (CH 2) 2 NH 2 [ Sun Techno Chemical Co., Ltd. "Jeffamine EDR148" (of ethene oxide skeleton diamine) such as Polyether skeleton diamine with methylene group bonded to amine nitrogen, 1,5-diamino-2-methylpentane ("MPMD" manufactured by DuPont Japan), metaxylylenediamine (MXDA), polyamidoamine (Sanwa Chemical Co., Ltd.) "X2000"), isophoronediamine, 1,3-bisaminomethylcyclohexane ("1,3BAC" manufactured by Mitsubishi Gas Chemical Company), 1-cyclohexylamino-3-aminopropane, 3-aminomethyl-3,3,5 -Trimethyl-cyclohexylamine, dimethyleneamine with norbornane skeleton (Mitsui Mention may be made of the Gakusha made "NBDA"), and the like.
Among these, since the crosslinking rate is particularly high, 1,3-bisaminomethylcyclohexane, dimethyleneamine having a norbornane skeleton, metaxylylenediamine, H ₂ N (CH ₂ CH ₂ O) ₂ (CH ₂ ) ₂ NH ₂ (Ethene oxide skeleton diamine), propene skeleton diamine, propene skeleton triamine, and polyamidoamine (trade name: X2000) are useful.
The melamine compound is a compound having a triazine ring in the molecule, and examples thereof include melamine, benzoguanamine, cyclohexanecarboguanamine, methylguanamine, ethenylguanamine, hexamethoxymethylmelamine, tetramethoxymethylbenzoguanamine and the like. These low-condensates, alkyl etherified formaldehyde resins and aminoplast resins may also be used.

  Ketimine, which is a reaction product of these polyamines and ketones, is also included in the amino compound, and from the viewpoints of stability, reactivity adjustment and overcoatability, acetophenone or propiophenone and 1,3-bisaminomethylcyclohexane Obtained from acetophenone or propiophenone and dimethyleneamine (NBDA) having a norbornane skeleton; obtained from acetophenone or propiophenone and metaxylylenediamine; acetophenone or propiophenone; Also obtained from Jeffamine EDR148, Jeffamine D230 and Jeffamine D400, which are diamines having an ethene oxide skeleton or propene oxide skeleton, or Jeffamine T403, which is a triamine having a propylene skeleton. Etc. can also be used.

  Examples of aziridine compounds having an aziridyl group include N, N′-diphenylmethane-4,4′-bis (1-aziridinecarboxite), N, N′-toluene-2,4-bis (1-aziridinecarboxite). ), Bisisophthaloyl-1- (2-methylaziridine), tri-1-aziridinylphosphine oxide, N, N′-hexamethylene-1,6-bis (1-aziridinecarboxite), 2-methyl Pentane-2,4-diol-tri-β-aziridinylpropionate, 2,2-bis (hydroxymethyl) 1,3-propanediol-tri-β-aziridinylpropionate, tris-2, 4,6- (1-aziridinyl) -1,3,5-triazine, 2-methylpentane-2,4-diol tris [3- (1-aziridinyl) pro Pionate], 2-methylpentane-2,4-diol tris [3- (1-aziridinyl) butyrate], 2-methylpentane-2,4-diol tris [3- (1- (2-methyl) aziridinyl) propionate ], 2-methylpentane-2,4-diol tris [3- (1-aziridinyl) -2-methylpropionate], 2,2-bis (hydroxymethyl) 1,3-propanediol tetra [3- ( 1-aziridinyl) propionate], diphenylmethane-4,4-bis-N, N′-ethyleneurea, 1,6-hexamethylenebis-N, N′-ethyleneurea, 2,4,6- (triethyleneimino) -Syn-triazine, bis [1- (2-ethyl) aziridinyl] benzene-1,3-carboxylic acid amide and the like.

  As the carbodiimide compound, a compound having two or more carbodiimide groups (—N═C═N—) in the molecule is preferably used, and known polycarbodiimides can be used.

Moreover, as a carbodiimide compound having a carbodiimide group, a high molecular weight polycarbodiimide produced by a decarboxylation condensation reaction of diisocyanate in the presence of a carbodiimidization catalyst can also be used.
Examples of such compounds include those obtained by subjecting the following diisocyanates to a decarboxylation condensation reaction.
As the diisocyanate, 4,4′-diphenylmethane diisocyanate, 3,3′-dimethoxy-4,4′-diphenylmethane diisocyanate, 3,3′-dimethyl-4,4′-diphenylmethane diisocyanate, 4,4′-diphenyl ether diisocyanate, 3,3′-dimethyl-4,4′-diphenyl ether diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1-methoxyphenyl-2,4-diisocyanate, isophorone diisocyanate, 4,4′- One of dicyclohexylmethane diisocyanate, tetramethylxylylene diisocyanate, or a mixture thereof can be used.

  As the carbodiimidization catalyst, 1-phenyl-2-phospholene-1-oxide, 3-methyl-2-phospholene-1-oxide, 1-ethyl-3-methyl-2-phospholene-1-oxide, 1-ethyl- Phosphorene oxides such as 2-phospholene-1-oxide or their 3-phospholene isomers can be used.

  An example of such a high molecular weight polycarbodiimide is a carbodilite series manufactured by Nisshinbo Industries, Ltd. Of these, Carbodilite V-01, 03, 05, 07, 09 is preferable because of its excellent compatibility with organic solvents.

