WO2006033147A1 - Polymère greffé de polysilsesquioxane, procédé servant à produire celui-ci et adhésif autocollant - Google Patents

Polymère greffé de polysilsesquioxane, procédé servant à produire celui-ci et adhésif autocollant Download PDF

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Publication number
WO2006033147A1
WO2006033147A1 PCT/JP2004/013842 JP2004013842W WO2006033147A1 WO 2006033147 A1 WO2006033147 A1 WO 2006033147A1 JP 2004013842 W JP2004013842 W JP 2004013842W WO 2006033147 A1 WO2006033147 A1 WO 2006033147A1
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group
formula
polysilsesquioxane
graft polymer
meth
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PCT/JP2004/013842
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English (en)
Japanese (ja)
Inventor
Atsuko Kimura
Mikihiro Kashio
Toshio Sugizaki
Osamu Moriya
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Lintec Corporation
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Priority to PCT/JP2004/013842 priority Critical patent/WO2006033147A1/fr
Publication of WO2006033147A1 publication Critical patent/WO2006033147A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/442—Block-or graft-polymers containing polysiloxane sequences containing vinyl polymer sequences
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/08—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C09J151/085—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds on to polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/10—Block or graft copolymers containing polysiloxane sequences

Definitions

  • 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.
  • 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.
  • bar code printed adhesive sheets labels are attached to parts.
  • 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.
  • 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.
  • rubber-based or acrylic pressure-sensitive adhesives are used as the pressure-sensitive adhesive constituting the heat-resistant pressure-sensitive adhesive layer.
  • 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.
  • a 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.
  • 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.
  • 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.
  • 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.
  • 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
  • kl, k2 and k3 each independently represent an arbitrary natural number.
  • the groups can be the same or different.
  • the polysilsesquioxane graft polymer of the present invention preferably has a number average molecular weight of 5,000 to 1,000,000.
  • A represents a linking group
  • R 1 represents an optionally substituted hydrocarbon group.
  • m and n each independently represents 0 or an arbitrary natural number.
  • 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
  • R 3 has a polar group or a substituent, and may represent an aryl group.
  • a method for producing a polysilsesquioxane graphene polymer comprises reacting with a vinyl compound represented by formula (I).
  • 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
  • X 1 represents a halogen atom
  • p represents an integer of 0-3.
  • an adhesive comprising the polysilsesquioxane graft polymer 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.
  • 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.
  • 1) a polysilsesquioxane graft polymer 2) a process for producing a polysilsesquioxane graft polymer, 3) an adhesive, and 4) an adhesive sheet.
  • the polysilsesquioxane graft polymer of the present invention has a repeating unit represented by the formula (1) in the molecule.
  • 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.
  • a saturated or unsaturated alkylene group which may have a substituent, It may have a substituent and may be a / or a arylene group.
  • 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.
  • 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.
  • 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.
  • substituents 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.
  • A is a saturated or unsaturated alkylene group which may have a substituent.
  • 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;
  • 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.
  • 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.
  • aryl groups such as phenol-nolesnorehoninole group and p-methylphenolsulfonyl group.
  • 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 may be used. Examples thereof include a naphthyl group and a 2-naphthyl group.
  • kl, k2 and k3 each independently represent an arbitrary natural number.
  • 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
  • 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 ⁇ . 10 000—
  • 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.
  • 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
  • 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.
  • 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.
  • 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.
  • 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
  • polyfunctional (meta) attareito toy compounds such as hydroxy (propyl) isocyanurate tri (meth) acrylate.
  • Examples of the aromatic bur compound include styrene, ⁇ -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.
  • two or more of the vinyl compounds (3) may be used in combination.
  • a polymer can be obtained.
  • 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). .
  • organic peroxides include disilver oxides such as lauroyl peroxide and benzoyl peroxide, 1, 1 bis (t-butylperoxy) cyclohexane, 1
  • azo compound 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.
  • 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.
  • 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).
  • 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.
  • the solvent to be used is not particularly limited as long as it is inert to the reaction.
  • 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
  • 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).
  • 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.
  • 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.
  • 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”).
  • 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)"
  • 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.
  • 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-mercaptobutyltrime
  • silane compound (5) examples 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, acet
  • phenylhalogenosilanes methyl chloromethoxysilane, methyltributyl silane, methylchlorojetoxysilane, etyltrichlorosilane, ethylchlorodimethoxysilane, ethyldichloromethoxysilane, etyltribromosilane, n-propyltrichlorosilane, n-propyl Chlorodimethoxysilane, n-pro Alkylhalogenosilanes such as pyrdichloromethoxysilane; cyanomethyltrichlorosilane
  • 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.
  • aromatic hydrocarbons such as benzene, toluene and xylene
  • Esters such as acetone, ketones such
  • 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.
  • 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.
  • 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.
  • 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).
  • 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.
  • the repeating unit represented by (b) may be bonded in a form rotated up and down 180 °.
  • the repeating unit represented by (b) may be the repeating unit shown in (d) below.
  • 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.
  • 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).
  • 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.
  • 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.
  • the solvent to be used is not particularly limited as long as it dissolves the polysilsesquioxane graft polymer of the present invention.
  • 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 o
  • 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.
  • 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.
  • 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.
  • these substrate sheets can be printed by printing appropriate characters and designs on the surface as desired.
  • 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.
  • 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.
  • 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 ⁇ m, preferably 10-60 ⁇ m.
  • 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.
  • Mn number average molecular weight
  • MwZMn molecular weight distribution
  • 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.
  • V PPhMeSQ
  • (meth) acrylic acid ester and ethyl acetate were used as radical polymerization initiators, and stirred at 70 ° C. for 7 hours.
  • 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.
  • MMA, BMA, DMA and BA have the same meaning as above.
  • 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.
  • Mn number average molecular weight
  • MwZMn molecular weight distribution
  • 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.
  • PET film transparent polyethylene terephthalate film
  • 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.
  • the adhesive of this example was excellent in heat resistance with very little thermogravimetric loss as measured by TGA.
  • 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.
  • 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.

