WO2018168678A1 - 粘着剤組成物、粘着剤、粘着テープ並びに気密防水用粘着テープ - Google Patents
粘着剤組成物、粘着剤、粘着テープ並びに気密防水用粘着テープ Download PDFInfo
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- WO2018168678A1 WO2018168678A1 PCT/JP2018/009169 JP2018009169W WO2018168678A1 WO 2018168678 A1 WO2018168678 A1 WO 2018168678A1 JP 2018009169 W JP2018009169 W JP 2018009169W WO 2018168678 A1 WO2018168678 A1 WO 2018168678A1
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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
- 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
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
-
- 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
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
-
- 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
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/064—Copolymers with monomers not covered by C09J133/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
-
- 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
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
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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
- 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
- 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
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1806—C6-(meth)acrylate, e.g. (cyclo)hexyl (meth)acrylate or phenyl (meth)acrylate
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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
- C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
- C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
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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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/414—Additional features of adhesives in the form of films or foils characterized by the presence of essential components presence of a copolymer
-
- 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
- C09J2433/00—Presence of (meth)acrylic polymer
Definitions
- the present invention relates to a pressure-sensitive adhesive composition, and more specifically, a highly polar adherend, a low polarity adherend, a hardly adherent adherend such as ethylene propylene diene rubber (EPDM), and further a deposit.
- Adhesive composition with high adhesion to rough surfaces of the body, excellent holding power, excellent adhesion even in high temperature and high humidity environments, and suppressed deterioration of adhesion over time
- the present invention relates to an adhesive, an adhesive tape, and an airtight waterproof adhesive tape.
- adhesives and adhesive tapes using acrylic resins are, for example, kraft tapes, OPP (Oriented Poly Propylene) tapes, cloth adhesive tapes and other packaging tapes, light packaging cellophane adhesive tapes, temporary fixing tapes, automobiles, etc.
- an acrylic resin obtained by copolymerizing an alkyl (meth) acrylate as a main component is common, but in order to improve adhesion to an adherend.
- an acrylic resin having a carboxyl group-containing monomer as a copolymerization component is also used.
- an acrylic resin having an acid value of 1 to 50 mgKOH / g, a hydroxyl value of 10 to 60 mgKOH / g, and a number average molecular weight of 50,000 to 500,000, copolymerized with an acrylic acid adduct
- a pressure-sensitive adhesive composition excellent in stickiness / adhesive strength retention over time, moist heat resistance, heat resistance, and rework pressure-sensitive adhesive properties can be obtained.
- the content of the acrylic acid adduct is a relatively small content of 1% by weight with respect to the copolymer component, and this is insufficient in improving the adhesive strength.
- the adherend in Patent Document 2 is adhesion to a glass substrate or the like, and is different from an adherend having a rough surface.
- a pressure-sensitive adhesive composition containing a (meth) acrylic monomer having a range can be obtained a pressure-sensitive adhesive with little decrease in adhesive strength and holding power even in a high-temperature environment, the adhesion is low. The body was not evaluated, and further, the adhesive force and holding force on the rough surface were not considered, and it was still not satisfactory.
- an acrylic pressure-sensitive adhesive composition using an acrylic resin is also useful as an airtight waterproof pressure-sensitive adhesive tape
- the above airtight waterproof pressure-sensitive adhesive tape is a waterproof / airtight housing (waterproof and airtight).
- an airtight waterproofing adhesive tape is an adherend having a relatively high polarity such as an aluminum sash, an adherend having a relatively low polarity such as a moisture permeable waterproof sheet, and an OSB (Oriented Strand Board: thin).
- the airtight waterproof adhesive tape is a polymer roof sheet material used for waterproofing, such as ethylene propylene diene rubber (EPDM), butyl rubber (IIR), chloroprene rubber (CR), polyvinyl chloride, chlorinated polyethylene.
- EPDM ethylene propylene diene rubber
- IIR butyl rubber
- CR chloroprene rubber
- polyvinyl chloride chlorinated polyethylene.
- it may be used for the purpose of airtightness and waterproofing of the seam of a sheet composed of a hardly adhesive member such as thermoplastic polyolefin rubber and modified asphalt.
- a pressure-sensitive adhesive tape using butyl rubber or an asphalt having high adhesion to a hardly-adhesive adherend is often used.
- the adherend having a relatively high polarity, the adherend having a relatively low polarity, the adherend having a poor adhesion such as EPDM, and the rough surface are firmly provided.
- Adhesive, high holding power, excellent adhesiveness even in high temperature and high humidity environment, and reduced adhesive loss over time, especially useful as an airtight waterproof adhesive tape A pressure-sensitive adhesive composition is provided.
- the present inventors have, as a copolymer component constituting the acrylic resin, contained a specific terminal carboxyl group-containing monomer in the pressure-sensitive adhesive composition using the acrylic resin.
- the copolymer component including the alkyl (meth) acrylate to a specific composition, an adherend having a relatively high polarity, an adherend having a relatively low polarity, and an adherent having poor adhesion such as EPDM
- a pressure-sensitive adhesive composition that adheres firmly to a rough surface, has a high holding power, and is excellent in adhesiveness even in a high-temperature and high-humidity environment, in which a decrease in adhesiveness over time is suppressed.