  As the oxazoline compound having an oxazoline group, a compound having two or more oxazoline groups in the molecule is preferably used. Specifically, 2′-methylenebis (2-oxazoline), 2,2′-ethenebis (2-oxazoline) is used. ), 2,2′-ethenebis (4-methyl-2-oxazoline), 2,2′-propenebis (2-oxazoline), 2,2′-tetramethylenebis (2-oxazoline), 2,2′-hexa Methylene bis (2-oxazoline), 2,2'-octamethylene bis (2-oxazoline), 2,2'-p-phenylene bis (2-oxazoline), 2,2'-p-phenylene bis (4,4 '-Dimethyl-2-oxazoline), 2,2'-p-phenylenebis (4-methyl-2-oxazoline), 2,2'-p-phenylenebis 4-phenyl-2-oxazoline), 2,2'-m-phenylenebis (2-oxazoline), 2,2'-m-phenylenebis (4-methyl-2-oxazoline), 2,2'-m- Phenylene bis (4,4′-dimethyl-2-oxazoline), 2,2′-m-phenylene bis (4-phenylene bis-2-oxazoline), 2,2′-o-phenylene bis (2-oxazoline), 2,2′-o-phenylenebis (4-methyl-2-oxazoline), 2,2′-bis (2-oxazoline), 2,2′-bis (4-methyl-2-oxazoline), 2,2 Examples include '-bis (4-ethyl-2-oxazoline) and 2,2'-bis (4-phenyl-2-oxazoline). Alternatively, ethenyl monomers such as 2-isopropenyl-2-oxazoline and 2-isopropenyl-4,4-dimethyl-2-oxazoline and other monomers that can be copolymerized with these ethenyl monomers It may be a copolymer with the body.

  Examples of metal chelate compounds having metal chelate groups include aluminum, iron, copper, zinc, tin, titanium, titanium, nickel, antimony, magnesium, vanadium, chromium, zirconium and other polyvalent metals such as 2,4-pentanedione. And compounds coordinated to ethyl acetoethanoate.

  It is important that the pressure-sensitive adhesive of the present invention contains the silane compound (1). As described above, R1 to R3 adjacent to the Si atom are hydrogen atoms or alkyl groups having 1 to 30 carbon atoms, alkenyl groups, cycloalkyl groups, aryl groups, hydroxyl groups, alkoxyl groups, mercapto groups, amino groups, glycidyl groups. And R4 is any part of a group selected from the group consisting of halogen and R4 is an α, β-unsaturated group of the α, β-unsaturated group-containing monomer (X) on the hydrosilyl group of the compound (2). Since it contains the silane compound (1), which is a site to which a saturated double bond has been added, having this structure allows the silane site to be covered when the silane compound (1) moves to the adherend interface such as a glass plate. A silicate structure is formed with the surface of the adherend due to the polarity of the silane compound, which is oriented at the adherend interface. At this time, the intermolecular affinity with the polymer (D) increases, and as a result, the affinity with the polymer increases. Thereby, it is estimated that the releasability and durability are improved by increasing the bonding force between the adherend and the copolymer, and efficiently transferring the silane compound (1) to the contact interface. The Accordingly, when at least one of R1 to R3 adjacent to the Si element contains a hydroxyl group, an alkoxyl group, a mercapto group, an amino group, a glycidyl group, or a halogen, the polarity of the silane compound (1) is improved and the adhesion is improved. Therefore, the durability is also improved, which is more preferable.

The pressure-sensitive adhesive of the present invention preferably contains an organic solvent. As long as the effects of the present invention are not impaired, other silane coupling agents, softeners, dyes, pigments, antioxidants, tackifiers, etc. You may mix | blend a fire, a plasticizer, a filler, an anti-aging agent, etc.
For example, adding organic solvents such as acetone, methyl ethanoate, ethyl ethanoate, cyclohexane, toluene, methyl ethyl ketone, isopropyl alcohol, other hydrocarbon solvents, and water to adjust the viscosity of the pressure sensitive adhesive. Or the pressure sensitive adhesive can be heated to reduce the viscosity.

The pressure-sensitive adhesive of the present invention is further suitable as an optical pressure-sensitive adhesive. That is, it is preferably used for the formation of an optical adhesive film comprising an optical film as a substrate (H) and a pressure-sensitive adhesive layer located on at least one surface of the optical film.
The optical adhesive film of the present invention can be obtained as follows.
The pressure-sensitive adhesive is applied to the release-treated surface of the peelable film and dried, and the optical film as the base material (H) is laminated on the surface of the pressure-sensitive adhesive layer, or the optical film as the base material (H) An optical adhesive film can be obtained by coating and drying a pressure sensitive adhesive on the surface of the pressure sensitive adhesive layer and laminating the release treatment surface of the peelable film on the surface of the pressure sensitive adhesive layer. The cross-linking reaction between the polymer (D) and the cross-linking agent (G) is performed when the pressure-sensitive adhesive is dried and when a film-like optical film or a peelable film is laminated on the surface of the formed pressure-sensitive adhesive layer. Furthermore, it progresses after laminating.

First, a general description of the pressure-sensitive adhesive and the pressure-sensitive adhesive film will be given.
The pressure sensitive adhesive is used to form a pressure sensitive adhesive film.
The basic lamination structure of the pressure-sensitive adhesive film is as follows: film-like substrate (H) / pressure-sensitive adhesive layer / single-sided pressure-sensitive adhesive film such as peelable film, or peelable film / pressure-sensitive adhesive layer / film-like It is a double-sided pressure-sensitive adhesive adhesive film such as substrate (H) / pressure-sensitive adhesive layer / peelable film. At the time of use, the peelable film is peeled off, and the pressure-sensitive adhesive layer is attached to the adherend. The pressure-sensitive adhesive is not only a pressure-sensitive adhesive layer that has a tack at the moment when the pressure-sensitive adhesive layer touches the adherend but also an adhesive other than the pressure-sensitive adhesive (hereinafter simply referred to as a pressure-sensitive adhesive). Unlike adhesives), it is necessary to have a cohesive force for maintaining the sticking state while having a tack and appropriate hardness without being completely solidified even during sticking. The cohesive force greatly depends on the molecular weight.

  Examples of the peelable film include those obtained by subjecting the surface of a film-like substrate such as cellophane, various plastic films, and paper to a release treatment. Moreover, as a base material (H), various film base materials are used preferably, and it can also be used independently, The thing in the multilayer state formed by laminating | stacking a several base material can also be used.

  Various plastic films are also referred to as various plastic sheets. For example, polyhydroxyethene films, triacetylcellulose films, polypropenes, polyethenes, polycycloolefins, polyolefin resin films such as ethylene-vinyl acetate copolymers, and polyethenes. Polyester resin film such as terephthalate and polybutene terephthalate, polycarbonate resin film, polynorbornene resin film, polyarylate resin film, propenoic acid resin film, polyphenylene sulfide resin film, polyethenylbenzene resin Film, ethenyl resin film, polyamide resin film, polyimide resin film, oxirane resin film, etc.