Abstract

L'invention concerne un nouveau polymère greffé de polysilsesquioxane lequel a des motifs représentés par la formule (1) suivante dans la molécule et peut devenir un adhésif autocollant combinant une excellente résistance à la chaleur et une excellente force d'adhérence ; un procédé servant à produire le polymère ; et un adhésif autocollant et une feuille autoadhésive employant chacun ce polymère greffé de polysilsesquioxane. (Dans la formule, A représente un groupe de liaison ; R1 représente un groupe hydrocarboné facultativement substitué ; R2 représente un hydrogène ou un alkyle en C1-18 ; R3 représente un groupe polaire ou un aryle facultativement substitué ; l, m et n sont chacun 0 ou n'importe quel entier naturel, à condition que le cas où m = n = 0 soit exclu ; et k1, k2 et k3 sont chacun n'importe quel entier naturel.) (1)
PCT/JP2004/013842 2004-09-22 2004-09-22 Polymère greffé de polysilsesquioxane, procédé servant à produire celui-ci et adhésif autocollant WO2006033147A1 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013176238A1 (fr) 2012-05-25 2013-11-28 株式会社ダイセル Composition de résine durcissable, et produit durci, agent d'étanchéité, et dispositif optique à semi-conducteurs les utilisant
JP2019099775A (ja) * 2017-12-08 2019-06-24 日鉄ケミカル＆マテリアル株式会社 平坦化膜形成用塗布液およびその製造方法、ならびに平坦化膜付き金属箔コイルおよびその製造方法
JP2019099774A (ja) * 2017-12-08 2019-06-24 日鉄ケミカル＆マテリアル株式会社 平坦化膜形成用塗布液およびその製造方法、ならびに平坦化膜付き金属箔コイルおよびその製造方法
CN110494472A (zh) * 2017-10-30 2019-11-22 瓦克化学股份公司 用于生产球形聚倍半硅氧烷粒子的方法
US20210214584A1 (en) * 2020-01-09 2021-07-15 Tesa Se Adhesive printing form attachment layer, method for its manufacture, and printing form attachment cylinder comprising the same

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JPH06279586A (ja) * 1993-03-25 1994-10-04 Showa Denko Kk ポリメチルシルセスキオキサン系重合体およびポリメチルシルセスキオキサン構造を有するポリマー
JPH06306173A (ja) * 1993-04-26 1994-11-01 Showa Denko Kk 反応性ポリオルガノシロキサン
JPH09216922A (ja) * 1996-02-08 1997-08-19 Showa Denko Kk 耐水性付与剤
JPH09324054A (ja) * 1996-06-06 1997-12-16 Showa Denko Kk ポリオルガノシロキサン変性重合体及びその製造方法
JPH10130393A (ja) * 1996-09-03 1998-05-19 Showa Denko Kk 全側鎖メルカプト基含有ポリオルガノシルセスキオキサンおよびその製造方法

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JPH06279586A (ja) * 1993-03-25 1994-10-04 Showa Denko Kk ポリメチルシルセスキオキサン系重合体およびポリメチルシルセスキオキサン構造を有するポリマー
JPH06306173A (ja) * 1993-04-26 1994-11-01 Showa Denko Kk 反応性ポリオルガノシロキサン
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JPH09324054A (ja) * 1996-06-06 1997-12-16 Showa Denko Kk ポリオルガノシロキサン変性重合体及びその製造方法
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013176238A1 (fr) 2012-05-25 2013-11-28 株式会社ダイセル Composition de résine durcissable, et produit durci, agent d'étanchéité, et dispositif optique à semi-conducteurs les utilisant
CN110494472A (zh) * 2017-10-30 2019-11-22 瓦克化学股份公司 用于生产球形聚倍半硅氧烷粒子的方法
JP2019099775A (ja) * 2017-12-08 2019-06-24 日鉄ケミカル＆マテリアル株式会社 平坦化膜形成用塗布液およびその製造方法、ならびに平坦化膜付き金属箔コイルおよびその製造方法
JP2019099774A (ja) * 2017-12-08 2019-06-24 日鉄ケミカル＆マテリアル株式会社 平坦化膜形成用塗布液およびその製造方法、ならびに平坦化膜付き金属箔コイルおよびその製造方法
JP7020889B2 (ja) 2017-12-08 2022-02-16 日鉄ケミカル＆マテリアル株式会社 平坦化膜形成用塗布液およびその製造方法、ならびに平坦化膜付き金属箔コイルおよびその製造方法
JP7020890B2 (ja) 2017-12-08 2022-02-16 日鉄ケミカル＆マテリアル株式会社 平坦化膜形成用塗布液およびその製造方法、ならびに平坦化膜付き金属箔コイルおよびその製造方法
US20210214584A1 (en) * 2020-01-09 2021-07-15 Tesa Se Adhesive printing form attachment layer, method for its manufacture, and printing form attachment cylinder comprising the same

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