WO2006033147A1

WO2006033147A1 - Polysilsesquioxane graft polymer, process for producing the same, and pressure-sensitive adhesive

Info

Publication number: WO2006033147A1
Application number: PCT/JP2004/013842
Authority: WO
Inventors: Atsuko Kimura; Mikihiro Kashio; Toshio Sugizaki; Osamu Moriya
Original assignee: Lintec Corporation
Priority date: 2004-09-22
Filing date: 2004-09-22
Publication date: 2006-03-30

Abstract

A novel polysilsesquioxane graft polymer which has repeating units represented by the following formula (1) in the molecule and can become a pressure-sensitive adhesive combining excellent heat resistance with excellent cohesive force; a process for producing the polymer; and a pressure-sensitive adhesive and a pressure-sensitive adhesive sheet each employing this polysilsesquioxane graft polymer. (In the formula, A represents a connecting group; R1 represents an optionally substituted hydrocarbon group; R2 represents hydrogen or C1-18 alkyl; R3 represents a polar group or optionally substituted aryl; l, m, and n each is 0 or any natural number, provided that the case where m=n=0 is excluded; and k1, k2, and k3 each is any natural number.) (1)

Description

Specification

Polysilsesquioxane graft polymer, process for producing the same, and pressure-sensitive adhesive

[0001] The present invention relates to a polysilsesquioxane graft polymer obtained by graft-polymerizing a butyl compound such as a methacrylate with a polysilsesquioxane compound having a mercapto group at a terminal portion, and The present invention relates to a production method, and a pressure-sensitive adhesive and pressure-sensitive adhesive sheet using the polysilsesquioxane graft polymer.

Background art

[0002] Conventionally, as a label sheet to be attached to various members and devices, an adhesive sheet formed by applying an adhesive to a base material sheet to form an adhesive layer is known.

This pressure-sensitive adhesive sheet is widely used in many industrial fields for printing labels, packaging, and the like because of the convenience that it can be applied immediately by pressing. For example, in production management in the production line of automobiles and electrical / electronic products, bar code printed adhesive sheets (labels) are attached to parts.

[0003] By the way, in the production management, etc. in the production line of automobiles and electrical / electronic products, there is a process in which heat treatment is performed depending on the part. When a label is used, the label is heat resistant. May be required. Conventionally, polyimide films and polyetherimide films have been used as such heat-resistant bar code labels, but these films are expensive, and the resulting bar code label is expensive. . Polyethylene terephthalate films and polyethylene films that are generally used as base materials for barcode labels have the problem that they are inferior in heat resistance, although they are inexpensive.

[0004] Japanese Patent Application Laid-Open No. 2002-275438, which solves such a problem, has a coating layer for printing on one surface of a base material having a polyethylene naphtharate film force, and the base material. There has been proposed a heat-resistant label characterized by having a heat-resistant pressure-sensitive adhesive layer having an adhesive strength at a temperature of 150 ° C of 0.5 NZ25 mm or more on the opposite surface. Here, rubber-based or acrylic pressure-sensitive adhesives are used as the pressure-sensitive adhesive constituting the heat-resistant pressure-sensitive adhesive layer. Yes.

[0005] Further, JP-A-2003-138229 discloses a pressure-sensitive adhesive sheet comprising a heat-sensitive pressure-sensitive adhesive layer containing a heat-resistant water-based pressure-sensitive adhesive on at least one surface of a base sheet. Is described. As the heat-resistant water-based pressure-sensitive adhesive, a general water-based pressure-sensitive adhesive mainly composed of an acrylic polymer emulsion or rubber latex and blended with a tackified resin emulsion is used.

[0006] However, the pressure-sensitive adhesives used in the pressure-sensitive adhesive sheets described in these documents are conventionally known, and are not sufficient in terms of heat resistance and the like. Therefore, there has been a demand for the development of new pressure-sensitive adhesives that are more excellent in heat resistance and adhesive strength!

[0007] The present invention has been made in view of such a state of the art, and a novel polysilsesquioxane graft polymer that can be an adhesive having both excellent heat resistance and cohesive force, and production thereof It is an object to provide a method, and a pressure-sensitive adhesive and pressure-sensitive adhesive sheet using the polysilsesquioxane graft polymer.

Disclosure of the invention

[0008] The present inventors synthesized a polysilsesquioxane compound having a ladder type structure by reacting 3-mercaptopropyltrimethoxysilane with phenol trimethoxysilane in the presence of an acid catalyst. The inventors have found that a polysilsesquioxane graft polymer can be efficiently obtained by a graft polymerization reaction with a methacrylic ester having a terminal mercapto group of the obtained polysilsesquioxane compound as a reaction initiation point. Further, the pressure-sensitive adhesive containing the obtained polysilsesquioxane graft polymer was found to have excellent heat resistance and cohesive strength, and the present invention was completed.

[0009] According to the first aspect of the present invention, in the molecule, the formula (1) [0010] [Chemical 1]

(Wherein A represents a linking group, R ¹ represents an optionally substituted hydrocarbon group, R ² represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, R ³ represents an aryl group which may have a polar group or a substituent, 1, m and n each independently represent 0 or an arbitrary natural number, except when m = n = 0. kl, k2 and k3 each independently represent an arbitrary natural number.When kl, k2 and k3 are each 2 or more, the formula: -CH -C (R ² ) (R ³ )-

2

The groups can be the same or different. And a polysilsesquioxane graft polymer having a repeating unit represented by the following formula:

[0012] The polysilsesquioxane graft polymer of the present invention preferably has a number average molecular weight of 5,000 to 1,000,000.