As the base material (H) in the present invention, among the various plastic films, an optical film mainly used for optical applications is preferably used. Examples of the optical film include a polarizing film, a retardation film, an elliptically polarizing film, an antireflection film, and a brightness enhancement film.
The polarizing film is also called a polarizing plate, and is a multilayer structure film in which both sides of a polyhydroxyethene polarizer are sandwiched between two triacetyl cellulose-based protective films and two cycloolefin-based films.

After applying a pressure-sensitive adhesive to a peelable film or optical film by an appropriate method in accordance with a conventional method, if the pressure-sensitive adhesive contains a liquid medium such as an organic solvent or water, it can be heated. If the liquid medium is removed or the pressure-sensitive adhesive does not contain a liquid medium that should be volatilized, the resin layer in the molten state is cooled and solidified, and the pressure-sensitive adhesive is placed on the peelable film or optical film. An adhesive layer can be formed.
The thickness of the pressure sensitive adhesive layer is preferably 0.1 μm to 200 μm, and more preferably 0.1 μm to 100 μm. If the thickness is less than 0.1 μm, sufficient adhesive strength may not be obtained, and if the thickness exceeds 200 μm, characteristics such as adhesive strength are often not improved further.

The method for applying the pressure-sensitive adhesive of the present invention to a peelable film is not particularly limited, and may be a Meyer bar, applicator, brush, spray, roller, gravure coater, die coater, lip coater, comma coater, knife coater. Various coating methods such as reverse coater and spin coater can be mentioned.
There is no restriction | limiting in particular in a drying method, The thing using hot air drying, infrared rays, and the pressure reduction method is mentioned. As drying conditions, although depending on the crosslinked form of the pressure-sensitive adhesive, the film thickness, and the selected solvent, heating with hot air at about 60 to 180 ° C. is usually sufficient.

  The pressure-sensitive adhesive film using the pressure-sensitive adhesive of the present invention is preferably used by being attached to a glass plate such as a liquid crystal cell or a PDP module or the above-mentioned various plastic films.

  Specific examples of the present invention will be described below together with comparative examples, but the present invention is not limited to the following examples. In the following examples and comparative examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively.

<Production of Silane Compound (1)>
(Synthesis Example 1)
The following α, β-unsaturated group-containing monomer (X), compound (compound) are added to a reaction vessel and a dropping device of a polymerization reactor equipped with a reaction vessel, a stirrer, a thermometer, a reflux condenser, a dropping device, and an air introduction pipe. 2) The catalyst and the organic solvent were charged at the following ratios.

[Reaction tank]
N-Butyl propenoate 128 parts Methyl ethyl ketone (organic solvent) 10 parts Hydroquinone monomethyl ether (polymerization inhibitor) 0.1 part [Drip device]
Dimethylethoxysilane (2) 104 parts Hexachloroplatinic acid (IV) hexahydrate
0.1 mol / l methanol solution (catalyst) 3 parts methyl ethyl ketone (organic solvent) 14 parts

After substituting the air in a reaction tank with nitrogen gas, it heated up to 90 degreeC in air atmosphere, stirring. Next, the mixture of the compound (2), the catalyst, and the organic solvent was dropped from the dropping device over 1 hour. After the completion of the dropwise addition, the reaction was continued for 6 hours with further stirring, and then 30 g of methyl ethyl ketone (hereinafter referred to as MEK) was added and cooled to room temperature to obtain a transparent solution containing about 80% of the nonvolatile content containing the silane compound (1). It was. The progress of the reaction was confirmed by the disappearance of the infrared absorption spectrum 2190 cm ⁻¹ of the silyl group.

(Synthesis Example 2)
MEK was reacted in the same manner as in Synthesis Example 1 except that the α, β-unsaturated group-containing monomer (X) used in Synthesis Example 1 was changed to 144 parts of 2-methylethyl 2-methylpropenoate. The non-volatile content was adjusted to about 80% to obtain a colorless transparent solution containing the compound (1). The progress of the reaction was confirmed in the same manner as in Synthesis Example 1 by the disappearance of the infrared absorption spectrum of 2190 cm ⁻¹ of each silyl group.

(Synthesis Example 3)
The following α, β-unsaturated compound (X), compound (2), catalyst are added to a reaction vessel and a dropping device of a polymerization reactor equipped with a reaction vessel, a stirrer, a thermometer, a reflux condenser, a dropping device, and an air introduction pipe. And the organic solvent were charged at the following ratios.

[Reaction tank]
N-butyl propenoate 96 parts methyl propenoate 16 parts propenoic acid 3.6 parts methyl ethyl ketone (organic solvent) 10 parts hydroquinone monomethyl ether (polymerization inhibitor) 0.1 part [drip device]
Dimethylethoxysilane (2) 104 parts Hexachloroplatinic acid (IV) hexahydrate
0.1 mol / l methanol solution (catalyst)
3 parts Methyl ethyl ketone (organic solvent) 14 parts

After substituting the air in a reaction tank with nitrogen gas, it heated up to 90 degreeC in air atmosphere, stirring. Next, the mixture of the compound (2), the catalyst, and the organic solvent was dropped from the dropping device over 1 hour. After the completion of the dropwise addition, the reaction was continued for 6 hours with further stirring, and then 30 g of methyl ethyl ketone (hereinafter referred to as MEK) was added and cooled to room temperature to obtain a transparent solution containing about 80% of the nonvolatile content containing the silane compound (1). It was. The progress of the reaction was confirmed by the disappearance of the infrared absorption spectrum 2190 cm ⁻¹ of the silyl group.

