WO2015098314A1 - 粘着剤用組成物、粘着剤および粘着シート - Google Patents
粘着剤用組成物、粘着剤および粘着シート Download PDFInfo
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- WO2015098314A1 WO2015098314A1 PCT/JP2014/079600 JP2014079600W WO2015098314A1 WO 2015098314 A1 WO2015098314 A1 WO 2015098314A1 JP 2014079600 W JP2014079600 W JP 2014079600W WO 2015098314 A1 WO2015098314 A1 WO 2015098314A1
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- Prior art keywords
- meth
- pressure
- group
- sensitive adhesive
- acrylate
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- IYKBWQFWWASFAR-UHFFFAOYSA-N CCOC(SC(C)(C)C#N)=S Chemical compound CCOC(SC(C)(C)C#N)=S IYKBWQFWWASFAR-UHFFFAOYSA-N 0.000 description 1
- HYURBBIIHCNUSC-UHFFFAOYSA-N CCOC(SCC#N)=S Chemical compound CCOC(SCC#N)=S HYURBBIIHCNUSC-UHFFFAOYSA-N 0.000 description 1
- VZERTPFKMKYOGV-UHFFFAOYSA-N CCOC(SCc1ccccc1)=S Chemical compound CCOC(SCc1ccccc1)=S VZERTPFKMKYOGV-UHFFFAOYSA-N 0.000 description 1
- KZYBHGZYLWGLCP-UHFFFAOYSA-N CCOCSC(C)c1ccccc1 Chemical compound CCOCSC(C)c1ccccc1 KZYBHGZYLWGLCP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
-
- 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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
- C08F220/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/625—Polymers of alpha-beta ethylenically unsaturated carboxylic acids; hydrolyzed polymers of esters of these acids
- C08G18/6254—Polymers of alpha-beta ethylenically unsaturated carboxylic acids and of esters of these acids containing hydroxy groups
-
- 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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
-
- 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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
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- 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
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
Definitions
- the present invention provides a pressure-sensitive adhesive composition containing a (meth) acrylic acid ester polymer obtained by reversible addition-fragmentation chain transfer (RAFT) polymerization and an isocyanate compound, a pressure-sensitive adhesive formed from the composition, And a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer formed from the composition.
- RAFT reversible addition-fragmentation chain transfer
- Acrylic polymer is used from the viewpoint of weather resistance and transparency as a conventional adhesive composition for a protective film.
- Acrylic polymers are generally synthesized by so-called free radical polymerization.
- the acrylic polymer obtained by free radical polymerization produces a low molecular weight component and a polymer component having no functional group, and these components are deteriorated in removability or adherend when the adhesive sheet is peeled off. It was difficult to satisfy the required performance required for the pressure-sensitive adhesive layer for the protective film at the same time.
- Patent Document 1 RAFT obtained by subjecting a vinyl monomer to RAFT polymerization using a RAFT polymerization agent obtained by a RAFT polymerization method using a dibenzyltrithiocarbonate derivative having a hydroxyl group at both ends as a starting material. Polymers are described. Moreover, the polymer obtained by making a diisocyanate compound react with the hydroxyl group which this RAFT polymer has is described.
- Patent Document 1 does not particularly examine the use of a polymer obtained by reacting a diisocyanate compound with the hydroxyl group of the RAFT polymer as an adhesive.
- Patent Document 2 discloses a pressure-sensitive adhesive comprising a (meth) acrylate copolymer having a weight average molecular weight of 200,000 to 2,000,000 and a molecular weight distribution of less than 2.5, obtained by living radical polymerization, and a crosslinking agent.
- a protective film having a pressure-sensitive adhesive layer formed by the composition is described.
- Patent Document 3 discloses that a weight average molecular weight obtained by copolymerizing a (meth) acrylic acid alkyl ester and a vinyl monomer having a reactive functional group by a living radical polymerization method using an organic tellurium compound is 300,000 to A pressure-sensitive adhesive obtained by blending 2 million copolymers and a crosslinking agent is described.
- An object of the present invention is to provide a pressure-sensitive adhesive composition capable of forming a pressure-sensitive adhesive that exhibits excellent adhesive properties even when exposed to heat-resistant conditions and that reduces the degree of contamination of the adherend when the pressure-sensitive adhesive sheet is peeled off. To provide things.
- the present inventors diligently studied to solve the above problems. As a result, the inventors found that the above-mentioned problems can be solved by a composition for pressure-sensitive adhesives containing a specific (meth) acrylic acid ester polymer and an isocyanate compound having 3 or more isocyanate groups in one molecule, and the present invention is completed. It came to.
- the present invention includes, for example, the following [1] to [4].
- the weight average molecular weight (Mw) obtained by RAFT polymerization and measured by gel permeation chromatography is 60,000 to 200,000, and the molecular weight distribution (Mw / Mn) is 3.0.
- the composition for adhesives which is the following and contains the (meth) acrylic acid ester polymer which has a structural unit derived from a hydroxyl-containing monomer, and (B) the isocyanate compound in which the number of isocyanate groups in 1 molecule is 3 or more.
- the isocyanate compound (B) is contained in a range of 0.1 to 50 parts by mass in solid content ratio with respect to 100 parts by mass of the (meth) acrylic acid ester polymer (A). Composition for pressure-sensitive adhesives.
- a pressure-sensitive adhesive sheet having a base material and a pressure-sensitive adhesive layer formed from the composition according to [1] or [2].
- the composition for adhesives which can form the adhesive which shows the outstanding adhesion characteristic when exposed to heat-resistant conditions, and the contamination degree with respect to the adherend at the time of adhesive sheet peeling is reduced is formed. Things can be provided. Moreover, the said composition can form the adhesive with a small raise with time of adhesive force, and low peeling rate dependence and peeling temperature dependence of adhesive force.
- polymer is used to include homopolymers and copolymers
- polymerization is used to include homopolymerization and copolymerization.
- the compound represented by formula (i) (i is a formula number) is also simply referred to as “compound (i)”.