According to a second of the invention, in the molecule, the formula (2) [0013] [Chemical 2]

(In the formula, A represents a linking group, R ¹ represents an optionally substituted hydrocarbon group. 1, m and n each independently represents 0 or an arbitrary natural number. However, except for the case where m = n = 0, a polysilsesquioxane compound having a repeating unit represented by formula (3): CH = C ( R ² ) -R ³ (wherein R ² is a hydrogen atom or a carbon number of 1

2 1

8 represents an alkyl group, and R ³ has a polar group or a substituent, and may represent an aryl group. A method for producing a polysilsesquioxane graphene polymer is provided, which comprises reacting with a vinyl compound represented by formula (I).

[0015] The method for producing a polysilsesquioxane sesqui O hexanes graft polymer of the present invention have the formula (4): (ASH) Si (OR 4) (X 1) ( wherein, A represents as defined above, R ⁴ is an alkyl group with 1 to 6 carbon atoms

P 3-p

X ¹ represents a halogen atom, and p represents an integer of 0-3. ) And the silane compound represented by the above formula (4) and 1 part by weight of the silane compound represented by the above formula (4), 0—100 times the amount of the formula (5): R ¹ Si (OR ⁵ ) (X ² ) (In the formula, R ¹ has the same meaning as described above, and R ⁵ has 1 carbon atom.

q 3-q represents 16 alkyl groups, X ² represents a halogen atom, and q represents an integer of 0-3. The polysilsesquioxane compound having a repeating unit represented by the formula (2) in the molecule by condensing the silane compound represented by formula (2) in the presence of an acid catalyst or a base catalyst. And a step of reacting the obtained polysilsesquioxane compound with the vinyl chloride compound represented by the formula (3) in the presence of a radical polymerization initiator. Preferably there is.

[0016] According to a third aspect of the present invention, there is provided an adhesive comprising the polysilsesquioxane graft polymer of the present invention.

According to the fourth of the present invention, a base sheet and the adhesive of the present invention formed on the base sheet A pressure-sensitive adhesive sheet comprising the pressure-sensitive adhesive layer is provided. BEST MODE FOR CARRYING OUT THE INVENTION

[0017] Hereinafter, the present invention is classified into 1) a polysilsesquioxane graft polymer, 2) a process for producing a polysilsesquioxane graft polymer, 3) an adhesive, and 4) an adhesive sheet. Explain in detail.

[0018] 1) Polysilsesquioxane graft polymer

The polysilsesquioxane graft polymer of the present invention has a repeating unit represented by the formula (1) in the molecule.

[0019] In the repeating unit represented by the formula (1), A represents a linking group.

The linking group is not particularly limited as long as it plays a role of linking a key atom as a central metal and a mercapto group. For example, a saturated or unsaturated alkylene group which may have a substituent, It may have a substituent and may be a / or a arylene group.

[0020] Specific examples of the saturated alkylene group include a saturated alkylene group having 1 to 20 carbon atoms such as a methylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group. Can be mentioned. Specific examples of the unsaturated alkylene group include unsaturated alkylene groups having 2 to 20 carbon atoms such as a beylene group, a probelene group, a butylene group, and a pentylene group. Specific examples of the arylene group include o-phenylene group, m-phenylene group, p-phenylene group and the like.

[0021] The saturated and unsaturated alkylene group may have a substituent such as an amino group, a methylamino group, or a dimethylamino group, and may have an amino group; a hydroxyl group; a mercapto group; an amide group, N , An amide group which may have a substituent such as N-dimethylamide group; a carboxyl group

A halogen atom such as a fluorine atom, a chlorine atom or a bromine atom; an alkoxy group such as a methoxy group or an ethoxy group; an alkylthio group such as a methylthio group or an ethylthio group; an alkoxycarbon such as a methoxycarbonyl group or an ethoxycarbonyl group; Group; etc. are mentioned. Examples of the substituent for the arylene group include cyano group; nitro group; halogen atom such as fluorine atom, chlorine atom and bromine atom; alkoxy group such as methoxy group and ethoxy group; alkylthio group such as methylthio group and ethylthio group. ; Etc. are mentioned. These substituents may be bonded to any position of the alkylene group or arylene group, and a plurality of these substituents may be bonded to each other. You may do it.

Among these, in the present invention, since a graft polymer having excellent heat resistance and adhesive strength can be obtained, A is a saturated or unsaturated alkylene group which may have a substituent. A saturated alkylene group having 11 to 20 carbon atoms, which is more preferably a saturated alkylene group which may have a preferable substituent, is particularly preferable.

[0023] R ¹ may have a substituent and may represent a hydrocarbon group.

The hydrocarbon group for R ¹ includes methyl, ethyl, n propyl, isopropyl, n butyl, sec butyl, isobutyl, t butyl, n pentyl, n-hexyl, n − Alkyl groups such as heptyl group, n-octyl group, n-nor group, n-decyl group; beer group, 1 prop group, 2 prop group, isopropyl group, Alkyl groups such as 3-butyl group, 4-pentyl group, and 5-hexyl group; alkyl groups such as ethur group, propargyl group, and butur group; phenol group, 1 naphthyl group, 2 — Aryl group such as naphthyl group;

[0024] Examples of the substituent for the hydrocarbon group of R ¹ include the same groups as those exemplified as the substituent for the alkylene group and arylene group of A. Further, the substituents may be bonded to any position of the hydrocarbon group, or a plurality of substituents may be bonded to each other or the same or different.

[0025] R ² is a hydrogen atom; or a methyl group, an ethyl group, an n propyl group, an isopropyl group, an n-butyl group, a t-butyl group, an n pentyl group, an n-hexyl group, an n-heptyl group, n —Denotes an alkyl group having 1 to 18 carbon atoms such as a cutyl group, an n-nor group, an n-decyl group, and an n-dodecyl group.