(Synthesis Examples 4 to 12)
Compound (2) used in Synthesis Example 1 was prepared by using 103 parts of dimethyldimethylaminosilane (Synthesis Example 4), 102 parts of diethylmethylsilane (Synthesis Example 5), 136 parts of dimethylphenylsilane (Synthesis Example 6), and 219 parts of diphenylchlorosilane (Synthesis). Example 7), 258 parts of tripentyloxysilane (Synthesis Example 8), 148 parts of pentamethyldisiloxane (Synthesis Example 9), 222 parts of 1,1,1,3,5,5,5-heptamethyltrisiloxane (Synthesis) Example 10) A reaction was conducted in the same manner as in Synthesis Example 1 except that 297 parts of tris (trimethylsiloxy) silane (Synthesis Example 11) and 164 parts of Triethoxysilane (Synthesis Example 12) were respectively changed. Was adjusted to about 80% to obtain a colorless transparent solution containing the compound (1). The progress of the reaction was confirmed in the same manner as in Synthesis Example 1 by the disappearance of the infrared absorption spectrum of 2190 cm ⁻¹ of each silyl group.

(Synthesis Example 13)
The α, β-unsaturated group-containing monomer (X) used in Synthesis Example 1 is 98 parts of n-butyl propenoate, 20 parts of methyl 2-methylpropenoate, 4 parts of 2-hydroxyethyl 2-methylpropenoate, The reaction was conducted in the same manner as in Synthesis Example 1 except that the amount was changed to 0.1 part of 2-methylpropenamide, and the non-volatile content was adjusted to about 80% with MEK to obtain a colorless transparent solution containing the compound (1). . The progress of the reaction was confirmed in the same manner as in Synthesis Example 1.

(Synthesis Example 14)
Synthesis example except that α, β-unsaturated group-containing monomer (X) used in Synthesis Example 1 was changed to 144 parts of 2-ethylhexyl propenoate, 17 parts of methyl propenoate and 3 parts of 4-hydroxybutyl propenoate Reaction was performed in the same manner as in Example 1, and the non-volatile content was adjusted to about 80% with MEK to obtain a colorless transparent solution containing the compound (1). The progress of the reaction was confirmed in the same manner as in Synthesis Example 1.

(Synthesis Example 15)
Synthesis example except that α, β-unsaturated group-containing monomer (X) used in Synthesis Example 1 was changed to 2-methylpropenoic acid methoxypolyethene oxide (EO addition mole number: 9) (C) 468 parts Reaction was performed in the same manner as in Example 1, and the non-volatile content was adjusted to about 80% with MEK to obtain a colorless transparent solution containing the compound (1). The progress of the reaction was confirmed in the same manner as in Synthesis Example 1.

(Synthesis Example 16)
Α, β-unsaturated group-containing monomer (X) used in Synthesis Example 1 is 600 parts of macromonomer AA-6 (manufactured by Toa Gosei Co., Ltd., methyl 2-methylpropenoate macromonomer, molecular weight of about 6000), The reaction was conducted in the same manner as in Synthesis Example 1 except that the dimethylethoxysilane of the compound (2) was changed to 11 parts, the nonvolatile content was adjusted to about 80% with MEK, and a colorless transparent solution containing the compound (1) was obtained. Obtained. The progress of the reaction was confirmed in the same manner as in Synthesis Example 1.

<Production of Resin Composition for Adhesive (Production Method II)>
(Synthesis Example 17)
A polymerization reaction apparatus in which a stirrer, a thermometer, a reflux condenser, a dropping apparatus, and a nitrogen introducing tube are attached to a polymerization tank is prepared. The following α, β-unsaturated group-containing monomer (X) The initiator and the organic solvent were charged at the following ratios.

[Polymerization tank]
N-butyl propenoate 27.9 parts methyl propenoate 20 parts propenoic acid 2 parts 2-hydroxyethyl propenoate 0.1 part ethyl ethanoate 30 parts 2,2'-azobisisobutyronitrile 0.05 part [drip apparatus]
N-butyl propenoate 48.9 parts propenoic acid 1 part 2-hydroxyethyl propenoate 0.1 part ethyl ethanoate 36 parts 2,2'-azobisisobutyronitrile 0.05 part

After the air in the polymerization tank was replaced with nitrogen gas, the reaction was started at a reflux temperature in a nitrogen atmosphere while stirring. After the start of the reaction, the mixture was maintained at the reflux temperature, and dropping of the mixture of the α, β-unsaturated compound, the polymerization initiator and the organic solvent was started from the dropping device. After completion of the dropwise addition, the polymerization rate reacted to about 90% with further stirring. Next, a mixed solution of 10 parts of dimethylethoxysilane (2), 0.5 part of hexachloroplatinic acid (IV) hexahydrate 0.1 mol / l methanol solution (catalyst), and 6 parts of ethyl ethanoate (organic solvent) For about 6 hours in a nitrogen atmosphere with further stirring. Thereafter, 184 parts of ethyl ethanoate was added to adjust the non-volatile content to about 30% by weight and cooled to room temperature to obtain a solution of an adhesive resin composition containing the silane compound (1). This solution was colorless and transparent, and had a nonvolatile content of 30.1% and a viscosity of 4,200 mPa · s. The polymer (D) had a glass transition temperature of −25 ° C., a weight average molecular weight of 1,500,000, and an unreacted α, β-unsaturated compound content of 20 ppm or less. The polymerization rate during the reaction was judged from the measurement results of the nonvolatile content at appropriate times. The progress of the reaction of the compound (1) was confirmed by disappearance of the infrared absorption spectrum of 2190 cm ⁻¹ of the silyl group in the same manner as in Synthesis Example 1.

(Synthesis Examples 18 to 26)
The compound (2) used in Synthesis Example 17 was mixed with 10 parts of dimethyldimethylaminosilane (Synthesis Example 18), 10 parts of diethylmethylsilane (Synthesis Example 19), 12 parts of dimethylphenylsilane (Synthesis Example 20), and 20 parts of diphenylchlorosilane (Synthesis). Example 21), 23 parts of tripentyloxysilane (Synthesis Example 22), 14 parts of pentamethyldisiloxane (Synthesis Example 23), 20 parts of 1,1,1,3,5,5,5-heptamethyltrisiloxane (Synthesis) Example 24), reaction was carried out in the same manner as in Synthesis Example 17 except that each was changed to 27 parts of tris (trimethylsiloxy) silane (Synthesis Example 25) and 15 parts of triethoxysilane (Synthesis Example 26). The non-volatile content was adjusted to about 30%, and a colorless and transparent solution of the adhesive resin composition containing the silane compound (1) was obtained. The polymerization rate during the reaction was judged from the measurement result of the nonvolatile content in a timely manner in the same manner as in Synthesis Example 17. The progress of the reaction was confirmed by disappearance of the infrared absorption spectrum 2190 cm ⁻¹ of each silyl group in the same manner as in Synthesis Example 1.