- the gist of the present invention is from the group consisting of (meth) acrylate having an alkyl group having 1 to 3 carbon atoms, t-butyl (meth) acrylate, a cyclic structure-containing monomer, and a vinyl ester monomer having 3 to 10 carbon atoms.
- a copolymerization component (a) comprising 1 to 20% by weight of a terminal carboxyl group-containing monomer (a3) represented by (1) and 0.1 to 5% by weight of (meth) acrylic acid (a4); It is related with the adhesive composition containing acrylic resin (A) which becomes.
- R 1 is hydrogen or a methyl group
- R 2 is a saturated aliphatic, unsaturated aliphatic, aromatic, saturated alicyclic or divalent unsaturated alicyclic hydrocarbon
- n is a positive number of 1 or more. Indicates.
- the present invention relates to a pressure-sensitive adhesive, a pressure-sensitive adhesive tape and an airtight waterproof pressure-sensitive adhesive tape obtained by crosslinking the above pressure-sensitive adhesive composition.
- the adhesive force is improved. Containing such a terminal carboxyl group-containing monomer (a3) is likely to cause a decrease in the normal holding power, for example, because the distance between the cross-linking points is increased. Therefore, both adhesiveness and holding power are compatible. It was considered difficult. However, in the present invention, even when such a terminal carboxyl group-containing monomer (a3) is used as a copolymerization component, it has an alkyl group having 1 to 3 carbon atoms by setting the copolymerization component to a specific composition.
- the holding power can be increased. It has been found that the pressure-sensitive adhesive composition is excellent in adhesiveness without being lowered.
- the present invention provides at least one selected from the group consisting of (meth) acrylates having an alkyl group having 1 to 3 carbon atoms, t-butyl (meth) acrylate, cyclic structure-containing monomers, and vinyl ester monomers having 3 to 10 carbon atoms.
- the content ratio of the (meth) acrylate (a2-1) having an alkyl group having 4 to 7 carbon atoms to the (meth) acrylate (a2-2) having an alkyl group having 8 to 24 carbon atoms is in a weight ratio.
- (a2-1) / (a2-2) 1/99 to 85/15, the adhesion to the adherend is excellent and the holding power is also excellent.
- the copolymer component (a) further contains a hydroxyl group-containing monomer (a5), the adhesive strength and the holding power are further improved.
- the pressure-sensitive adhesive obtained by crosslinking the pressure-sensitive adhesive composition becomes more excellent in heat and moisture resistance.
- (meth) acryl means acryl or methacryl
- (meth) acryloyl means acryloyl or methacryloyl
- (meth) acrylate means acrylate or methacrylate.
- the acrylic resin is a resin obtained by polymerizing a polymerization component containing at least one (meth) acrylate monomer.
- the pressure-sensitive adhesive composition of the present invention contains an acrylic resin (A) obtained by copolymerizing a copolymer component (a) containing a specific monomer component at a specific ratio.
- the acrylic resin (A) used in the present invention includes (meth) acrylate having 1 to 3 carbon atoms, t-butyl (meth) acrylate, a cyclic structure-containing monomer, and vinyl ester having 3 to 10 carbon atoms. At least one selected from the group consisting of monomers (a1), excluding t-butyl (meth) acrylate, (meth) acrylate (a2) having an alkyl group having 4 to 24 carbon atoms, represented by the following general formula (1)
- the terminal carboxyl group-containing monomer (a3) and the copolymer component (a) containing a specific amount of (meth) acrylic acid (a4) are copolymerized.
- a hydroxyl group-containing monomer (a5) and other polymerizable monomers (a6) are contained as necessary.
- each copolymerization component (a) is demonstrated in order.
- the component (a1) is selected from the group consisting of (meth) acrylates having 1 to 3 carbon atoms, t-butyl (meth) acrylate, cyclic structure-containing monomers, and vinyl ester monomers having 3 to 10 carbon atoms. At least one kind. Of these, (meth) acrylates having an alkyl group having 1 to 3 carbon atoms are preferred.
- the content ratio of the above (a1) is usually 1 to 20% by weight, particularly 1 to 18% by weight, more preferably 2 to 15% by weight of the entire copolymer component (a).
- the content of the component (a1) is too small, the holding power tends to decrease, and when the content is too large, the adhesion to an adherend having a low polarity tends to decrease.
- Examples of the (meth) acrylate having an alkyl group having 1 to 3 carbon atoms include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate and the like. Of these, methyl (meth) acrylate and ethyl (meth) acrylate are preferable.
- the cyclic structure-containing monomer is usually an acrylic monomer having a substituent containing a cyclic structure.
- heterocyclic-containing (meth) acrylate having a morpholine ring is preferable because of a good balance of various physical properties, and N- (meth) acryloylmorpholine is particularly preferable from the viewpoints of availability and safety.
- Examples of the vinyl ester monomer having 3 to 10 carbon atoms include vinyl formate, vinyl acetate, vinyl propionate, vinyl valerate, vinyl butyrate, vinyl isobutyrate, and vinyl pivalate. Among these, vinyl acetate is preferable because it is easily available.