R ³ has a polar group or a substituent, and may represent an aryl group.

Examples of the polar group include a carboxyl group; an alkoxy carbo group such as a methoxy carbo ol group, an ethoxy carbo ol group, a propoxy carboxy group, an isopropoxy carbonyl group, a butoxy carbo ol group, and a t butyl carboxy group. Groups: acetyl groups, propiol groups, benzol groups and other acyl groups; cyano groups; methoxy groups, ethoxy groups and other alkoxy groups; methylseno-noreno groups, ethenolesnoreno-noreno groups, etc. And aryl groups such as phenol-nolesnorehoninole group and p-methylphenolsulfonyl group.

[0027] It may have a substituent! /, But as an aryl group, a phenyl group, a double-opened phenyl group, 3 —Substituents such as black-opened phenyl group, 4-black-opened phenyl group, 4-methylphenol group, 4-methoxyphenyl group, 4 t-butoxyphenyl group, 2,4,6-trimethylphenol group, etc. A naphthyl group or the like. A naphthyl group or the like may be used. Examples thereof include a naphthyl group and a 2-naphthyl group.

[0028] 1, m and n each independently represent 0 or an arbitrary natural number. However, except when m = n = 0.

kl, k2 and k3 each independently represent an arbitrary natural number. When kl, k2 and k3 are each 2 or more, a group represented by the formula: CH-C (R ² ) (R ³ ) — Are the same but different

2

You may go on.

[0029] The number average molecular weight (Mn) of the polysilsesquioxane graft polymer used in the present invention is not particularly limited, and it is usually 5,000—1,000,000, preferably <ί. 10 000—

1,000,000, more preferred <50,000—500,000.

The molecular weight distribution (Mw / Mn) of the polysilsesquioxane graft polymer used in the present invention is not particularly limited, but is usually 1.0 to 5.0, preferably 1.5 to 3.0.

[0030] The polysilsesquioxane graft polymer of the present invention has a weight loss rate (WL) of 10% or less, preferably 7% when heated to 300 ° C in thermogravimetric analysis (TGA) measurement. Less than

300

It is below and has excellent heat resistance.

[0031] Further, the polysilsesquioxane graft polymer of the present invention exhibits a cohesive force equal to or greater than that of a conventional acrylic pressure-sensitive adhesive. That is, the probe tack measured according to JIS Z0237 is 400 or more, preferably 450 or more, the holding power is lOOsec or more, preferably 1500 sec or more, more preferably 1800 sec or more, and the adhesive strength is 15NZ25mm or more. Preferably, it is 18 NZ25 mm or more, more preferably 19 NZ25 mm or more.

[0032] 2) Process for producing polysilsesquioxane graft polymer

The method for producing a polysilsesquioxane graft polymer of the present invention comprises a polysilsesquioxane compound (hereinafter referred to as “polysilsesquioxane compound”) having a repeating unit represented by the above formula (2) in the molecule. . 2) "and abbreviated) the presence of a radical polymerization initiator, formula (3): Table in ^{CH = C (R 2) -R} 3 (R 2, R 3 are as defined above). Berui composite (below)

2

Hereinafter, it is abbreviated as “bulu compound (3)”. ). [0033] The vinyl compound (3) to be used is not particularly limited as long as it is a compound having a radical polymerizable vinyl group (double bond). Examples thereof include acrylic compounds, aromatic vinyl compounds, bur-tolyl compounds, benzene ketone compounds, butyl ether compounds, vinyl sulfone compounds, vinyl ester compounds.

[0034] The acrylic compound is not particularly limited as long as it is a compound having a (meth) atalyloyl group in the molecule. Specific examples of the acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl. (Meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethyl hexyl (meth) acrylate, octyl (meta ) Atalylate, Nor (meth) Atalylate, Decyl (meth) Atalylate, Undecyl (meth) acrylate, Dodecyl (meth) atylate, Methoxymethyl (meth) atylate, Methoxyethylene glycol (meth) atylate , Methoxypolyethylene glycol (meth) attalylate, norphenoloxyl (meth) attaly , 3-black mouth-polyethylene glycol (meth) acrylate, butoxy polyethylene glycol (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobol (meta ) Atarylate, benzyl (meth) atarylate, 2-hydroxyethyl (meth) acrylate, 2- (meth) attayllooxychetyl 2-hydroxyethyl phthalate, glycerin mono (meth) acrylate, 2 —Hydroxybutyl (meth) acrylate, Polypropylene glycol (meth) acrylate, Polyethylene glycol mono (meth) acrylate, poly ε—force pro-latathone mono (meth) acrylate, dialkylaminoethyl (meth) acrylate, glycidyl (Meta) Atarilate, Mono [ (Meth) acryloxychetyl] acid phosphate, trifluorate cetyl (meth) ate, 2, 2, 3, 3—tetrafluoropropyl (meth) ate, 2, 2, 3, 4, 4, 4 monohexafluorobutyl (meth) acrylate, perfluorooctyl cetyl (meth) acrylate, dicyclopente-loxyalkyl (meth) acrylate, tricyclodeca-lukichetyl (meth) acrylate, isovol-luccietyl Monofunctional (meth) acrylate compounds such as (meth) acrylate, morpholine (meth) acrylate, Ν, Ν'-dimethylacrylimide; [0035] 2,2-dimethyl-3-hydroxypropyl 2,2dimethyl-3-hydroxypropionate di (meth) acrylate, ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, Polyethylene glycol di (meth) acrylate, propylene glycol diol (meth) acrylate, polypropylene glycol di (meth) acrylate, 1, 4 butanediol (meth) acrylate, 1, 6 xanediol di (meth) acrylate, Diglycerin di (meth) acrylate, neopentyl glycol di (meth) acrylate, bisphenol A ethylenide di- (meth) acrylate, bisphenol A propylene oxide di-carbide di (Meth) atarylate, 2, 2'-di (hydroxypropoxyphenyl) propane (Meth) atarylate, 2, 2'-di (hydroxyethoxyphenol) propane di (meth) acrylate, tricyclodecane dimethylol di (meth) acrylate, dicyclopentadiene (meta ) Atallate, pentanedi (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, 2, 2'-di (glycidyloxyphenyl) propane with (meth) acrylic acid, 2 —Hydroxy 1— (Meth) Atalyloxy 3—Bifunctional (Meth) Atalylate compounds such as (Meth) Atalyloxypropane;