- the pressure-sensitive adhesive composition of the present invention has a weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) obtained by RAFT polymerization of 60,000 to 200,000, and a molecular weight distribution (Mw / Mn) is 3.0 or less, a (meth) acrylic acid ester polymer (A) having a structural unit derived from a hydroxyl group-containing monomer, an isocyanate compound (B) having 3 or more isocyanate groups in one molecule, and Containing.
- GPC gel permeation chromatography
- the weight average molecular weight (Mw) measured by the GPC method of the RAFT polymer (A) is 60,000 to 200,000, preferably 70,000 to 180,000, more preferably 80,000 to 160, 000.
- “Peeling speed dependence of adhesive strength” refers to the degree to which the adhesive strength (peeling strength) is affected by the peeling speed when peeling an adhesive sheet. “Peeling temperature dependence of adhesive strength” refers to the degree to which the adhesive strength (peeling strength) is affected by the peeling temperature when peeling an adhesive sheet.
- the molecular weight distribution (Mw / Mn) measured by the GPC method of the RAFT polymer (A) is 3.0 or less, preferably 2.8 or less, more preferably 2.5 or less. Since the RAFT polymer (A) having Mw / Mn in the above range has a uniform molecular weight and a small amount of low molecular weight components, the resulting pressure-sensitive adhesive sheet is excellent in heat resistance and is attached by a low molecular weight material when the pressure-sensitive adhesive sheet is peeled off. It can reduce body contamination. When Mw / Mn exceeds the above range, the adherence to the adherend under heat resistant conditions increases, and the dependency of the adhesive force on the peeling rate and the peeling temperature increases.
- the conventional pressure-sensitive adhesive composition requires that the polymer Mw is about 250,000 or more in order to ensure cohesion.
- the polymer exhibits excellent cohesive force despite the polymer Mw being 200,000 or less, and low molecular weight components adhere to the adherend even under heat resistant conditions. This prevents contamination of the adherend.
- the RAFT polymer (A) has a small molecular weight distribution, and the RAFT polymer (A) contains a number of hydroxyl groups derived from a hydroxyl group-containing monomer that serves as a crosslinking point with the polyfunctional isocyanate compound (B). It is considered that a highly cohesive pressure-sensitive adhesive layer can be formed. For this reason, by using the composition for pressure-sensitive adhesives of the present invention, it has excellent adhesive performance that suppresses an increase in adhesive strength over time even under heat-resistant conditions, and also depends on the peeling speed dependence and peeling temperature dependence of adhesive strength. It is possible to form an adhesive having excellent re-peeling performance such as low property.
- the hydroxyl group of the structural unit derived from the hydroxyl group-containing monomer is a crosslinking point that is crosslinked by the polyfunctional isocyanate compound (B).
- the content of the structural unit derived from the hydroxyl group-containing monomer is usually 0.1 to 30% by mass, preferably 0.5 to 20% by mass, more preferably based on the total structural unit amount. Is 1 to 10% by mass. When this content is in the above range, it is preferable from the viewpoint of crosslinkability of the RAFT polymer (A).
- the content of the RAFT polymer (A) in the pressure-sensitive adhesive composition of the present invention is usually 50 to 99.9% by mass, more preferably 70 to 99.%, based on 100% by mass of the solid content excluding the solvent of the composition. It is 9% by mass, particularly preferably 80 to 99.9% by mass.
- the content of the RAFT polymer (A) is in the above range, the performance as an adhesive is balanced and the adhesive properties are excellent.
- the (meth) acrylic acid ester polymer (A) is obtained, for example, by RAFT polymerization using at least a hydroxyl group-containing monomer as a raw material monomer.
- the RAFT polymerization method is a method of polymerizing a radically polymerizable compound as a raw material monomer in the presence of a RAFT agent. The whole amount of the raw material monomers may be batch charged and polymerized, or after a part of the raw material monomers are polymerized, the remaining monomer components may be added continuously or intermittently for polymerization.
- RAFT agent a conventionally known compound can be used and is not particularly limited.
- the RAFT agent include thiocarbonylthio compounds such as dithioesters, trithiocarbonates, dithiocarbamates, and xanthates.
- xanthate represented by the formula (a1-4) thiocarbonylthio compounds
- Z 1 is an aryl group or an alkyl group, for example, an aryl group having 6 to 8 carbon atoms such as a phenyl group or a cyanophenyl group, or an alkyl group having 2 to 8 carbon atoms such as an ethyl group.
- Z 2 is an alkyl group, for example, an alkyl group having 2 to 18 carbon atoms such as a dodecyl group.
- Z 3 and Z 4 are each independently an alkyl group, an aryl group or a 4-pyridyl group, such as an alkyl group having 1 to 8 carbon atoms such as a methyl group or an aryl group having 6 to 8 carbon atoms such as a phenyl group. .
- Z 3 and Z 4 may combine with each other to form a heterocyclic ring such as a pyrrole ring or a pyrrolidone ring together with the N atom in formula (a1-3).
- Z 5 is an alkyl group, for example, an alkyl group having 1 to 8 carbon atoms such as an ethyl group.
- R is a monovalent organic group, for example (I) an alkyl group, and (ii) one or more of the hydrogen atoms of the alkyl group are a phenyl group, a cyano group, a hydroxyl group, a carboxyl group, an alkoxycarbonyl group having 1 to 4 carbon atoms, a phenoxycarbonyl group, an acetoxy And a group substituted with at least one group selected from the group R s consisting of the following g1 to g4.
- two Rs may be the same or different.
- the carbon number of the alkyl group in R is usually 1-18, preferably 2-12.
- A is an alkylene group having 2 to 5 carbon atoms
- n is an integer of 10 to 300.
- R is a hydrogen atom bonded to a carbon atom bonded to S, which (I) the carbon bonded to S has a tertiary carbon alkyl group and (II) the alkyl group has A group in which one or two or more are substituted with at least one group selected from the group R s is preferable.
- Examples of the dithioester (a1-1) include the following compounds.
- trithiocarbonates (a1-2) and (a1-2 ') include the following compounds.
- n is an integer from 10 to 300.