- the above (a2) is a main component of the copolymer component (a), and has an alkyl group having 4 to 24 carbon atoms, preferably 4 to 12 carbon atoms, excluding t-butyl (meth) acrylate ( (Meth) acrylate.
- the content ratio of the component (a2) is usually 55 to 97% by weight, particularly 70 to 95% by weight, more preferably 80 to 90% by weight, based on the entire copolymer component (a).
- the content is too small, the adhesiveness to a low-polarity adherend tends to decrease, and when it is too large, the adhesiveness decreases and the holding power tends to decrease.
- the (meth) acrylate (a2) having an alkyl group having 4 to 24 carbon atoms includes the (meth) acrylate (a2-1) having an alkyl group having 4 to 7 carbon atoms and the alkyl group having 8 to 24 carbon atoms. From the viewpoint of adhesion to the adherend, it is preferable to contain (meth) acrylate (a2-2) having the following.
- the content ratio of the component (a2-1) is too small, the holding power tends to decrease, and when it is too large, the adhesion to a low-polarity adherend tends to decrease.
- Examples of the (meth) acrylate (a2-1) having an alkyl group having 4 to 7 carbon atoms include n-butyl (meth) acrylate, isobutyl (meth) acrylate, n-hexyl (meth) acrylate and the like. Of these, n-butyl (meth) acrylate is preferred because it is readily available and economical.
- Examples of the (meth) acrylate (a2-2) having an alkyl group having 8 to 24 carbon atoms include 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meta) ) Acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, isotridecyl (meth) acrylate, myristyl (meth) acrylate, isomyristyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) Acrylates, isostearyl (meth) acrylates, behenyl (meth) acrylates and the like.
- (meth) acrylates having an alkyl group having 8 to 12 carbon atoms are preferred because of their low
- the component (a3) is a terminal carboxyl group-containing monomer represented by the following general formula (1).
- R 1 is hydrogen or a methyl group
- R 2 is a saturated aliphatic, unsaturated aliphatic, aromatic, saturated alicyclic or divalent unsaturated alicyclic hydrocarbon
- n is a positive number of 1 or more. Indicates.
- the substituent of R 2 is preferably alkylene having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms such as methylene group, phenyl or phenylene, and n is preferably 1 to 10, more preferably. 1-5.
- the content ratio of the component (a3) is usually 1 to 20% by weight, particularly 1.5 to 15% by weight, more preferably 2 to 8.5% by weight, based on the entire copolymer component (a). . If the content is too small, the adhesion to various adherends tends to decrease, and if it is too large, the adhesion to low-polar adherends tends to decrease.
- the content ratio of (meth) acrylic acid (a4) is usually from 0.1 to 5% by weight, particularly from 0.5 to 4.5% by weight, more preferably from 1 to 4% by weight, based on the entire copolymer component (a). It is preferable that If the content is too small, the adhesion to various adherends tends to decrease, and if it is too large, the adhesion to low-polar adherends tends to decrease.
- the content ratio of the component (a3) and the component (a4) is a weight ratio
- the component (a4) is usually 10 to 400 parts by weight, particularly 20 to 200 parts by weight with respect to 100 parts by weight of the component (a3). Parts, more preferably 25 to 100 parts by weight, particularly 30 to 75 parts by weight.
- the acrylic resin (A) obtained by copolymerizing the above components (a1) to (a4) is used, but it is desirable to further copolymerize the hydroxyl group-containing monomer (a5).
- the hydroxyl group-containing monomer (a5) include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8- Hydroxyalkyl esters of (meth) acrylic acid such as hydroxyoctyl (meth) acrylate, caprolactone-modified monomers such as caprolactone-modified 2-hydroxyethyl (meth) acrylate, and oxyalkylene modifications such as diethylene glycol (meth) acrylate and polyethylene glycol (meth) acrylate Monomer, primary hydroxyl group-containing monomer such as 2-acryloyloxyethyl-2-
- a primary hydroxyl group-containing monomer is preferable in view of excellent reactivity with a crosslinking agent, and 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate are particularly preferable.
- the hydroxyl group-containing monomer (a5) is useful because it serves as a crosslinking point when a crosslinking agent is blended, and is particularly effective when an isocyanate crosslinking agent is used as the crosslinking agent.
- the amount is usually 0.01 to 5% by weight, particularly 0.05 to 3% by weight, more preferably 0.05 to 2% by weight, based on the total copolymer component (a).
- the amount of the component (a5) is too small, the holding power tends to decrease, and when the amount is too large, the adhesion to various adherends tends to decrease.
- ⁇ Other polymerizable monomer (a6)> other polymerizable monomer (a6) may be used as necessary.
- the other polymerizable monomer (a6) include acetoacetyl group-containing monomer, isocyanate group-containing monomer, glycidyl group-containing monomer, Examples thereof include amino group-containing monomers, amide group-containing monomers, functional group-containing monomers, and other copolymerizable monomers.