[0036] Trimethylolpropane tritalylate, trimethylolpropane tri (oxetyl) (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hex (meta ) Atarylate, tetramethylol methane tri (meth) acrylate, tetramethylol methane tetra (meth) acrylate, tris (ataryloxy) isocyanurate, tris (2-hydroxyethyl) isocyanurate And polyfunctional (meta) attareito toy compounds such as hydroxy (propyl) isocyanurate tri (meth) acrylate.

[0037] Examples of the aromatic bur compound include styrene, α-methylstyrene, 4-methylstyrene, 4-methoxystyrene, 4 t-butoxystyrene, 3-chlorostyrene and the like. Examples of bur nitrile compounds include acrylonitrile and meta-tallow-tolyl. Examples of the burketone compound include burmethyl ketone and burphe ketone. Examples of the butyl ether compound include ethyl butyl ether and propyl butyl ether. Examples of the bulsulfone compound include bulmethylsulfone. Examples of the bull ester compound include bull acetate. Among these, heat resistance The use of acrylic compounds is particularly preferred because a graft polymer having excellent properties and cohesive strength can be obtained efficiently.

In the present invention, two or more of the vinyl compounds (3) may be used in combination. In this case, a graft copolymer in which a vinyl copolymer (3) block copolymer is grafted to the molecular ends by gradually adding different types of vinyl compounds (3) to the polymerization reaction solution. A polymer can be obtained.

[0039] The amount of the vinyl compound (3) used is usually in the range of 1000 parts by weight, preferably 10-200 parts by weight, per 1 part by weight of the polysilsesquioxane compound (2). .

[0040] As the radical polymerization initiator, organic peroxides, azo compounds and the like can be used. Organic peroxides include disilver oxides such as lauroyl peroxide and benzoyl peroxide, 1, 1 bis (t-butylperoxy) cyclohexane, 1

, 1 Bis (t-butylperoxy) 3, 3, 5-peroxyketals such as trimethylcyclohexane, diisopropylperoxydicarbonate, peroxydicarbonates such as diethylhexyloxydicarbonate, t-butylperoxy 2 —Peroxyesters such as ethylhexanoate and t-butylperoxyisobutyrate. Examples of the azo compound include azobisisobutyoxy-tolyl and 1,1-azobiscyclohexane t carbo-tolyl. These can be used alone or in combination of two or more.

[0041] The amount of the radical polymerization initiator used is the formula introduced into the polysilsesquioxane compound (2).

The ratio is usually 0.25-4 mol times, preferably 0.4-2 mol times the amount of the Silane compound represented by (4).

[0042] In the method for producing a polysilsesquioxane graft polymer of the present invention, a predetermined amount of a radical polymerization initiator and a vinyl compound (3) is added to a solvent solution of a polysilsesquioxane compound (2). It can be carried out by adding and stirring the whole volume. This reaction is preferably carried out in an inert gas atmosphere such as nitrogen gas, argon gas or helium gas.

[0043] The solvent to be used is not particularly limited as long as it is inert to the reaction. For example, aromatic hydrocarbons such as benzene, toluene, xylene; aliphatic hydrocarbons such as n pentane, n-hexane, n-hexane, n-octane; cyclopentane, cyclohexane, cyclohexane Cycloaliphatic hydrocarbons such as heptane and cyclooctane; ethers such as jetyl ether, diisopropyl ether, 1,2-dimethoxyethane, dibutyl ether, tetrahydrofuran and dioxane; black mouth form, carbon tetrachloride, 1, 2 —Halogenated hydrocarbons such as dichloroethane and black benzene; Esters such as ethyl acetate, propyl acetate, butyl acetate, and methyl propionate; Ketones such as acetone, methyl ethyl ketone, jetyl ketone, methyl isobutyl ketone, and cyclohexanone Amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone; -tolyls such as acetonitrile and benzo-tolyl; sulfoxides such as dimethyl sulfoxide and sulfolane; . These solvents can be used alone or in combination of two or more.

[0044] The amount of the solvent to be used is generally 0.5-10,000 ml, preferably 1000 ml, per lg of the polysilsesquioxane compound (2).

[0045] The reaction temperature is not particularly limited! However, it is usually in the temperature range up to the boiling point of the solvent to be used, preferably 20-100 ° C.

The reaction time is usually several minutes to several tens of hours, preferably 1 hour to 20 hours. After completion of the reaction, the target polymer can be isolated by pouring the reaction solution into a large amount of insoluble solvent and collecting the precipitated solid by filtration.

[0046] The polysilsesquioxane compound (2) can be produced as follows. That is, a silanic compound represented by the formula (4): (ASH) Si (OR ⁴ ) (X ¹ ) (hereinafter referred to as “silanic compound”).

P 3-p

(4) ". ) And Silane compounds (4) 0 to 100 times the amount of 1 part by weight of Silane compounds represented by formula (5): R'SKOR ⁵ ) (X ² ) Q 3-q abbreviated as "Composite (5)"

. ) Can be condensed in the presence of an acid catalyst or a base catalyst to obtain a polysilsesquioxane compound (2).