- dithiocarbamate (a1-3) examples include the following compounds.
- Examples of xanthate (a1-4) include the following compounds.
- trithiocarbonate examples include compounds represented by the formula (a1-2 ′′).
- each R 1 is independently a divalent organic group.
- the compound (a1-2 ′′) has a trithiocarbonate structure near the center or the center of the molecule and has hydroxyl groups at both ends of the molecule.
- the compound (a1-2 ′′) is disclosed, for example, in JP-A-2007-230947. It can synthesize
- the structural units derived from the radical polymerizable compound are bonded almost uniformly on both sides of the trithiocarbonate structure in the center of the molecule or in the vicinity of the center.
- a highly symmetrical chain polymer having hydroxyl groups bonded to both ends of the molecule can be obtained.
- Examples of the compound (a1-2 ′′) include a compound represented by the formula (a1-2 ′′ -1) and a compound represented by the formula (a1-2 ′′ -2).
- Compound (a1-2 ′′ -1) has a trithiocarbonate structure near the center or center of the molecule, and has one hydroxyl group at each end of the molecule.
- each X is independently —COO—, —CONR 3 — or a direct bond
- R 3 is each independently an alkyl group, and the number of carbon atoms of the alkyl group is preferably 1 to 4, more preferably 1 to 3
- each R 2 is independently an alkylene group, and the alkylene group preferably has 1 to 4 carbon atoms, more preferably 1 to 3
- Ar is each independently Are groups in which at least one of the aromatic ring hydrogen contained in the phenylene group, naphthylene group, phenylene group, or naphthylene group is substituted with a substituent, such as an alkyl group or an alkoxy group.
- X represents a carbonyl group in —COO— and —CONR 3 — bonded to Ar.
- Two Xs are preferably the same group, and two R 2 are The same group is preferable, and two R 3 are preferably the same group, and two Ar are preferably the same group.
- Compound (a1-2 ′′ -2) has a trithiocarbonate structure near the center or the center of the molecule, and has two hydroxyl groups at both ends of the molecule.
- X and Ar have the same meanings as the same symbols in formula (a1-2 ′′ -1);
- R 4 is independently an alkylene group, and R 5 is independently It is a direct bond or an alkylene group, and these alkylene groups preferably have 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms.
- Two X are preferably the same group, two R 4 are preferably the same group, two R 5 are preferably the same group, and two Ar are the same group It is preferable.
- trithiocarbonate (a1-2 ′′) examples include the following compounds.
- the amount of the RAFT agent used is usually 0.05 to 20 parts by mass, preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the total amount of raw material monomers. If the amount of RAFT agent used is not less than the lower limit of the above range, the reaction control is easy, and if it is not more than the upper limit of the above range, it is easy to adjust the weight average molecular weight of the resulting polymer to the above range. .
- ⁇ Raw material monomer> In RAFT polymerization, it is preferable to use at least a hydroxyl group-containing monomer as a raw material monomer. Moreover, it is preferable to use (meth) acrylic acid ester other than a hydroxyl-containing monomer as a raw material monomer. In addition, functional group-containing monomers other than hydroxyl group-containing monomers and other copolymerizable monomers can be used.
- hydroxyl group-containing monomer examples include a hydroxyl group-containing (meth) acrylate, and specific examples include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. And hydroxyalkyl (meth) acrylates such as 6-hydroxyhexyl (meth) acrylate and 8-hydroxyoctyl (meth) acrylate.
- the number of carbon atoms in the alkyl group in the hydroxyalkyl (meth) acrylate is usually 2 to 8, preferably 2 to 6.
- the amount of the hydroxyl group-containing monomer used in the RAFT polymerization is usually 0.1 to 30% by mass, preferably 0.5 to 20% by mass, more preferably 1 to 10% by mass, based on the total mass of all raw material monomers. .
- the amount of the hydroxyl group-containing monomer is within the above range, it is preferable from the viewpoint of crosslinkability of the resulting RAFT polymer (A).
- the hydroxyl group-containing monomer can be used alone or in combination of two or more.
- (Meth) acrylic acid ester examples include alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, alkoxypolyalkylene glycol mono (meth) acrylate, alicyclic group, and aromatic ring-containing (meth) acrylate.
- functional group-containing (meth) acrylates such as hydroxyl group-containing (meth) acrylate; carboxyl group-containing (meth) acrylate and amino group-containing (meth) acrylate are excluded from (meth) acrylic acid esters.
- the number of carbon atoms of the alkyl group in the alkyl (meth) acrylate is preferably 1-20.
- the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl ( (Meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, Decyl (meth) acrylate, undeca (meth) acrylate, lauryl (meth) acrylate, o
- alkoxyalkyl (meth) acrylate examples include methoxymethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3-methoxypropyl (meth) acrylate, 3-ethoxypropyl ( And (meth) acrylate, 4-methoxybutyl (meth) acrylate, and 4-ethoxybutyl (meth) acrylate.
- alkoxypolyalkylene glycol mono (meth) acrylate examples include methoxydiethylene glycol mono (meth) acrylate, methoxydipropylene glycol mono (meth) acrylate, ethoxytriethylene glycol mono (meth) acrylate, ethoxydiethylene glycol mono (meth) acrylate, And methoxytriethylene glycol mono (meth) acrylate.
- Examples of the alicyclic group or aromatic ring-containing (meth) acrylate include cyclohexyl (meth) acrylate, benzyl (meth) acrylate, and phenyl (meth) acrylate.
- the total amount of (meth) acrylic acid ester used in the RAFT polymerization is usually 70 to 99.9% by mass, preferably 80 to 99.5% by mass, more preferably 89.95% to the total mass of all raw material monomers. It is 98.95 mass%.
- (Meth) acrylic acid ester can be used alone or in combination of two or more.
- Examples of the functional group-containing monomer include an acid group-containing monomer, an amino group-containing monomer, an amide group-containing monomer, a nitrogen-based heterocyclic ring-containing monomer, and a cyano group-containing monomer.
- Examples of the acid group include a carboxyl group, an acid anhydride group, a phosphoric acid group, and a sulfuric acid group.