- acetoacetyl group-containing monomer examples include 2- (acetoacetoxy) ethyl (meth) acrylate and allyl acetoacetate.
- isocyanate group-containing monomer examples include 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate and their alkylene oxide adducts.
- Examples of the glycidyl group-containing monomer include glycidyl (meth) acrylate and allyl glycidyl (meth) acrylate.
- amino group-containing monomer examples include monomers having an ethylenically unsaturated double bond and an amino group (unsubstituted or substituted amino group), such as aminomethyl (meth) acrylate and aminoethyl (meth) acrylate.
- amide group-containing monomer examples include monomers having an ethylenically unsaturated double bond and an amide group (group having an amide bond), such as (meth) acrylamide; N-methyl (meth) acrylamide, N-ethyl.
- Examples of the other copolymerizable monomers include 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, and methoxypolyethylene glycol (meth).
- Monomers containing alkoxy groups or oxyalkylene groups such as acrylate, polypropylene glycol mono (meth) acrylate; acrylonitrile, methacrylonitrile, vinyl stearate, vinyl chloride, vinylidene chloride, alkyl vinyl ether, vinyl toluene, itaconic acid dialkyl ester, Dialkyl ester of fumaric acid, allyl alcohol, acrylic chloride, methyl vinyl ketone, allyltrimethylammonium chlora De, dimethylallyl vinyl ketone, and the like.
- the other polymerizable monomer (a6) is contained to the extent that the effects of the present invention are not hindered in order to adjust the physical properties according to the application.
- the acrylic resin (A) is produced by polymerizing the above components (a1) to (a4) and, if necessary, further using components (a5) and (a6) as copolymerization components.
- Each of the components (a1) to (a6) can be used alone or in combination of two or more.
- Such solution polymerization may be carried out in a conventional manner, for example, by mixing or dropping the copolymerization component (a) such as (a1) to (a4) and a polymerization initiator in an organic solvent, in a reflux state or 50 Polymerization may be performed at -98 ° C for 0.1-20 hours.
- polymerization initiators examples include azo-based polymerization initiators such as azobisisobutyronitrile and azobisdimethylvaleronitrile, which are ordinary radical polymerization initiators, benzoyl peroxide, lauroyl peroxide, and di-t-butyl peroxide.
- azo-based polymerization initiators such as azobisisobutyronitrile and azobisdimethylvaleronitrile
- benzoyl peroxide lauroyl peroxide
- di-t-butyl peroxide examples include peroxide-based polymerization initiators such as cumene hydroperoxide. These may be used alone or in combination of two or more.
- the weight average molecular weight of the acrylic resin (A) thus obtained is usually 100,000 to 5,000,000, preferably 300,000 to 1,500,000, particularly preferably 500,000 to 900,000. If the weight average molecular weight is too small, the durability performance tends to decrease, and if it is too large, the production tends to be difficult.
- the degree of dispersion (weight average molecular weight / number average molecular weight) determined from the weight average molecular weight and number average molecular weight of the acrylic resin (A) is preferably 20 or less, particularly preferably 15 or less, and more preferably 10 The following is preferable, and 7 or less is particularly preferable.
- the lower limit of the degree of dispersion is usually 1.1 from the viewpoint of production limit.
- the weight average molecular weight of the acrylic resin (A) is a weight average molecular weight in terms of standard polystyrene molecular weight, and is a high performance liquid chromatograph (manufactured by Waters, Japan, “Waters 2695 (main body)” and “Waters 2414 (detector)).
- the glass transition temperature (Tg) of the acrylic resin (A) is preferably ⁇ 80 to 10 ° C., particularly preferably ⁇ 70 to ⁇ 10 ° C., more preferably ⁇ 65 to ⁇ 20 ° C., and the glass transition temperature is If it is too high, tack tends to be insufficient, and if it is too low, heat resistance tends to decrease.
- the glass transition temperature is a value calculated by applying the glass transition temperature and the weight fraction when each monomer constituting the acrylic resin (A) is a homopolymer to the following Fox equation.
- the glass transition temperature when the monomer constituting the acrylic resin (A) is a homopolymer is usually measured by a differential scanning calorimeter (DSC) by a method according to JIS K7121-1987 and JIS K6240. And the value described in the catalog.
- DSC differential scanning calorimeter
- the viscosity of the acrylic resin (A) is adjusted with a solvent or the like, and is used for coating as an acrylic resin (A) solution.
- the viscosity of the acrylic resin (A) solution is preferably 500 to 20000 mPa ⁇ s, particularly preferably 1000 to 18000 mPa ⁇ s, and more preferably 2000 to 15000 mPa ⁇ s from the viewpoint of easy handling. If the viscosity is too high, the fluidity tends to be lowered and difficult to handle, and if it is too low, the application of the pressure-sensitive adhesive tends to be difficult.
- the pressure-sensitive adhesive composition of the present invention preferably contains a crosslinking agent (B) in addition to the acrylic resin (A) from the viewpoint of adhesiveness.
- the crosslinking agent (B) reacts with a functional group in the acrylic resin (A) to form a crosslinked structure.