In the above formulas (4) and (5), A and R ¹ represent the same meaning as described above.

R ⁴ and R ⁵ each independently represent an alkyl group having 1 to 16 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, or an n-butyl group, and a methyl group or an ethyl group is preferred. .

X ¹ and X ² each independently represent a halogen atom such as a chlorine atom or a bromine atom, and a chlorine atom is preferred. P and q represent an integer of 0-3.

[0048] Specific examples of the Silane compound (4) include mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, mercaptomethyltripropoxysilane, mercaptomethyltributoxysilane, 2-mercaptoethyltrimethoxysilane, 2-Mercaptoethyltriethoxysilane, 2-Mercaptoethyltripropoxysilane, 2-Mercaptoethyltributoxysilane, 1 Mercaptoethyltrimethoxysilane, 1 Mercaptoethyltriethoxysilane, 1-mercapto Tiltripropoxysilane, 1 Mercaptotiltriboxysilane, 3 Mercaptopropyltrimethoxysilane, 3-Mercaptopropyltriethoxysilane, 3-Mercaptopropyltripropoxysilane, 3-Mercaptopropyltributoxy 4-mercaptobutyltrimethoxysilane, 4-mercaptobutyltriethoxysilane, 4-mercaptobutyltripropoxysilane, 4-mercaptobutyltributoxysilane, 5-mercaptopentyltrimethoxysilane, 5-mercaptopentyltriethoxysilane, 5-mercapto Pentiltripropoxysilane, 5-Mercaptopentylriboxysilane, 4 Mercaptophenyltrimethoxysilane, 4 Mercaptophenyltriethoxysilane, 4 Mercaptophenyltripropoxysilane, 4 Mercaptophenyltributoxysilane, 4 Mercaptophenyltriethoxysilane Alkoxysilane compounds such as 6-mercaptohexyltrimethoxysilane;

[0049] Mercaptomethyltrichlorosilane, mercaptomethylchlorodimethoxysilane, mercaptomethyldichloromethoxysilane, mercaptomethylchlorojetoxysilane, mercaptomethyldichloroethoxysilane, mercaptomethyltrib mouth silane, 2-mercaptoethyltrichlorosilane, 2-mercapto Ethyl chlorodimethoxysilane, 2-mercaptoethyl dichloromethoxysilane, 2-mercaptoethyl chlorojetoxysilane, 2-mercaptoethyl dichlorosilane, ethoxysilane, 2-mercaptoethyl rib ribose silane, 1 mercaptoethyltrichlorosilane Orchid, 1 mercaptoethyl chlorodimethoxysilane, 1 mercaptoethyl dichloromethoxysilane, 1 mercaptoethyl chlorodoxysilane, 1 mercaptoethyl Black-Ethoxysilane, 1 Mercaptoetiltrib Mosilane, 3 Mercaptopropyltrichlorosilane, 3-Mercaptopropylchlorodimethoxysilane, 3-Mercaptopropyldichloromethoxysilane, 3-Mercaptopropylchlorojetoxysilane, 3-Mercaptopropyldichloro Ethoxysilane, 3-mercaptopropyltribromosilane, 4 mercaptobutyl tricloate Silane, 4-mercaptobutylchlorodimethoxysilane, 4-mercaptobutyldichloromethoxysilane, 4-mercaptobutylchlorojetoxysilane, 4-mercaptobutyldichloroethoxysilane, 4-mercaptobutyltributylsilane, 5-mercaptopentyltrichlorosilane, 5-mercaptopentyl Chlorodimethoxysilane, 5-Mercaptopentyldichloromethoxysilane, 5-Mercaptopentylchlorojetoxysilane, 5-Mercaptopentyldichloroethoxysilane, 5-Mercaptopentyl ribose silane, 6-Mercaptotrichlorosilane, 4 Mercaptophenyltri Chlorosilane, 4 mercaptophenylchlorodimethoxysilane, 4 mercaptophenyldichloromethoxysilane, 4 mercaptophenyltrib mouth Down, 4 Merukaputofue - Le triethoxysilane halosilane compounds such; and combinations of two or more force thereof.

[0050] Specific examples of the silane compound (5) include (substituted) phenols such as phenyltrimethoxysilane, 4-chloropolymethoxysilane, phenyltriethoxysilane, and 2-methoxyphenyltriethoxysilane. Alkyltrialkoxysilanes; methyltrimethoxysilane, methyltriethoxysilane, etyltrimethoxysilane, etyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, and other alkyltrialkoxysilanes; cyanomethyltrimethoxy Silane, Cyanomethyltriethoxysilane, 2-Chanoethyltrimethoxysilane, 2-Chanoethyltriethoxysilane, 3-Cyanopropyltrimethoxysilane, 3-Cyanopropyltriethoxysilane, 4-Cyanobutyltrimethoxy Silane, 4-Syanobuchi Cyanoalkyltrialkoxysilanes such as triethoxysilane; Acetoxy groups such as acetomethylmethyltrimethoxysilane, acetomethymethyloletriethoxysilane, 3-acetoxypropinoletrimethoxysilane, 3-acetoxypropyltriethoxysilane Alkoxysilanes having the following:

[0051] Phenyltrichlorosilane, phenylchlorodimethoxysilane, phenyldichloromethoxysilane, phenyltrib mouth silane, 4-chlorophenyltrichlorosilane, phenyltrichlorosilane, 2-methoxyphenyltrichlorosilane, etc. (Substituted) phenylhalogenosilanes: methyl chloromethoxysilane, methyltributyl silane, methylchlorojetoxysilane, etyltrichlorosilane, ethylchlorodimethoxysilane, ethyldichloromethoxysilane, etyltribromosilane, n-propyltrichlorosilane, n-propyl Chlorodimethoxysilane, n-pro Alkylhalogenosilanes such as pyrdichloromethoxysilane; cyanomethyltrichlorosilane

Bromosilane, 3-cyanopropyltrichlorosilane, 3-cyanopropyltribromosilane, 4 halogenosilanes; acetomethylmethyltrichlorosilane, acetomethylmethyltrib-mouthed silane, 3-acetoxypropyltrichlorosilane, 3— And halogenosilanes having a cetoxy group such as acetoxiprovir trib mouth silane; and combinations of two or more thereof.