- carboxyl group-containing monomer examples include ⁇ -carboxyethyl (meth) acrylate, 5-carboxypentyl (meth) acrylate, mono (meth) acryloyloxyethyl ester succinate, and ⁇ -carboxypolycaprolactone mono (meth) acrylate.
- Carboxyl group-containing (meth) acrylates such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid, and maleic acid.
- acid anhydride group-containing monomer examples include maleic anhydride.
- Examples of the phosphate group-containing monomer include (meth) acrylic monomers having a phosphate group in the side chain, and examples of the sulfate group-containing monomer include (meth) acrylic monomers having a sulfate group in the side chain.
- amino group-containing monomer examples include amino group-containing (meth) acrylates such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate.
- Examples of the amide group-containing monomer include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, and N-hexyl (meth) acrylamide.
- Examples of the nitrogen heterocycle-containing monomer include vinyl pyrrolidone, acryloyl morpholine, and vinyl caprolactam.
- Examples of the cyano group-containing monomer include cyano (meth) acrylate and (meth) acrylonitrile.
- the total amount of functional group-containing monomers used in the RAFT polymerization is preferably 0 to 10% by mass, more preferably 0.05 to 5% by mass, based on the total mass of all raw material monomers.
- the functional group-containing monomer can be used alone or in combination of two or more.
- Copolymerizable monomers examples include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, propyl styrene, butyl styrene, hexyl styrene, heptyl styrene, octyl styrene, and other alkyl styrenes, fluorostyrene, chlorostyrene, bromostyrene, dibromo.
- styrene monomers such as styrene, iodinated styrene, nitrostyrene, acetylstyrene, and methoxystyrene, and vinyl acetate.
- the copolymerizable monomer can be used alone or in combination of two or more.
- RAFT polymerization is preferably performed in the presence of a polymerization initiator.
- the polymerization initiator include ordinary organic polymerization initiators, specifically, peroxides such as benzoyl peroxide and laurium peroxide, and azo such as 2,2′-isobisisobutyronitrile. Compounds. Among these, an azo compound is preferable.
- azo compound examples include 2,2′-azobisisobutyronitrile, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2-cyclopropyl). Propionitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile) 2- (carbamoylazo) isobutyronitrile, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis ( N, N′-dimethyleneisobutylamidine), 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) -propionamide], , 2′-azobis (isobutyramide) dihydrate, 4,4′-azobis (4-cyan
- the polymerization initiator can be used alone or in combination of two or more.
- the amount used is usually 0.001 to 2 parts by mass, preferably 0.002 to 1 part by mass with respect to 100 parts by mass of the raw material monomer.
- the amount of the polymerization initiator used is usually 0.1 to 3000 mol, preferably 1 to 10000 mol, per 1 mol of the RAFT agent.
- the reaction temperature in the RAFT polymerization method is usually 60 to 120 ° C., preferably 80 to 110 ° C., and is usually carried out in an inert gas atmosphere such as nitrogen, argon or helium.
- the reaction can be performed under any of the conditions of reduced pressure and reduced pressure, and is usually performed at normal pressure.
- the reaction time is usually 1 to 14 hours, preferably 2 to 12 hours.
- JP-A-2007-230947 and JP-A-2011-52057 can be referred to.
- reaction solvent examples include aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane and n-octane; cyclopentane, cyclohexane and cycloheptane.
- Cycloaliphatic hydrocarbons such as cyclooctane; ethers such as diethyl ether, diisopropyl ether, 1,2-dimethoxyethane, dibutyl ether, tetrahydrofuran, dioxane, anisole, phenylethyl ether, diphenyl ether; chloroform, carbon tetrachloride, Halogenated hydrocarbons such as 1,2-dichloroethane and chlorobenzene; esters such as ethyl acetate, propyl acetate, butyl acetate and methyl propionate; acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, cyclohexane Ketones such as non; amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone; nitriles such as ace
- polyfunctional isocyanate compound (B) is an isocyanate compound having 3 or more isocyanate groups in one molecule.
- a crosslinked body can be formed by crosslinking the polymer (A) with the compound (B).
- the number of isocyanate groups in the polyfunctional isocyanate compound (B) is 3 or more, preferably 3 to 6, and more preferably 3 to 4. It is preferable for the number of isocyanate groups to be in the above range from the viewpoint of the crosslinking reaction efficiency between the polymer (A) and the compound (B) and the flexibility of the pressure-sensitive adhesive.
- the molecular weight of the polyfunctional isocyanate compound (B) is usually 200 to 2,000, preferably 350 to 1,000. Since the cross-linking agent having a molecular weight of 350 or more has low volatility, the odor derived from the cross-linking agent can be reduced.
- polyfunctional isocyanate compound (B) examples include multimers (for example, dimers or trimers, isocyanurates) and derivatives (for example, polyhydric alcohols and 3 or more molecules) of difunctional or trifunctional isocyanates. Product of addition reaction with diisocyanate) and polymer. Moreover, aromatic polyisocyanate, aliphatic polyisocyanate, and alicyclic polyisocyanate having 3 or more isocyanate groups can also be mentioned.
- diisocyanate in the multimer, the derivative and the polymer examples include ethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 2-methyl-1,5-pentane diisocyanate, and 3-methyl-1,5.
- aliphatic diisocyanates such as pentane diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate; isophorone diisocyanate, cyclopentyl diisocyanate, cyclohexyl diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tolylene diene 7 to 3 carbon atoms such as isocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated tetramethylxylene diisocyanate Alicyclic diisocyanate; phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, naphthylene diisocyanate, diphenyl ether diisocyanate, diphenylmethane diisocyanate, and aromatic diisocyanates having 8 to 30 carbon atoms, such as diphenyl propane diisocyanate.
- polyhydric alcohol in the above derivative examples include trivalent or higher alcohols such as trimethylolpropane, glycerin, and pentaerythritol as low molecular weight polyhydric alcohols; examples of high molecular weight polyhydric alcohols include polyether polyols, A polyester polyol is mentioned.