- an epoxy crosslinking agent, an isocyanate crosslinking agent, an aziridine crosslinking agent examples include melamine crosslinking agents, aldehyde crosslinking agents, amine crosslinking agents, and metal chelate crosslinking agents.
- an isocyanate-based cross-linking agent in order to obtain an effect that is excellent in stability and further excellent in adhesion and heat-and-moisture resistance.
- epoxy crosslinking agent examples include 1,3-bis (N, N′-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′-tetraglycidyl-m-xylylenediamine, ethylene glycol diene
- examples thereof include glycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane diglycidyl ether, diglycidyl aniline, diglycidyl amine and the like. Of these, 1,3-bis (N, N'-diglycidylaminomethyl) cyclohexane is preferred.
- the isocyanate-based crosslinking agent contains at least two isocyanate groups.
- aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate and xylylene diisocyanate
- aliphatic polyisocyanates such as hexamethylene diisocyanate
- isophorone Contains diisocyanates, alicyclic polyisocyanates such as hydrogenated diphenylmethane diisocyanate, etc., and their biurets, isocyanurates, and low molecular active hydrogen such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, castor oil, etc.
- Examples thereof include adducts that are a reaction product with a compound.
- an adduct body of aromatic polyisocyanate, aromatic polyisocyanate and trimethylolpropane is preferable, and an adduct body of tolylene diisocyanate and trimethylolpropane is particularly preferable.
- aziridine-based crosslinking agent examples include diphenylmethane-4,4′-bis (1-aziridinecarboxamide), trimethylolpropane tri- ⁇ -aziridinylpropionate, and tetramethylolmethanetri- ⁇ -aziridini. Lupropionate, toluene-2,4-bis (1-aziridinecarboxamide), triethylenemelamine, bisisophthaloyl-1- (2-methylaziridine), tris-1- (2-methylaziridine) phosphine And trimethylolpropane tri- ⁇ - (2-methylaziridine) propionate.
- the melamine crosslinking agent examples include, for example, melamine, amino group-containing methylol melamine obtained by condensation of melamine and formaldehyde, methylol melamine derivatives such as imino group-containing methylol melamine, hexamethylol melamine, methylol melamine derivatives, methyl alcohol and butyl
- methylol melamine derivatives such as imino group-containing methylol melamine, hexamethylol melamine, methylol melamine derivatives, methyl alcohol and butyl
- aldehyde-based crosslinking agent examples include formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, glyoxal, glutaraldehyde, dialdehyde starch, hexamethylenetetramine, 1,4-dioxane-2,3-diol, 1,3-bis.
- Aldehyde compounds that liberate aldehydes in aqueous solutions such as (hydroxymethyl) -2-imidazolidine, dimethylolurea, N-methylolacrylamide, urea formalin resin, melamine formalin resin, or benzaldehyde, 2-methylbenzaldehyde, 4-methyl Aromatic aldehyde compounds such as benzaldehyde, p-hydroxybenzaldehyde, m-hydroxybenzaldehyde and the like can be mentioned.
- amine-based crosslinking agent examples include 4,4′-methylene-bis (2-chloroaniline) (hereinafter abbreviated as “MOCA”), modified MOCA, and diethyltoluenediamine.
- MOCA 4,4′-methylene-bis (2-chloroaniline)
- modified MOCA modified MOCA
- diethyltoluenediamine diethyltoluenediamine
- Examples of the metal chelate-based crosslinking agent include chelate compounds whose metal atoms are aluminum, zirconium, titanium, zinc, iron, tin and the like, and aluminum chelate compounds are preferable from the viewpoint of performance.
- Examples of the aluminum chelate compound include diisopropoxy aluminum monooleyl acetoacetate, monoisopropoxy aluminum bis oleyl acetoacetate, monoisopropoxy aluminum monooleate monoethyl acetoacetate, diisopropoxy aluminum monolauryl acetoacetate, diisopropoxy Examples thereof include aluminum monostearyl acetoacetate and diisopropoxyaluminum monoisostearyl acetoacetate.
- the above crosslinking agent (B) may be used alone or in combination of two or more.
- the content of the crosslinking agent (B) is usually 0.01 to 5 parts by weight, particularly 0.01 to 4 parts by weight, and more preferably 0.02 to 3 parts per 100 parts by weight of the acrylic resin (A). It is preferable that it is a weight part. If the content is too small, the holding power tends to decrease, and if it is too large, the adhesion to various adherends tends to decrease.
- the cross-linking agents (B) it is preferable to use the above-mentioned epoxy-based cross-linking agents in terms of being able to balance both adhesion and holding power to various adherends in a balanced manner.
- the content in the case of using the epoxy-based crosslinking agent is usually 0.01 to 0.1 parts by weight, particularly 0.01 to 0.08 parts by weight, with respect to 100 parts by weight of the acrylic resin (A). Further, it is preferably 0.02 to 0.05 parts by weight. If the content is too small, the holding power tends to decrease, and if it is too large, the adhesion to various adherends tends to decrease.
- the isocyanate-based cross-linking agents (B) it is preferable to use the isocyanate-based cross-linking agents in terms of strong bonds and excellent durability.