(Synthesis Example 27)
The composition of the α, β-unsaturated compound (X) used in Synthesis Example 17 was changed, and charged into the polymerization tank and the dropping device at the following ratios respectively. A transparent solution containing the resin composition for an adhesive containing the compound (1) was obtained.

[Polymerization tank]
N-butyl propenoate 29 parts methyl 2-methylpropenoate 10 parts methyl propenoate 10 parts 4-hydroxybutyl propenoate 0.5 parts ethyl ethanoate 30 parts 2,2'-azobisisobutyronitrile 0.05 part [Drip device]
N-butyl propenoate 50 parts 4-hydroxybutyl propenoate 0.5 parts ethyl ethanoate 36 parts 2,2′-azobisisobutyronitrile 0.05 part

(Synthesis Example 28)
The composition of the α, β-unsaturated compound (X) used in Synthesis Example 17 was changed, and charged into the polymerization tank and the dropping device at the following ratios respectively. A transparent solution of the adhesive resin composition containing the compound (1) was obtained.

[Polymerization tank]
2-Methylpropenoate lauryl 24.9 parts Ethyl propenoate 20 parts Ethanylpyrrolidone 5 parts 2-Hydroxyethyl propenoate 0.1 parts Ethyl ethanoate 30 parts 2,2'-azobisisobutyronitrile 0.05 part [Drip device]
Lauryl 2-methylpropenoate 9.9 parts ethyl propenoate 40 parts 2-hydroxyethyl propenoate 0.1 part ethyl ethanoate 36 parts 2,2'-azobisisobutyronitrile 0.05 part

(Synthesis Example 29)
With the composition of the α, β-unsaturated compound (X) used in Synthesis Example 17, the reaction was conducted in the same manner as in Synthesis Example 17, and the polymerization rate was matured to about 97%. Next, a mixed solution of 3 parts of dimethylethoxysilane (2), 0.2 part of hexachloroplatinum (IV) acid hexahydrate 0.1 mol / l methanol solution (catalyst), and 4 parts of ethyl ethanoate (organic solvent) The reaction was continued for about 6 hours in a nitrogen atmosphere with further stirring. Thereafter, the non-volatile content was adjusted to about 30% with ethyl ethanoate to obtain a colorless and transparent solution of the resin composition for an adhesive containing the compound (1).

<Production of polymer (D)>
(Synthesis Examples 30 to 32)
During the polymerization of a mixed solution of dimethylethoxysilane (2), hexachloroplatinum (IV) acid hexahydrate 0.1 mol / l methanol solution (catalyst) and ethyl ethanoate used in Synthesis Examples 17 and 27.28 The reaction was continued for 8 hours without addition, and the nonvolatile content was adjusted to about 30% with ethyl ethanoate to obtain a colorless and transparent solution of the polymer (D) containing no compound (1).

About the solution of the compound (1) obtained in Synthesis Examples 1 to 12, the raw material composition and the solution appearance were determined according to the following methods, and the results are shown in Table 1.
Moreover, about the resin composition for adhesive agents obtained by the synthesis examples 13-29 and the polymer (D) which does not have the silane compound (1) obtained by the synthesis examples 30-32, solution appearance, non-volatile matter non-volatile matter (%), Solution viscosity, weight average molecular weight (Mw), glass transition temperature (Tg), and unreacted content (ppm) of α, β-unsaturated compounds were determined according to the following methods, and the results are shown in Table 2. It was.

<< Solution appearance >>
The appearance of the resin composition solution for adhesive or the polymer (D) solution was visually evaluated.

<Measurement of nonvolatile content and nonvolatile content>
About 1 g of each of the resin composition solution for an adhesive or the polymer (D) is weighed into a metal container, dried in an oven at 150 ° C. for 20 minutes, the residue is weighed, and the remaining rate is calculated. Nonvolatile content Nonvolatile content (%).

<< Measurement of solution viscosity >>
Conditions for rotating the resin composition solution for adhesive or each polymer (D) solution at 23 ° C. with a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd.) using a # 3 rotor at 12 rpm for 1 minute The solution viscosity (mPa · s) was measured.

<< Measurement of weight average molecular weight (Mw) >>
The resin composition solution for adhesives or the weight average molecular weight (Mw) of the polymer (D) was measured using GPC (gel permeation chromatography) “Shodex GPC System-21” manufactured by Showa Denko K.K. GPC is liquid chromatography that separates and quantifies substances dissolved in a solvent based on the difference in molecular size, and the weight average molecular weight (Mw) is determined in terms of polystyrene.

<< Measurement of glass transition temperature (Tg) >>
An “SSC5200 disk station” (manufactured by Seiko Instruments Inc.) was connected to a robot DSC (differential scanning calorimeter, “RDC220” manufactured by Seiko Instruments Inc.) and used for measurement.
The adhesive resin composition solution or polymer solution obtained in each synthesis example was applied to a release-treated polyester film and dried. About 10 mg of the dried polymer was scraped off and placed in an aluminum pan as a sample. The sample was weighed and set in a differential scanning calorimeter. The aluminum pan of the same type without a sample was used as a reference, heated at a temperature of 100 ° C. for 5 minutes, and then rapidly cooled to −120 ° C. using liquid nitrogen. Thereafter, the temperature was raised at 10 ° C./min, and the glass transition temperature (Tg, unit: ° C.) was determined from the DSC chart obtained during the temperature elevation.