- polyfunctional isocyanate compound (B) examples include a trimer of diphenylmethane diisocyanate, a polymethylene polyphenyl polyisocyanate, an isocyanurate of hexamethylene diisocyanate, a reaction product of trimethylolpropane and tolylene diisocyanate (for example, triethylene diisocyanate).
- Diisocyanate trimer adducts Diisocyanate trimer adducts
- reaction products of trimethylolpropane and hexamethylene diisocyanate eg, trimer adducts of hexamethylene diisocyanate
- polyether polyisocyanates polyether polyisocyanates
- polyester polyisocyanates 2,4,6- Examples thereof include triisocyanate toluene, 1,3,5-triisocyanatebenzene, and 4,4 ′, 4 ′′ -triphenylmethane triisocyanate.
- polyfunctional isocyanate compound (B) examples include, for example, a trade name “L-45” manufactured by Soken Chemical Co., Ltd., a trade name “Duranate TPA-100” manufactured by Asahi Kasei Chemicals Corporation, and a product name manufactured by Nippon Polyurethane Industry Co., Ltd. "Coronate L”, “Coronate HL”, “Coronate HK”, “Coronate HX”, “Coronate 2096", and "Millionate MR200".
- the content of the polyfunctional isocyanate compound (B) in the pressure-sensitive adhesive composition of the present invention is usually 0.1 to 50 parts by mass, preferably 100 parts by mass of the RAFT polymer (A) in terms of solid content. Is 0.5 to 30 parts by mass, more preferably 1 to 20 parts by mass.
- the content of the compound (B) is in the above range, the cohesiveness of the resulting composition is not lowered and the balance of the adhesive physical properties is excellent.
- the compound (B) is used at the above lower limit or more, the reaction rate between the hydroxyl group and the isocyanate group is improved. If it is less than the above lower limit value, curing may be insufficient and adhesive performance may not be exhibited.
- composition of the present invention may contain an isocyanate compound having 2 isocyanate groups in one molecule in addition to the polyfunctional isocyanate compound (B).
- isocyanate compound having 2 isocyanate groups in one molecule in addition to the polyfunctional isocyanate compound (B).
- diisocyanates such as aliphatic diisocyanate, alicyclic diisocyanate, and aromatic diisocyanate.
- composition for pressure-sensitive adhesives of the present invention is an organic solvent, an antistatic agent, an ultraviolet absorber, an antioxidant, a tackifying resin, in addition to the above components, as long as the transparency, visibility and effects of the present invention are not impaired.
- 1 type (s) or 2 or more types selected from a plasticizer, a filler, a stabilizer, a softening agent, and a wettability adjusting agent may be contained.
- the reaction solvent described in the RAFT polymerization column can be used.
- the polymer solution containing the RAFT polymer (A) and the reaction solvent obtained by RAFT polymerization and the polyfunctional isocyanate compound (B) can be mixed to prepare a pressure-sensitive adhesive composition.
- the content of the organic solvent is usually 0 to 90% by mass, preferably 10 to 80% by mass.
- the pressure-sensitive adhesive and pressure-sensitive adhesive layer of the present invention are formed from the above-described pressure-sensitive adhesive composition.
- the pressure-sensitive adhesive and pressure-sensitive adhesive layer of the present invention can be prepared by, for example, advancing the crosslinking reaction in the above-described pressure-sensitive adhesive composition, thereby specifically converting the (meth) acrylic acid ester polymer (A) to a polyfunctional isocyanate compound ( Obtained by crosslinking in B).
- the pressure-sensitive adhesive and pressure-sensitive adhesive layer thus obtained are excellent in, for example, pressure-sensitive adhesive strength under heat resistance and stability over time, and have a low degree of contamination to the adherend when peeling the pressure-sensitive adhesive sheet. It has a function that the dependence and the peeling temperature dependence are small.
- the pressure-sensitive adhesive composition is applied by a known method such as knife coating method, roll coating method, bar coating method, blade coating method, die coating method, gravure coating method, etc. -A drying method can be used.
- the conditions for forming the pressure-sensitive adhesive and the pressure-sensitive adhesive layer are as follows.
- the pressure-sensitive adhesive composition of the present invention is coated on a support and dried at 60 to 120 ° C., preferably 70 to 110 ° C., usually for 1 to 5 minutes, preferably 2 to 4 minutes. Form.
- the film thickness of the dried coating film is usually 3 to 100 ⁇ m, preferably 5 to 50 ⁇ m.
- the pressure-sensitive adhesive and the pressure-sensitive adhesive layer are preferably formed under the following conditions. After applying the pressure-sensitive adhesive composition of the present invention on a support and applying a cover film on the coating film formed under the above conditions, it is usually 3 days or more, preferably 7 to 10 days, usually 5 to 60 ° C. , Preferably under an environment of 15 to 40 ° C. When crosslinking is performed under the aging conditions as described above, a crosslinked body (network polymer) can be efficiently formed.
- support and cover film examples include polyester films such as polyethylene terephthalate; plastic films such as polyolefin films such as polyethylene, polypropylene, and ethylene-vinyl acetate copolymer.
- the gel fraction of the pressure-sensitive adhesive and pressure-sensitive adhesive layer of the present invention is preferably 50 to 99% by mass, more preferably 70 to 98% by mass. When the gel fraction is within the above range, it is preferable in terms of low contamination to the adherend.
- the adhesive sheet of this invention has a base material and the adhesive layer formed from the above-mentioned composition for adhesives.
- This pressure-sensitive adhesive sheet may have a protective film on the pressure-sensitive adhesive layer.
- polyester films such as polyethylene terephthalate
- plastic films such as polyolefin films such as polyethylene, polypropylene, and ethylene-vinyl acetate copolymer.
- the film thickness of the pressure-sensitive adhesive layer is usually 3 to 100 ⁇ m, preferably 5 to 50 ⁇ m.
- the thickness of the substrate and the protective film is not particularly limited, but is usually 10 to 100 ⁇ m, preferably 25 to 50 ⁇ m.