[0052] The mixing ratio of the silanic compound (4) and the silanic compound (5) can be arbitrarily set, but usually, the weight ratio of the silanic compound (4): the silanic compound (5) = The range is 100: 0-1:99.

[0053] Examples of the organic solvent used in the reaction for obtaining the polysilsesquioxane compound (2) include aromatic hydrocarbons such as benzene, toluene and xylene; methyl acetate, ethyl acetate, propyl acetate, and methyl propionate. Esters such as acetone, ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc .; methyl alcohol, ethyl alcohol, n propyl alcohol, isopropyl alcohol, n butyl alcohol, isobutyl alcohol, sec-butyl Alcohols such as alcohol and t-butyl alcohol; water; and the like. These solvents can be used alone or in admixture of two or more.

[0054] Examples of the acid catalyst used include inorganic acids such as hydrochloric acid and sulfuric acid; organic solvents such as p-toluenesulfonic acid, p-toluenesulfonic acid monohydrate, sulfonic acid, methanesulfonic acid, ethanesulfonic acid, acetic acid, and formic acid. Examples include acids.

[0055] Examples of the base catalyst used include metal hydroxides such as sodium hydroxide, potassium hydroxide, magnesium hydroxide, and calcium hydroxide; sodium methoxide, sodium ethoxide, potassium Metal alkoxides such as methoxide, potassium tert-butoxide, magnesium methoxide and magnesium ethoxide; primary amines such as methylamine, ethylamine and butylamine; secondary amines such as dimethylamine and dibutylamine; tertiary amines such as triethylamine and diisopropylethylamine Pyridine, nitrogen-containing heterocyclic compounds such as 1,8-diazabicyclo [5.4.0] undece-7-en (DB U); and the like. [0056] The amount of the acid catalyst or base catalyst used is usually in the range of 0.001% to 25% by weight, preferably 0.01% to 20% by weight, based on the silanic compound (4). is there.

The reaction temperature is usually in the temperature range from 0 ° C to the boiling point of the solvent used, preferably in the range of 40 ° C to 130 ° C. If the reaction temperature is too low, the progress of the condensation reaction may be insufficient. On the other hand, if the reaction temperature becomes too high, it is difficult to suppress gelling. The reaction is usually completed in minutes to hours.

[0057] The repeating unit of the copolycondensate obtained by the Silane compound (4) and the silane compound (5) is represented by any of the following formulas (a) to (c).

[0058] [Chemical 3]

[In the formula, A and R ¹ have the same meaning as described above.]

The polysilsesquioxane compound (2) used in the present invention is not particularly limited as long as it has at least the repeating units (a) and Z or (b) in the molecule. The polysilsesquioxane compound (2) used in the present invention has the above-mentioned (a) and (b), (a) and (c), (b) and (c), or (a), (b) And (c) a copolymer having a repeating unit, this copolymer may be any copolycondensate such as a random copolymer, a partial block copolymer, a complete block copolymer, etc. Good.

[0060] In the present invention, the repeating unit represented by (b) may be bonded in a form rotated up and down 180 °. For example, the repeating unit represented by (b) may be the repeating unit shown in (d) below. [0061] [Chemical 4]

(d)

As described above, a polysilsesquioxane compound (2) having a repeating unit structure called a linearly extending ladder structure can be obtained. Whether or not it has a ladder structure can be confirmed, for example, by performing an infrared absorption spectrum or X-ray diffraction measurement of the reaction product.

[0063] The number average molecular weight (Mn) of the resulting polysilsesquioxane compound (2) is usually in the range of 500-30000, preferably 1,000-20000. The number average molecular weight can be obtained, for example, by polystyrene conversion by SEC (size “exclusion” chromatography).

Further, the molecular weight distribution (Mw / Mn) of the polysilsesquioxane compound (2) is not particularly limited, but is usually in the range of 1.0 to 3.0.

[0064] 3) Adhesive

The pressure-sensitive adhesive of the present invention is characterized by containing the polysilsesquioxane graft polymer of the present invention.

The pressure-sensitive adhesive of the present invention can be produced by dissolving one or more of the polysilsesquioxane graft polymers of the present invention in a suitable solvent.

[0065] The solvent to be used is not particularly limited as long as it dissolves the polysilsesquioxane graft polymer of the present invention. For example, esters such as ethyl acetate, propyl acetate, butyl acetate, methyl propionate; acetone, methyl ethyl ketone, jetyl ketone, Ketones such as tilisobutylketone and cyclohexanone; amides such as N, N-dimethylformamide, N, N dimethylacetamide and N methylpyrrolidone; -tolyls such as acetonitrile and benzo-tolyl; dimethyl sulfoxide; Sulfoxides such as sulfolane; Aromatic hydrocarbons such as benzene, toluene, xylene; Aliphatic hydrocarbons such as n pentane, n-hexane, n heptane, n octane; Cyclopentane, cyclohexane, cycloheptane Cycloaliphatic hydrocarbons such as cyclooctane; ethers such as jetyl ether, diisopropyl ether, 1,2-dimethoxyethane, dibutyl ether, tetrahydrofuran, dioxane; black mouth form, carbon tetrachloride, 1, 2 —Halogenated hydrocarbons such as dichloroethane and black benzene; . These solvents can be used alone or in combination of two or more.