<< Measurement of Unreacted Content (ppm) of α, β-Unsaturated Compound >>
The unreacted content of the α, β-unsaturated compound in the produced adhesive resin composition or polymer was measured using GC (Gas Chromatograph, “GC4000” manufactured by GS Science Co., Ltd.).
About 1 g of the resin composition solution for adhesive or polymer solution obtained in each synthesis example was weighed into a 70 ml glass bottle, dissolved by adding 1 g of a 5% acetone solution of methyl isobutyl ketone and 8 g of acetone, and dissolved in a microsyringe. 1.2 μl was injected and measured. Apparatus conditions [column: capillary column TC-FFAP, D = 0.32 mm, DF: 0.25 × 60 m, oven temperature: 50 ° C. 5 minutes−6 ° C./minute temperature increase−200 ° C. 5 minutes, injection temperature 200 ° C., detector Temperature 230 ° C., carrier gas pressure 5.9 psi. MS; mode scan, mass range 50-550. The amount of gas generated was determined as the nonvolatile content (ppm) in terms of an internal standard 2-ethylhexyl propenoate.
The calibration curve is created by plotting the relationship between the [peak area] and the reference value [addition amount of 2-ethylhexyl propenoate] at the retention time under specific conditions of gas chromatograph using an acetone solution of 2-ethylhexyl propenoate as a standard sample. did.

  The symbols shown in Table 1 are as follows. PAEH: 2-ethylhexyl propenoate, PAB: n-butyl propenoate, PAM: methyl propenoate, MPAM: methyl 2-methylpropenoate, MPAAM: 2-methylpropenamide, PAHB: 4-hydroxybutyl propenoate, MPAHE: 2-Methylpropenoic acid 2-hydroxyethyl, MPAEO: 2-methylpropenoic acid methoxypolyethene oxide, AA-6: Macromonomer AA-6, DMEOS: Dimethylethoxysilane, DMDMAS: Dimethyldimethylaminosilane, DEMS: Diethylmethylsilane DMPS: dimethylphenylsilane, DPCS: diphenylchlorosilane, TPOS: tripentyloxysilane, PMDSL: pentamethyldisiloxane, HMTSL: 1,1,1,3,5,5,5-hepta Tilt polysiloxane, TTMSLS: tris (trimethylsiloxy) silane, TEOS: triethoxysilane.

  The new symbols shown in Table 2 are as follows. MPAL: lauryl 2-methylpropenoate, EP: ethanylpyrrolidone, EAc: ethyl ethanoate.

Example 1
With respect to 100 parts by weight of the polymer (D) solution obtained in Synthesis Example 30, 7.5 parts of the solution of the silane compound (1) prepared in Synthesis Example 1 and TDI / Add 10 parts of TMP (2-methylpentane-2,4-diol adduct of tolylene diisocyanate) and 60 parts of ethyl ethanoate so that the coating viscosity is 2000 to 3000 mPa · s, and stir well. Thus, a pressure sensitive adhesive was obtained.
This was coated on a peeled polyester film (hereinafter referred to as “peelable film”) so that the thickness after drying was 25 μm, and dried at 100 ° C. for 2 minutes to form a pressure-sensitive adhesive layer. did.
After drying, one side of a polarizing film with a multilayer structure in which both sides of a polyhydroxyethene (PHE) polarizer are sandwiched between triacetyl cellulose protective films (hereinafter referred to as “TAC film”) is bonded to the resin layer. A laminate having a configuration of “film / pressure-sensitive adhesive layer / TAC film / PHE / TAC film” was obtained.
Next, the obtained laminate was aged (dark reaction) for one week under the condition of a temperature of 23 ° C. and a relative humidity of 50%, and the reaction of the pressure-sensitive adhesive layer was advanced to obtain an optical pressure-sensitive adhesive film.

(Comparative Example 1)
An optical pressure-sensitive adhesive film was obtained in the same manner as in Example 1 except that the solution of the silane compound (1) prepared in Synthesis Example 1 was not added to the polymer (D) solution obtained in Synthesis Example 28. It was.

(Comparative Example 2)
In place of the solution of the silane compound (1) prepared in Synthesis Example 1 in the polymer (D) solution obtained in Synthesis Example 15, “X-41-1805” (Shin-Etsu Chemical Co., Ltd.) was added as a mercapto group-containing silane alkoxy oligomer. An optical pressure-sensitive adhesive film was prepared in the same manner as in Example 1 except that 6 parts of (made) were added.

(Examples 2 to 14)
Instead of the solution of the silane compound (1) prepared in Synthesis Example 1 for the polymer (D) solution obtained in Synthesis Example 30, the solution of the silane compound (1) obtained in Synthesis Examples 2 to 16 is used. An optical pressure-sensitive adhesive film was produced in the same manner as in Example 1 except that.

(Examples 17 and 18)
Optical pressure-sensitive adhesive in the same manner as in Example 1 except that the polymer (D) solution obtained in Synthesis Examples 31 and 32 was used instead of the polymer (D) solution obtained in Synthesis Example 30. A film was prepared.

(Comparative Examples 3 and 4)
Optical pressure-sensitive adhesive film for optical use in the same manner as in Example 1 except that the solution of the silane compound (1) prepared in Synthesis Example 1 is not added to the polymer (D) solution obtained in Synthesis Examples 31 and 32. Was made.

(Examples 19 to 22)
In Example 19, HBAP (2,2′-bishydroxymethylbutanol tris [3- (1-aziridinyl)) was used instead of 10 parts of TDI / TMP as a crosslinking agent (G) in the polymer solution used in Example 1. 1 part of propionate]), 5 parts of TGMXDA (N, N, N ′, N′-tetraglycidyl-m-xylylenediamine) in Example 20 and V-05 (carbodilite V— which is a carbodiimide compound in Example 21) 05 ": Nisshinbo Co., Ltd.) 5 parts, in Example 22, 1 part of Al chelate (aluminum tris (2,4-pentadionate)) was added in the same manner as in Example 1 except that 1 part was added. Thus, an optical pressure-sensitive adhesive film was produced. In Example 22, the solvent was changed from ethyl ethanoate to isopropyl alcohol (IPA).