- the pressure-sensitive adhesive sheet of the present invention has a good balance of pressure-sensitive adhesive performance, and has a feature that there is little contamination of the adherend when it is peeled off after being affixed to the adherend. For example, even when the pressure-sensitive adhesive sheet of the present invention is placed under a heat resistant condition of about 150 ° C., an increase in pressure-sensitive adhesive force with time can be suppressed.
- the difference in peeling force between the case where the pressure-sensitive adhesive sheet is peeled off at a low speed and the case where the pressure-sensitive adhesive sheet is peeled off at a high speed is small.
- the difference in peeling force between the case where it peels off and the case where it peels off in a low temperature environment is small.
- the pressure-sensitive adhesive sheet of the present invention can be widely used as an industrial pressure-sensitive adhesive sheet, it can be used as a heat-resistant protective film, particularly as a re-peeling protective film or an optical protective film.
- Measurement device HLC-8120GPC (manufactured by Tosoh Corporation) -GPC column configuration: The following five columns (all manufactured by Tosoh Corporation) (1) TSK-GEL HXL-H (guard column) (2) TSK-GEL G7000HXL (3) TSK-GEL GMHXL (4) TSK-GEL GMHXL (5) TSK-GEL G2500HXL ⁇ Sample concentration: diluted with tetrahydrofuran to 1.0 mg / cm 3 ⁇ Mobile phase solvent: tetrahydrofuran ⁇ Flow rate: 1.0 cm 3 / min -Column temperature: 40 ° C ⁇ 2.
- Nonvolatile content (%) 100 x [weight after heating (n3-n1) / weight before heating (n2-n1)] ⁇ 4.
- Production of (meth) acrylic acid ester polymer> [Production Example 1] In a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser, 18.98 parts of 2-ethylhexyl acrylate, 1.0 part of 2-hydroxyethyl acrylate, 0.02 part of acrylic acid, Bis [4- ⁇ ethyl- (2-hydroxyethyl) aminocarbonyl ⁇ -benzyl] trithiocarbonate represented by the formula (manufactured by Nippon Terpene Chemical Co., Ltd.) (hereinafter also referred to as “RAFT agent-1”) 4 parts were charged (initial charge), and the contents of the flask were heated to 90 ° C. while introducing nitrogen gas into the flask.
- RAFT agent-1 Bis [4- ⁇ eth
- AIBN 2,2′-azobisisobutyronitrile
- the molecular weight measured by GPC for the acrylic polymer (1) contained in the obtained polymer solution was Mn: 53,000, Mw: 90,000, and Mw / Mn: 1.7.
- the viscosity of the obtained polymer solution at 25 ° C. was 3.4 Pa ⁇ s, and the nonvolatile content was 70% by mass.
- Production Example 1 the same manner as in Production Example 1 except that the type and amount of raw material monomer (initial charge and additional charge of raw material monomer) and the type and amount of RAFT agent were changed as shown in Table 1. A polymer solution containing the polymer (2) to (7) or the acrylic polymer (c2) to (c4) was obtained.
- RAFT agent-2 is dibenzyltrithiocarbonate (“BlocBuilderDB” from Arkema), and RAFT agent-3 is 2-cyano-2-propylbenzodithioate (Aldrich).
- the molecular weight measured by GPC for the acrylic polymer (8) contained in the obtained polymer solution was Mn: 67,000, Mw: 145,000, and Mw / Mn: 2.2.
- the resulting polymer solution had a viscosity at 25 ° C. of 7.4 Pa ⁇ s and a nonvolatile content of 70% by mass.
- Example 1 The polymer solution containing the acrylic polymer (1) obtained in Production Example 1 and L-45 (manufactured by Soken Chemical Co., Ltd.) as the isocyanate compound were blended with 100 parts of the acrylic polymer (1). The mixture was mixed at a ratio (solid content ratio) of 9 parts to obtain an adhesive composition.
- the adhesive composition was applied to a polyethylene terephthalate (PET) separator (trade name: Therapy MFA; manufactured by Toray Film Co., Ltd.) using a doctor blade so that the dry film thickness was 25 ⁇ m.
- PET polyethylene terephthalate
- a coating film was formed on the PET separator by drying at 80 ° C. for 3 minutes. After the drying, a PET film having a thickness of 25 ⁇ m is pasted on the surface of the coating film opposite to the PET separator, and left to stand for 7 days under conditions of a room temperature of 23 ° C. and a humidity of 65%, whereby a PET separator / adhesive layer / The adhesive sheet which consists of PET films was obtained.
- Example 1 Comparative Examples 1 to 5
- Example 1 the composition for adhesives and an adhesive sheet were obtained similarly to Example 1 except having changed the kind and compounding quantity of an acrylic polymer and an isocyanate compound as having described in Table 2.
- the pressure-sensitive adhesive sheet was peeled from the SUS plate at 25 ° C./50% RH and a peeling angle of 180 ° at a peeling speed of 50 mm / min (A1), 300 mm / min (A2), and 1000 mm / min (A3). It peeled and the peeling force (adhesive force) of the adhesive layer of an adhesive sheet was measured, respectively. In the case of A3, the contamination state of the adherend after peeling was visually observed.
- the pressure-sensitive adhesive sheet was peeled from the SUS plate under the conditions of a peeling speed of 300 mm / min and a peeling angle of 180 °, -20 ° C., dry condition (B1), 25 ° C./50% RH condition (B2). It peeled on 105 degreeC and dry conditions (B3), and the peeling force (adhesive force) of the adhesive layer of an adhesive sheet was measured, respectively. In the case of B3, the contamination state of the adherend after peeling was visually observed.
- the isocyanate compounds used in Examples etc. are as follows.