The amount of the solvent used is arbitrary. The amount of the polysilsesquioxane graft polymer of the present invention is usually 10,000 parts by weight, preferably 10-1,000 parts by weight, based on 100 parts by weight of the polysilsesquioxane graft polymer of the present invention. Is

[0067] The pressure-sensitive adhesive of the present invention contains the polysilsesquioxane graft polymer of the present invention as a main component, and, if desired, other pressure-sensitive adhesives, tackifiers, antioxidants, ultraviolet absorbers, light stabilizers. Agents, softeners, fillers and the like can be added.

[0068] Since the pressure-sensitive adhesive of the present invention contains the polysilsesquioxane graft polymer of the present invention as a main component, it has excellent heat resistance and excellent cohesive strength.

[0069] 4) Adhesive sheet

The pressure-sensitive adhesive sheet of the present invention comprises a base sheet and a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive of the present invention on the base sheet.

As the base sheet to be used, paper base materials such as dalasin paper, coated paper and cast paper; polyester films such as polyethylene terephthalate film, polybutylene terephthalate film and polyethylene naphthalate film; polyolefin films such as polypropylene film and polyethylene film Polyvinyl chloride film; Polyurethane film; Synthetic paper, cellulose sheets and films, non-woven fabrics, woven fabrics and knitted fabrics made of various materials. In addition, these substrate sheets can be printed by printing appropriate characters and designs on the surface as desired. [0070] The method for forming the pressure-sensitive adhesive layer on the base sheet is as follows: (i) The pressure-sensitive adhesive of the present invention is applied on the base sheet so as to have a predetermined thickness, and is heated at 40-150 ° C. A method of drying, on the GO release sheet (or process paper), apply the pressure-sensitive adhesive of the present invention to a predetermined thickness, and paste a substrate sheet on the coated surface at 40-150 ° C. After drying, it can be produced by a method such as peeling the release sheet. In the case of the GO method, the release sheet may be adhered as it is without being peeled off if desired, and may be peeled off when the adhesive sheet is used.

[0071] Examples of release sheets include paper substrates such as dalasin paper, coated paper, cast paper; polyester films such as polyethylene terephthalate film, polybutylene terephthalate film, polyethylene naphthalate film; polypropylene film, polyethylene film, etc. Polyolefin film; etc. are mentioned. These release sheets are usually coated with a release agent such as silicone resin on the surface, but the release sheet itself has releasability.

[0072] The method of applying the pressure-sensitive adhesive on the base sheet is not particularly limited, and a known coating method can be employed. The thickness of the pressure-sensitive adhesive layer obtained is usually 5-100 μm, preferably 10-60 μm.

[0073] Since the pressure-sensitive adhesive sheet of the present invention has a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive of the present invention having excellent heat resistance and cohesive strength, the pressure-sensitive adhesive strength may be lowered even when used in a high temperature environment. Absent.

Example

[0074] Next, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

The number average molecular weight (Mn) and molecular weight distribution (MwZMn) were measured by size exclusion chromatography (SEC) using the obtained polymer as a developing solvent with tetrahydrofuran (THF). It calculated | required as a polystyrene conversion value.

1) Synthesis of polysilsesquioxane compound (PPhMeSQ) [0075] [Chemical 5]

CO—

[0076] (In the formula, a represents a natural number.)

To the eggplant flask, toluene Z water mixed solution (volume ratio = 2Zl, 15mL), 3-mercaptopropyltrimethoxysilane (2.00g, 10.18mmol) and phenol trimethoxysilane (2.00g, 10. 18 mmol) and 0.3 ml of hydrochloric acid having a concentration of 6 molZ liter were charged and stirred at 80 ° C. for 6 hours. After completion of the reaction, the reaction solution was added dropwise to a large amount of n-hexane, and the precipitated solid was filtered and dried to obtain the desired polysilsesquioxane compound (PPhMeSQ) (yield: 71 %).

The structure of the obtained polymer was confirmed by measuring NMR and ¹³ C-NMR. Moreover, the number average molecular weight (Mn) of the obtained polysilsesquioxane compound (PPhMeSQ) was 1,100, and molecular weight distribution (MwZMn) was 1.3.

2) Synthesis of graft polymer [0077] [Chemical 6]

[In the formula, a, b and b ′ represent natural numbers.]

Under a nitrogen atmosphere, V, PPhMeSQ, (meth) acrylic acid ester and ethyl acetate were used as radical polymerization initiators as radical polymerization initiators, and stirred at 70 ° C. for 7 hours.

[0079] The reaction charge was 0.2 g for AIBN, 1.34 g for PPhMeSQ, 100 g for ethyl acetate, and 100 g for (meth) acrylic acid ester.

Moreover, the following were used as (meth) acrylic acid ester.

Example 1: Methylmetatalylate (MMA)

Example 2: n-Butylmetatalylate (BMA)

Example 3: n-dodecyl metatalylate (DMA)

Example 4: n-Butyl acrylate (BA)

[0080] After completion of the reaction, the solution was added dropwise to a large amount of hexane, and the precipitated solid was separated by filtration and dried to obtain a polymer. It was. The type of (meth) acrylic acid ester used, the number average molecular weight (Mn), molecular weight distribution (MwZMn), and reaction yield of the obtained polymer are shown in Table 1 below.

In Table 1, MMA, BMA, DMA and BA have the same meaning as above.