- the content when the above isocyanate-based crosslinking agent is used is usually 0.1 to 5 parts by weight, particularly 0.1 to 1 part by weight, and more preferably 0.00 to 100 parts by weight of the acrylic resin (A). It is preferably 3 to 0.9 parts by weight. When the content is too small, the holding power tends to decrease, and when the content is too large, the adhesion to a low-polarity adherend tends to decrease.
- the tackifier (C) is used for further exhibiting good physical properties of the acrylic resin (A), and is preferably contained in the pressure-sensitive adhesive composition of the present invention.
- the tackifier (C) include resins that are compatible with the acrylic resin (A), such as rosin resins, terpene resins, xylene resins, phenol resins, coumarone resins, petroleum resins, and the like. It is done. These tackifiers (C) can be used alone or in combination of two or more.
- the pressure-sensitive adhesive composition of the present invention is used as a pressure-sensitive adhesive tape for airtight waterproofing
- rosin resins, terpene resins, and petroleum resins are preferable, and rosin is more preferable because it has an excellent balance of physical properties. Resin.
- the rosin resin examples include a rosin ester resin obtained by esterifying a raw material rosin obtained by hydrogenation (hydrogenation), disproportionation, dimerization, and acid addition with glycerin or pentaerythritol, or phenol. Added rosin phenol resin. Whichever rosin resin is used, the good physical properties of the acrylic resin (A) are further exhibited. Among them, the raw material rosin is disproportionated and esterified with glycerin or pentaerythritol, and the softening point is 70 ° C to 130 ° C.
- the disproportionated rosin ester in the range, the polymerized rosin ester in which the raw material rosin is dimerized and esterified with pentaerythritol and the softening point is in the range of 110 ° C to 170 ° C, and phenol is added to the raw material rosin. Rosin phenol having a softening point in the range of 120 to 160 ° C. is preferred.
- the terpene resin is a general term for compounds based on the isoprene rule represented by the molecular formula (C 5 H 8 ) n , and as the tackifier (C) used in the present invention, monoterpene (eg, ⁇ -pinene, ⁇ -pinene, limonene, etc.) are used as raw materials, and the resins are homo- or copolymerized with Friedel-Crafts catalysts.
- monoterpene eg, ⁇ -pinene, ⁇ -pinene, limonene, etc.
- a resin in which monoterpene is singly or copolymerized for example, ⁇ -pinene resin, ⁇ -pinene resin, dipentene resin, terpene phenol resin, aromatic modified terpene resin, and water obtained by hydrogenating these are used.
- examples thereof include terpene resins.
- the terpene phenol resin is preferable because it is compatible with the acrylic resin (A), and any terpene phenol resin further exhibits the good physical properties of the acrylic resin (A). Those having a point in the range of 90 ° C. to 170 ° C.
- hydroxylation in the range of 20 to 250 mgKOH / g are preferred, and those having a softening point in the range of 100 ° C. to 150 ° C. and hydroxylation in the range of 50 to 150 mgKOH / g are preferred.
- the petroleum-based resin is obtained, for example, by polymerization of C4-C5 and C9-C11 fraction monomers produced by thermal decomposition of naphtha or the like, and further hydrogenation.
- the content of the tackifier (C) is usually 1 to 50 parts by weight, particularly 5 to 30 parts by weight, and more preferably 5 to 20 parts by weight with respect to 100 parts by weight of the acrylic resin (A).
- an appropriate amount is blended according to the required physical properties.
- the pressure-sensitive adhesive composition of the present invention includes, as other components, resin components other than the acrylic resin (A), acrylic monomers, polymerization inhibitors, antioxidants, corrosion, as long as the effects of the present invention are not impaired.
- resin components other than the acrylic resin (A) acrylic monomers, polymerization inhibitors, antioxidants, corrosion, as long as the effects of the present invention are not impaired.
- Contains various additives such as inhibitors, crosslinking accelerators, radical generators, peroxides, radical scavengers, UV absorbers, plasticizers, pigments, stabilizers, fillers, flame retardants, metal and resin particles, etc. can do.
- a small amount of impurities and the like contained in the raw materials for producing the constituent components of the pressure-sensitive adhesive composition may be contained.
- the content of the other components is preferably 5 parts by weight or less, particularly preferably 1 part by weight or less, and further preferably 0.5 parts by weight or less with respect to 100 parts by weight of the acrylic resin (A).
- compatibility with acrylic resin (A) will fall, and there exists a tendency for durability to fall.
- additives that do not exhibit the effect do not inhibit the effect of the present invention while exhibiting the effect of the additive.
- An appropriate amount may be added in the range.
- the pressure-sensitive adhesive composition of the present invention contains, in addition to the acrylic resin (A), a crosslinking agent (B), a tackifier (C), and other components as necessary.
- the pressure-sensitive adhesive composition of the present invention can be obtained by mixing the above components.