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Abstract
Description
本発明の粘着剤用組成物は、RAFT重合によって得られる、ゲルパーミエーションクロマトグラフィー(GPC)法により測定される重量平均分子量(Mw)が60,000~200,000であり、分子量分布(Mw/Mn)が3.0以下であり、水酸基含有モノマーに由来する構成単位を有する(メタ)アクリル酸エステル重合体(A)と、1分子中のイソシアネート基数が3以上のイソシアネート化合物(B)とを含有する。以下、前記成分をそれぞれ「RAFT重合体(A)」および「多官能イソシアネート化合物(B)」ともいう。
RAFT重合体(A)のGPC法により測定される重量平均分子量(Mw)は、60,000~200,000であり、好ましくは70,000~180,000、より好ましくは80,000~160,000である。Mwが前記範囲にあるRAFT重合体(A)を用いることで、粘着力のバランスを取りやすい。Mwが前記範囲を上回ると、耐熱条件下で粘着力が経時で大きく上昇し、また粘着力の剥離速度依存性および剥離温度依存性が高くなる。Mwが前記範囲を下回ると、粘着シートを剥離した際に被着体の汚染の原因となる。
RAFT剤としては、従来公知の化合物を使用することができ、特に限定されない。RAFT剤としては、例えば、ジチオエステル、トリチオカーボネート、ジチオカーバメート、キサンタート等のチオカルボニルチオ化合物が挙げられ、具体的には式(a1-1)で表されるジチオエステル、式(a1-2)または式(a1-2’)で表されるトリチオカーボネート、式(a1-3)で表されるジチオカーバメート、式(a1-4)で表されるキサンタートが挙げられる。
(i)アルキル基、ならびに
(ii)アルキル基が有する水素原子の1または2以上が、フェニル基、シアノ基、ヒドロキシル基、カルボキシル基、炭素数1~4のアルコキシカルボニル基、フェノキシカルボニル基、アセトキシ基および下記g1~g4からなる群Rsから選ばれる少なくとも1種の基で置換された基
が挙げられる。
RAFT剤の使用量は、原料モノマーの総量100質量部に対して、通常0.05~20質量部、好ましくは0.1~10質量部である。RAFT剤の使用量が前記範囲の下限値以上であれば反応制御が容易であり、前記範囲の上限値以下であれば得られる重合体の重量平均分子量を上記範囲に調整することが容易である。
RAFT重合において、原料モノマーとして少なくとも水酸基含有モノマーを用いることが好ましい。また、原料モノマーとして水酸基含有モノマー以外の(メタ)アクリル酸エステルも用いることが好ましい。そのほか、水酸基含有モノマー以外の官能基含有モノマーや、これら以外の共重合性モノマーを用いることができる。
水酸基含有モノマーとしては、例えば、水酸基含有(メタ)アクリレートが挙げられ、具体的には、2-ヒドロキシエチル(メタ)アクリレート、3-ヒドロキシプロピル(メタ)アクリレート、4-ヒドロシキブチル(メタ)アクリレート、6-ヒドロキシヘキシル(メタ)アクリレート、8-ヒドロキシオクチル(メタ)アクリレート等のヒドロキシアルキル(メタ)アクリレートが挙げられる。ヒドロキシアルキル(メタ)アクリレートでのアルキル基の炭素数は、通常2~8、好ましくは2~6である。
(メタ)アクリル酸エステルとしては、例えば、アルキル(メタ)アクリレート、アルコキシアルキル(メタ)アクリレート、アルコキシポリアルキレングリコールモノ(メタ)アクリレート、脂環式基または芳香環含有(メタ)アクリレートが挙げられる。ただし、(メタ)アクリル酸エステルからは、水酸基含有(メタ)アクリレート;カルボキシル基含有(メタ)アクリレート、アミノ基含有(メタ)アクリレート等の官能基含有(メタ)アクリレートを除く。
官能基含有モノマーとしては、例えば、酸基含有モノマー、アミノ基含有モノマー、アミド基含有モノマー、窒素系複素環含有モノマー、シアノ基含有モノマーが挙げられる。酸基としては、例えば、カルボキシル基、酸無水物基、リン酸基、硫酸基が挙げられる。
共重合性モノマーとしては、例えば、スチレン、メチルスチレン、ジメチルスチレン、トリメチルスチレン、プロピルスチレン、ブチルスチレン、へキシルスチレン、ヘプチルスチレンおよびオクチルスチレン等のアルキルスチレン、フロロスチレン、クロロスチレン、ブロモスチレン、ジブロモスチレン、ヨウ化スチレン、ニトロスチレン、アセチルスチレンおよびメトキシスチレン等のスチレン系単量体、酢酸ビニルが挙げられる。
RAFT重合は、重合開始剤の存在下に行うことが好ましい。重合開始剤としては、例えば、通常の有機系重合開始剤が挙げられ、具体的には、過酸化ベンゾイル、過酸化ラウリウム等の過酸化物、2,2’-アソビスイソブチロニトリル等のアゾ化合物が挙げられる。これらの中でも、アゾ化合物が好ましい。
RAFT重合法での反応温度は、通常60~120℃、好ましくは80~110℃であり、通常は窒素、アルゴン、ヘリウム等の不活性ガス雰囲気下で行われる、この反応は常圧、加圧および減圧のいずれの条件で行うこともでき、通常は常圧で行われる。また、反応時間は通常1~14時間、好ましくは2~12時間である。重合条件については、例えば、特開2007-230947号公報および特開2011-52057号公報を参照することができる。
多官能イソシアネート化合物(B)は、1分子中のイソシアネート基数が3以上のイソシアネート化合物である。化合物(B)により重合体(A)を架橋することで、架橋体(ネットワークポリマー)を形成することができる。
本発明の粘着剤用組成物は、上記成分のほか、さらに透明性、視認性および本発明の効果を損なわない範囲で、有機溶媒、帯電防止剤、紫外線吸収剤、酸化防止剤、粘着付与樹脂、可塑剤、充填剤、安定剤、軟化剤、および濡れ性調整剤から選択される1種または2種以上を含有していてもよい。
本発明の粘着剤および粘着剤層は、上述の粘着剤用組成物から形成される。