(Examples 23 to 25)
In place of 10 parts of TDI / TMP as the crosslinking agent (G) in the polymer (D) solution obtained in Synthesis Example 31 used in Example 17, TDI / TMP was used in Example 23, and XDI was used in Example 24. / TMP (2-methylpentane-2,4-diol adduct of xylylene diisocyanate) and HMDI / burette (hexuremethylene diisocyanate burette adduct) in Example 25, except that 1 part each was added. In the same manner as in Example 17, an optical pressure-sensitive adhesive film was produced.

(Example 26)
TDI / TMP (2-methylpentane-2,4-diol adduct of tolylene diisocyanate) was used as a crosslinking agent (G) with respect to 100 parts by weight of the adhesive resin composition solution obtained in Synthesis Example 17. Body) 10 parts, and 40 parts of ethyl ethanoate was added and stirred well so that the coating viscosity would be 2000 to 3000 mPa · s, and a pressure-sensitive adhesive was obtained. A pressure adhesive film was obtained.

(Examples 27 to 38)
In the same manner as in Example 1 except that the polymer solution obtained in Synthesis Examples 18 to 29 was used instead of the polymer solution obtained in Synthesis Example 17 used in Example 26, an optical pressure-sensitive type was used. An adhesive film was prepared.

(Examples 39 to 42)
In Example 39, instead of 10 parts of TDI / TMP, the polymer solution obtained in Synthesis Example 17 used in Synthesis Example 17 was replaced with HBAP (2,2′-bishydroxymethylbutanol tris [G). 3- (1-aziridinyl) propionate]), 1 part in Example 40, 5 parts TGMXDA (N, N, N ′, N′-tetraglycidyl-m-xylylenediamine) in Example 40, V-05 (carbodiimide in Example 41) An optical pressure-sensitive adhesive film was prepared in the same manner as in Example 1 except that 1 part of each compound “carbodilite V-2,4-pentadionate) was added. In 42, the solvent was changed from ethyl ethanoate to isopropyl alcohol (IPA).

(Examples 43 to 45)
Instead of 10 parts of TDI / TMP as the crosslinking agent (G), the polymer solution obtained in Synthesis Example 29 used in Example 38 was replaced with TDI / TMP in Example 43 and XDI / TMP (in Example 44). Except that 1 part of xylylene diisocyanate 2-methylpentane-2,4-diol adduct) and HMDI / burette (hexuremethylene diisocyanate burette adduct) in Example 45 were added respectively. In the same manner as in Example 1, an optical pressure-sensitive adhesive film was produced.

  Various performances of the optical pressure-sensitive adhesive films obtained in the respective Examples and Comparative Examples were evaluated by the following methods. The results are shown in Table 3.

<< Evaluation method of optical characteristics >>
After the pressure sensitive adhesive film sandwiched between the peelable films obtained in each Example and Comparative Example was aged for one week at a temperature of 23 ° C. and a relative humidity of 50%, both peelable films were removed and pressure sensitive While visually judging the appearance of the adhesive layer alone, HAZE was measured by “NDH-300A” [manufactured by Nippon Denshoku Industries Co., Ltd.].
○: No problem in practical use and very good. HAZE: less than 1.
(Triangle | delta): Cloudiness etc. are not recognized, but HAZE: 1 or more and less than 3 can be used without a problem practically.
X: Some cloudiness is recognized or HAZE: 3 or more. There are practical problems.

<Peelability of peelable film>
After aging the laminates obtained in each Example and Comparative Example for 1 week at a temperature of 23 ° C. and a relative humidity of 50%, the release film covering one surface of the pressure-sensitive adhesive layer was peeled off. The peelability (peel strength according to JIS K6301 and transferability of the pressure-sensitive adhesive layer to the peelable film) was evaluated.
Separately, the obtained laminate was aged at a temperature of 23 ° C. and a relative humidity of 50% for 3 weeks, and then the peelable film was peeled off in the same manner, and the peelability at that time was evaluated.
○: “The peel strength after 3 weeks is less than 1.2 times after aging for 1 week, the peelable film has no adhesive transfer, and is practically satisfactory and very good.”
Δ: “The peel strength after 3 weeks is 1.2 times or more and less than 1.5 times after aging for 1 week, and there is no transfer of the adhesive to the peelable film.
X: “The peel strength after 3 weeks is 1.5 times or more after aging for 1 week, or the transfer of the adhesive is observed on the peelable film.

<< Evaluation method of optical characteristics >>
After the pressure sensitive adhesive film sandwiched between the peelable films obtained in each Example and Comparative Example was aged for one week at a temperature of 23 ° C. and a relative humidity of 50%, both peelable films were removed and pressure sensitive While visually judging the appearance of the adhesive layer alone, HAZE was measured by “NDH-300A” [manufactured by Nippon Denshoku Industries Co., Ltd.].
○: No problem in practical use and very good. HAZE: less than 1.
(Triangle | delta): Cloudiness etc. are not recognized, but HAZE: 1 or more and less than 3 can be used without a problem practically.
X: Some cloudiness is recognized or HAZE: 3 or more. There are practical problems.

<Evaluation method of removability (reworkability)>
The pressure-sensitive adhesive film for optics obtained in each example and comparative example was cut into a size of 25 mm × 150 mm, the peelable film was peeled off, and attached to a float glass plate having a thickness of 1.1 mm using a laminator, A laminate of a polarizing film and a glass plate was obtained by holding in an autoclave at 50 ° C. and 5 atm for 20 minutes.
The laminate was allowed to stand at 23 ° C. and 50% relative humidity for 1 week, and then peeled off at a speed of 300 mm / min in the direction of 180 °. The haze on the glass surface after peeling was visually observed and evaluated in three stages.
○: No fogging, no problem in practical use, very good.
Δ: Some fogging is observed, but no problem in practical use and good.
X: Transfer of the adhesive layer was observed over the entire surface, which is impractical.