Column 1

[0081] [Chemical 7]

[0082] (where n represents a natural number)

Under a nitrogen atmosphere, AIBN was used as a radical polymerization initiator, and the corresponding monomers (MMA, BMA, DMA, BA) and ethyl acetate were charged into a glass tube and stirred at 75 ° C for 15 hours. After completion of the reaction, the reaction mixture was added dropwise to a large amount of n-hexane, and the precipitated solid was separated by filtration and dried to obtain a polymer. The reaction charge was 2 g of AIBNO., 100 g of ethyl acetate, and 100 g of (meth) acrylic acid ester.

[0083] Table 1 below shows the types of (meth) acrylic acid esters, the number average molecular weight (Mn), molecular weight distribution (MwZMn), and reaction yield of the obtained polymer.

In addition, the number average molecular weight (Mn) and the molecular weight distribution (MwZMn) were measured by SEC in the same manner as in Examples, and were obtained as polystyrene conversion values.

[0084] [Table 1]

Table 1

[0085] 3) Preparation of adhesive

By adding 100 ml of ethyl acetate to the solid content of 50 parts by weight of the polymer obtained in Example 3 and Comparative Example 3 and mixing them well, the adhesives of Examples and Comparative Examples were respectively obtained. Prepared.

[0086] 4) Preparation of adhesive sheet

Each adhesive obtained above is applied to a transparent polyethylene terephthalate film (PET film) with a thickness of 50 m so that the dry film thickness is 20 im, and heated at 100 ° C for 2 minutes. The membrane was dried. Next, a PET film that had been subjected to a release treatment with silicone resin was attached to the surface of the pressure-sensitive adhesive layer as a release sheet.

[0087] Thermal ¾ loss test

Thermogravimetric analysis (TGA) measurement was performed using a thermogravimetric analyzer (manufactured by Shimadzu Corporation). The measurement was carried out by accurately weighing lOmg of the polymer and raising the temperature at 10 ° CZ in an air stream (lOOmlZ). Table 2 shows the measurement results. In Table 2, WL is the weight at 300 ° C.

300

Indicates the quantity loss rate.

[0088] Viscous property test

With respect to the pressure-sensitive adhesive sheet obtained above, the holding power, probe tack and pressure-sensitive adhesive strength were measured according to JIS Z0237. Table 2 shows the measurement results. [0089] [Table 2] Number: Table 2

*: Cohesive failure

[0090] From Table 2, the adhesive of this example (Example 3) was excellent in heat resistance with very little thermogravimetric loss as measured by TGA. In addition, the probe tack is equivalent to the adhesive of the comparative example (Comparative Example 3), and the holding power and adhesive strength are much better than the adhesive of the comparative example, and it has excellent cohesive strength. It was.

Industrial applicability

[0091] According to the present invention, a novel polysilsesquioxane graft polymer that can be a pressure-sensitive adhesive having both excellent heat resistance and cohesion, a method for producing the same, a pressure-sensitive adhesive using the polysilsesquioxane graft polymer, and An adhesive sheet is provided.

Claims

(In the formula, A represents a linking group, R ¹ represents an optionally substituted hydrocarbon group, R ² represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, and R ³ is polar. Represents an aryl group which may have a group or a substituent 1, m and n each independently represents 0 or any natural number, except when m = n = 0 kl, k2 And k3 each independently represents an arbitrary natural number.When kl, k2 and k3 are each 2 or more, the formula: -CH -C (R ² ) (R ³ )-

2

The groups to be used may be the same or different. A polysilsesquioxane graft polymer having a repeating unit represented by

[2] The polysilsesquioxane graft polymer according to [1], which has a number average molecular weight of 5,000 to 1,000,000.

[3] In the molecule, the formula (2)

[Chemical 2]

(In the formula, A represents a linking group, R ¹ represents a hydrocarbon group which may have a substituent. 1, m and n each independently represents 0 or an arbitrary natural number, provided that except for the case where m = n = 0.) In the presence of a radical polymerization initiator, a polysilsesquioxane compound having a repeating unit represented by formula (3): CH = C (R ² ) -R ³ (wherein R ² is a hydrogen atom or 1 carbon atom)

2 1

8 represents an alkyl group, and R ³ has a polar group or a substituent, and may represent an aryl group. The method for producing a polysilsesquioxane graft polymer according to claim 1 or 2, characterized in that the polysilsesquioxane graft polymer according to claim 1 or 2 is reacted.

[4] Formula (4): (ASH) Si (OR ⁴ ) (X ¹ ) (wherein A represents the same meaning as described above, and R ⁴ has 1 carbon atom)

P 3-p

16 represents an alkyl group, X ¹ represents a halogen atom, and p represents an integer of 0-3. ) And 1 part by weight of the silane compound represented by the formula (4), 0 to 100 times the amount of the formula (5): R′SKOR ⁵ ) (X ² ) ( In the formula, R ¹ represents the same meaning as described above, R ⁵ represents carbon q 3-q

X 1 represents an alkyl group of 1 to 6, X ² represents a halogen atom, and q represents an integer of 0-3. The polysilsesquioxane compound having a repeating unit represented by the formula (2) in the molecule is obtained by condensing the silane compound represented by the formula (2) in the presence of an acid catalyst or a base catalyst. A process of obtaining

The method according to claim 3, further comprising a step of reacting the obtained polysilsesquioxane compound with the vinyl compound represented by the formula (3) in the presence of a radical polymerization initiator. Of producing a polysilsesquioxane graft polymer.

[5] An adhesive comprising the polysilsesquioxane graft polymer according to claim 1 or 2.

[6] A base sheet and an adhesive formed on the base sheet from the adhesive according to claim 5. A pressure-sensitive adhesive sheet comprising an agent layer.