本発明の粘着シートは、基材と、上述の粘着剤用組成物から形成された粘着剤層とを有する。この粘着シートは、粘着剤層上に保護フィルムを有していてもよい。
<1.分子量および分子量分布>
(メタ)アクリル酸エステル重合体について、ゲルパーミエーションクロマトグラフィー(GPC)法により、下記条件で標準ポリスチレン換算による重量平均分子量(Mw)および数平均分子量(Mn)を求めた。
・測定装置:HLC-8120GPC(東ソー(株)製)
・GPCカラム構成:以下の5連カラム(すべて東ソー(株)製)
(1)TSK-GEL HXL-H (ガードカラム)
(2)TSK-GEL G7000HXL
(3)TSK-GEL GMHXL
(4)TSK-GEL GMHXL
(5)TSK-GEL G2500HXL
・サンプル濃度:1.0mg/cm3となるように、テトラヒドロフランで希釈
・移動相溶媒:テトラヒドロフラン
・流量:1.0cm3/min
・カラム温度:40℃
<2.粘度測定>
実施例等で得られたアクリル系ポリマー溶液について、前記溶液入りの500ml瓶を25℃の恒温水槽に浸し12時間静置後、B型粘時計の測定方法に従い、25℃における粘度を測定した。
精秤したブリキシャーレ(n1)に、製造例等で得られたアクリル系ポリマー溶液1gを入れ、合計重量(n2)を精秤した後、105℃で3時間加熱した。その後、当該ブリキシャーレを室温のデシケータ内に1時間静置し、次いで再度精秤し、加熱後の合計重量(n3)を測定した。得られた重量測定値(n1~n3)を用いて、下記式から不揮発分を算出した。
<4.(メタ)アクリル酸エステル重合体の製造>
[製造例1]
攪拌装置、窒素ガス導入管、温度計および還流冷却管を備えたフラスコに、2-エチルヘキシルアクリレート18.98部と、2-ヒドロキシエチルアクリレート1.0部と、アクリル酸0.02部と、下記式で表されるビス[4-{エチル-(2-ヒドロキシエチル)アミノカルボニル}-ベンジル]トリチオカーボネート(日本テルペン化学(株)製)(以下「RAFT剤-1」ともいう。)0.4部とを仕込み(初期仕込み)、フラスコ内に窒素ガスを導入しながらフラスコの内容物を90℃に加熱した。
製造例1において、原料モノマーの種類・量(原料モノマーの初期仕込みおよび追加仕込み)およびRAFT剤の種類・量を表1に記載したとおりに変更したこと以外は製造例1と同様にして、アクリル系ポリマー(2)~(7)、またはアクリル系ポリマー(c2)~(c4)を含むポリマー溶液を得た。
攪拌装置、窒素ガス導入管、温度計および還流冷却管を備えたフラスコに、2-エチルヘキシルアクリレート94.9部と、2-ヒドロキシエチルアクリレート5.0部と、アクリル酸0.1部と、n-ドデシルメルカプタン0.25部と、酢酸エチル100部とを仕込み、フラスコ内に窒素ガスを導入しながらフラスコの内容物を66~67℃に加熱した。次いで、ジメチル-2,2’-アゾビス(2-メチルプロピオネート)(V-601;和光純薬工業(株)製)0.1部を攪拌下にフラスコ内に添加した。フラスコ内の内容物の温度を66~67℃に維持できるように加熱および冷却を4時間行った。このようにして、アクリル系ポリマー(c1)を含むポリマー溶液を得た。
攪拌装置、窒素ガス導入管、温度計および還流冷却管を備えたフラスコに、n-ブチルアクリレート94.9部と、4-ヒドロキシブチルアクリレート5.0部と、アクリル酸0.1部と、RAFT剤-1 0.2部と、酢酸エチル40部とを仕込み、フラスコ内に窒素ガスを導入しながらフラスコの内容物を90℃に加熱した。次いで、ジメチル-2,2’-アゾビス(2-メチルプロピオネート)(V-601;和光純薬工業(株)製)0.1部を攪拌下にフラスコ内に添加し、フラスコ内の内容物の温度を90℃に維持できるように加熱および冷却を続け、6時間反応を行った。
製造例1で得られたアクリル系ポリマー(1)を含むポリマー溶液と、イソシアネート化合物としてL-45(綜研化学(株)製)とを、アクリル系ポリマー(1)100部に対するL-45の配合量が9部となる割合(固形分比)で混合し、粘着剤用組成物を得た。
実施例1において、アクリル系ポリマーおよびイソシアネート化合物の種類および配合量を表2に記載したとおりに変更したこと以外は実施例1と同様にして、粘着剤用組成物および粘着シートを得た。
サンプル瓶に、実施例等で得られた粘着剤層0.1gを入れ、酢酸エチル30ccを加えて24時間浸透させた後、該サンプル瓶の内容物を200メッシュのステンレス製金網で濾別し、金網上で100℃にて2時間乾燥させた後の残留物重量を乾燥重量とした。得られた重量測定値を用いて、下記式からゲル分率を算出した。
〔粘着シート〕
<1.耐熱性試験>
25℃/50%RH条件下で、実施例等で得られた粘着シートのPETセパレーターを剥がし、露出した粘着剤層面をSUS板に2kgのローラーを用いて圧着(貼付)した。
25℃/50%RH条件下で、実施例等で得られた粘着シートのPETセパレーターを剥がし、露出した粘着剤層面をSUS板に2kgのローラーを用いて圧着した。
Claims (4)
- (A)RAFT重合によって得られる、ゲルパーミエーションクロマトグラフィー法により測定される重量平均分子量(Mw)が60,000~200,000であり、分子量分布(Mw/Mn)が3.0以下であり、水酸基含有モノマーに由来する構成単位を有する(メタ)アクリル酸エステル重合体と、
(B)1分子中のイソシアネート基数が3以上のイソシアネート化合物と
を含有する粘着剤用組成物。 - (メタ)アクリル酸エステル重合体(A)100質量部に対し、前記イソシアネート化合物(B)を、固形分比で0.1~50質量部の範囲で含有する請求項1に記載の粘着剤用組成物。
- 請求項1または2に記載の組成物から形成された粘着剤。
- 基材と、
請求項1または2に記載の組成物から形成された粘着剤層と
を有する粘着シート。
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