<Method for evaluating heat resistance and heat and humidity resistance>
The pressure-sensitive adhesive film for optics obtained in each example and comparative example was cut into a size of 150 mm × 80 mm, the peelable film was peeled off, and each polarizing film was placed on both surfaces of a 1.1 mm thick float glass plate. A laminator was used so that the absorption axes of these were orthogonal to each other. Subsequently, the glass plate on which the polarizing film was attached was held in an autoclave at 50 ° C. and 5 atm for 20 minutes to obtain a laminate of a polarizing plate and a glass plate.
As evaluation of heat resistance, floating peeling after leaving the laminate at 95 ° C. for 1000 hours, and light leakage (white spots) when light was transmitted through the laminate were visually observed.
In addition, as an evaluation of moisture and heat resistance, the laminate was left to stand for 1000 hours at 80 ° C. and a relative humidity of 90%, and light leakage (white spots) when light was transmitted through the laminate was visually observed. did.
The heat resistance and moist heat resistance were evaluated based on the following four-stage evaluation criteria.
A: No floating peeling, foaming or whitening is observed, there is no practical problem at all, and it is very good.
○: No floating peeling or whitening was observed, the deviation was less than 0.2 mm, and there was no problem in practical use.
Δ: Slightly floating peeling, foaming, and whitening are observed, but the deviation is less than 02 to 0.5 mm, and there is no problem in practical use. ×: There are floating peeling, foaming, whitening, and practical use. It is impossible.

  The new symbols shown in Table 3 are as follows. TDI / TMP: 2-methylpentane-2,4-diol adduct of tolylene diisocyanate, XDI / TMP: 2-methylpentane-2,4-diol adduct of xylylene diisocyanate, HMDI / burette: Bullet adduct of hexamethylene diisocyanate, HBAP: 2,2′-bishydroxymethylbutanol tris [3- (1-aziridinyl) propionate], TGMXDA: N, N, N ′, N′-tetraglycidyl-m-xylylene Amine, V-05: “Carbodilite V-05” which is a carbodiimide compound, Al chelate: Aluminum tris (2,4-pentadionate), IPA: Isopropyl alcohol, X41-1805: “X” as mercapto group-containing silane alkoxy oligomer -41 805 "(manufactured by Shin-Etsu Chemical Co., Ltd.).

As described above, it can be seen that the pressure-sensitive adhesive of the present invention is excellent in heat resistance, heat and humidity resistance, optical properties, peelability of the peelable film, and reworkability.
On the other hand, in Comparative Examples 1, 3, and 4 that do not contain the silane compound (1), the reworkability is poor, and after sticking to a glass plate, the film is kept at high temperature or high temperature and high humidity for a long period of time. When it is peeled off, foaming, floating and the like are generated, and it is recognized that the durability is inferior. Moreover, in the comparative example 2 using a commercially available silane compound "X-41-1805", it is recognized that the peelability of a peelable film becomes bad.

Claims (8)

A resin composition for an adhesive comprising a silane compound represented by the following general formula (1) and a polymer (D) of an α, β-unsaturated group-containing monomer (X) .
General formula (1)

[In General Formula (1), R1 to R3 are a hydrogen atom or an alkyl group having 1 to 30 carbon atoms, an alkenyl group, a cycloalkyl group, an aryl group, a hydroxyl group, an alkoxyl group, a mercapto group, an amino group, a glycidyl group, and Represents a halogen group. R4 is a Si—C bond formed by hydrosilylation reaction with an α, β-unsaturated group of a monomer selected from the group consisting of propenoic acid, 2-methylpropenoic acid, propenoic acid derivatives, and 2-methylpropenoic acid derivatives. Represents a generated substituent. ] A resin composition for an adhesive comprising a silane compound represented by the following general formula (1) and a polymer (D) of an α, β-unsaturated group-containing monomer (X).
General formula (1)

[In General Formula (1), R1 to R3 are a hydrogen atom or an alkyl group having 1 to 30 carbon atoms, an alkenyl group, a cycloalkyl group, an aryl group, a hydroxyl group, an alkoxyl group, a mercapto group, an amino group, a glycidyl group, and Represents a halogen group. R4 represents a substituent in which a Si—C bond formed by hydrosilylation reaction is formed on the α, β-unsaturated group of the copolymer (A) having a weight average molecular weight of 200 to 2,000,000. The union (A) represents a polymer obtained by polymerizing a monomer selected from the group consisting of propenoic acid, 2-methylpropenoic acid, a propenoic acid derivative, and a 2-methylpropenoic acid derivative. ] Reacting a monomer selected from the group consisting of propenoic acid, 2-methylpropenoic acid, a propenoic acid derivative, and a 2-methylpropenoic acid derivative with a compound (2) represented by the following general formula (2);
polymer (D) of α, β-unsaturated group-containing monomer (X);
A mixture of a silane compound (1), which is a reaction product of a monomer selected from the group consisting of propenoic acid, 2-methylpropenoic acid, a propenoic acid derivative, and a 2-methylpropenoic acid derivative and the compound (2); The manufacturing method of the resin composition for adhesive agents characterized by obtaining.
General formula (2)

[In General Formula (2), R1 to R3 are a hydrogen atom or an alkyl group having 1 to 30 carbon atoms, an alkenyl group, a cycloalkyl group, an aryl group, a hydroxyl group, an alkoxyl group, a mercapto group, an amino group, a glycidyl group, and Represents a halogen group. ] A first step of polymerizing a monomer selected from the group consisting of propenoic acid, 2-methylpropenoic acid, a propenoic acid derivative, and a 2-methylpropenoic acid derivative until the reaction rate becomes 70 to 99.9%;
Next, the compound (2) is added, the monomer remaining in the first step and the compound (2) are reacted, and a silane compound (the reaction product of the monomer and the compound (2)) ( 1) and a second step of obtaining a polymer (D) of an α, β-unsaturated group-containing monomer (X);
The manufacturing method of the resin composition for adhesive agents of Claim 3 characterized by the above-mentioned. The resin composition for adhesive agents obtained by the manufacturing method of Claim 3 or 4 . A pressure-sensitive adhesive comprising the resin composition for an adhesive according to any one of claims 1, 2, and 5 , and a crosslinking agent (G). A pressure-sensitive adhesive film for optical use, comprising a pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive according to claim 6 formed on a substrate (H). 8. The pressure-sensitive adhesive film for optics according to claim 7, wherein the substrate (H) is an optical film.