- the adhesive of this invention is obtained by bridge
- the pressure-sensitive adhesive tape of the present invention contains a pressure-sensitive adhesive obtained by crosslinking (curing) the pressure-sensitive adhesive composition as a pressure-sensitive adhesive layer. Specifically, the pressure-sensitive adhesive composition is dissolved in a solvent such as ethyl acetate to prepare a pressure-sensitive adhesive composition solution for coating so that the solid concentration is 10 to 70%. It can be set as the adhesive layer of an adhesive tape by apply
- a publicly known method for manufacturing a pressure-sensitive adhesive tape may be used.
- a pressure-sensitive adhesive is applied to one surface of a substrate and dried, and then released onto the surface of the formed pressure-sensitive adhesive layer. It can be manufactured by a method of stacking a liner or a method of applying and drying a pressure-sensitive adhesive on one surface of a release liner and stacking a substrate on the surface of the formed pressure-sensitive adhesive layer.
- a method of applying and drying the pressure-sensitive adhesive on one surface of the release liner and stacking the base material on the surface of the formed pressure-sensitive adhesive layer is preferable from the viewpoint of handling and the like.
- the base material preferably has a hand-cut product
- the surface of the base material having a hand-cut property is, for example, a corona discharge treatment, a physical treatment such as a plasma treatment, a chemical treatment such as an undercoat treatment, etc.
- the known and usual surface treatment may be appropriately performed.
- the base material is not particularly limited as long as it is a conventionally known base material.
- a laminated film in which a plastic film is laminated on a yarn cloth are preferred from the viewpoint of high tensile strength in the longitudinal direction.
- Flat yarn cloth is a woven fabric made by weaving a flat yarn, which is made of polyethylene or polypropylene, called flat yarn, cut into strips and stretched to give strength.
- a flat yarn that intersects horizontally is fixed by heat fusion so as not to be misaligned.
- release liner examples include polyolefin resins such as polyethylene, polyester resins such as polyethylene terephthalate, plastic films made of plastics such as vinyl acetate resins, polyimide resins, fluorine resins, and cellophane; kraft paper, Japanese paper, etc. Paper, rubber sheets made of natural rubber, butyl rubber, etc .; foam sheets made by foaming polyurethane, polychloroprene rubber, etc .; metal foils such as aluminum foil and copper foil; and composites thereof.
- surface treatments such as a corona treatment, may be given to the single side
- release liner for example, glassine paper, kraft paper, paper coated with a film such as polyethylene on clay coated paper, paper coated with a resin such as polyvinyl alcohol or acrylate copolymer, polyester, polypropylene, etc.
- a fluororesin or silicone resin as a release agent to a synthetic resin film or the like.
- a paper release liner is preferable in that it is easily teared by hand, and a paper release liner having a basis weight of 40 to 120 g / m 2 , preferably 50 to 80 g / m 2 is particularly preferable.
- the thickness of the release liner is preferably 40 to 180 ⁇ m, particularly 60 to 140 ⁇ m, and more preferably 80 to 120 ⁇ m. If the thickness is too thin, the production tends to be difficult, such as wrinkling at the time of winding, and if it is too thick, the hand cutting property tends to decrease.
- a coating apparatus used when coating the adhesive on one surface of the substrate or the release liner a commonly used coating apparatus may be used.
- a roll knife coater, a die coater, a roll coater , Bar coater, gravure roll coater, reverse roll coater, dipping, blade coater and the like may be used.
- the thickness of the pressure-sensitive adhesive layer after drying is preferably 5 to 200 ⁇ m, particularly preferably 10 to 150 ⁇ m, and more preferably 15 to 130 ⁇ m. When the thickness is too thick, it tends to be difficult to apply the pressure-sensitive adhesive, and when it is too thin, there is a tendency that sufficient adhesive strength cannot be obtained.
- the adhesive tape of the present invention may be a single-sided adhesive tape or a double-sided adhesive tape. Further, the pressure-sensitive adhesive layers of the double-sided pressure-sensitive adhesive tape may be the same pressure-sensitive adhesive layer or may be pressure-sensitive adhesive layers having different compositions.
- each release liner should be selected so that the release liners laminated on both sides have different peel forces in order to improve workability. Is preferred. For example, when the release liner that is lightly peeled from the release liner on the surface side to be bonded next is selected as the release force of the release liner on the surface side to be bonded next, the workability is improved.
- the drying conditions are such that the solvent and residual monomer in the adhesive are dried and removed during drying, and when a crosslinking agent is used, the functional group of the base resin reacts with the crosslinking agent to form a crosslinked structure.
- Any condition can be used.
- the drying conditions are preferably 60 to 120 ° C. and about 1 to 5 minutes. After drying, aging (aging) is performed with the pressure-sensitive adhesive layer sandwiched between sheet-like substrates, and the crosslinking reaction can further proceed.
- the pressure-sensitive adhesive tape of the present invention may be in a roll shape, in a single wafer state, or may be processed into various shapes.
- a release liner is preferably provided on both surfaces of the two pressure-sensitive adhesive layers in a single wafer state, and in a roll state, It is preferable that a release liner is provided only on one surface.
- the pressure-sensitive adhesive tape of the present invention can be obtained, but the pressure-sensitive adhesive tape of the present invention has no decrease in the pressure-sensitive adhesive performance against the adherend or base material that reduces the pressure-sensitive adhesive performance, and even under wet heat conditions. It has good adhesive performance.
- a base film when using a base material having hand cutting properties, it can be easily cut by hand at any position without using a tape cutter or the like for the width direction of the tape, This is particularly useful as an adhesive tape.
- the 180 ° peel strength according to JIS Z0237 is usually 1 to 100 N / 25 mm with respect to the adherend used.
- the 180 ° peel strength according to JIS Z0237 is preferably 25 N or more / 25 mm, particularly preferably 30 N or more / 25 mm. More preferably, it is 35 N or more / 25 mm.
- the upper limit is usually about 100 N / 25 mm.
- the 180 ° peel strength according to JIS Z0237 is preferably 3N or more / 25 mm, particularly preferably 5N or more / 25 mm. More preferably, it is 10 N or more / 25 mm. The upper limit is usually about 100 N / 25 mm.
- the 90 ° peel strength according to JIS Z0237 is preferably 3N or more / 25 mm, particularly preferably 5N or more / 25 mm, Preferably it is 6N or more / 25mm.
- the upper limit is usually about 50 N / 25 mm.
- the 180 ° peel strength according to JIS Z0237 is preferably 10 N or more / 25 mm, particularly preferably 15 N or more / 25 mm, and more preferably Is 20 N or more / 25 mm.
- the upper limit is usually about 100 N / 25 mm.
- the adhesive strength is not limited to the above range of peel strength because it varies depending on the composition (material), surface condition (surface roughness), treatment (cleaning) conditions, etc. of the adherend.
- the measurement of the adhesive force is a value measured according to JIS Z0237, and specifically, it can be measured by the method described in Examples below.
- the pressure-sensitive adhesive surface not to be tested can be measured by covering with a polyethylene terephthalate film (Lumirror S10, manufactured by Toray Industries Inc.) having a nominal thickness of 25 ⁇ m as defined in JIS C 2318. .
- a polyethylene terephthalate film Limirror S10, manufactured by Toray Industries Inc.
- the holding power of the pressure-sensitive adhesive layer when measured by the method described in Examples below, even if the test piece is displaced from the test plate after 24 hours, it is 3.0 mm or less, or the test piece is Even if it falls within 24 hours, the holding time is preferably 150 minutes or more.
- the moisture and heat resistance of the pressure-sensitive adhesive layer when measured by the method described in Examples below, that is, in the adhesion evaluation (1) test using a SUS304 steel test plate as an adherend, After 24 hours “was replaced with” Leave for 30 minutes after crimping, exposed to 60 ° C and 90% RH for 7 days, return to 23 ° C and 50% RH for 1 hour " In this case, it is preferable that the adhesive force is hardly decreased or even if it is decreased, the adhesive force is maintained at 65% or more of the initial adhesive force.
- the adhesive tape of the present invention preferably has a high tensile strength, and when it is attached to an aluminum sash or wall material, it is required to have a strength necessary for pulling so as not to be distorted or peeling off for position correction.
- the tensile strength of the adhesive tape is preferably 20 N or more / 25 mm, more preferably 30 N or more / 25 mm, and even more preferably 50 N or more / 25 mm.
- the upper limit of the tensile strength is usually 250 N / 25 mm.
- To make a double-sided adhesive tape with high tensile strength use a film that has a tensile strength equal to or higher than the tensile strength of the target adhesive tape. Can be achieved.
- the adhesive tape of the present invention includes, for example, kraft tape, OPP tape, cloth adhesive tape and other packaging tape, light packaging cellophane adhesive tape, automotive foam tape, vibration damping sheet, flame retardant adhesive tape, residential curing tape, Soundproof seal, double-sided tape for fixing carpet, vinyl tape for electrical insulation, outdoor anti-corrosion tape, indoor display tape, anti-slip tape, adhesive tape for airtight waterproofing, medical emergency adhesive plaster, surgical tape, adhesive bandage, It can be used in a wide range of applications as electrical and electronic equipment tapes, optical double-sided tapes, semiconductor dicing tapes, thermal conductive tapes, heat-resistant tapes, conductive tapes, etc. is there.
- an adherend using the adhesive tape of the present invention it is not particularly limited, but as a suitable adherend when used as an airtight waterproof adhesive tape, for example, a housing structure or its Examples include members and gaps between members. Among these, an adherend having a relatively high polarity such as an aluminum sash, an adherend having a relatively low polarity such as a moisture-permeable waterproof sheet, and an adherend having a rough surface such as OSB can be given.
- the airtight waterproof adhesive tape is attached to an opening of a window or the like, a sash frame is attached, or the outer peripheral edge of the sash frame is attached, It is possible to increase the airtightness and heat insulation of the house.
- polymer roof sheet materials such as ethylene propylene diene rubber (EPDM), butyl rubber (IIR), chloroprene rubber (CR), polyvinyl chloride, chlorinated polyethylene, thermoplastic polyolefin rubber and modified asphalt It can also be used for the purpose of hermetic sealing and waterproofing.
- acrylic resins (A) were prepared as follows.
- the viscosity, weight average molecular weight, dispersity and glass transition temperature of the acrylic resin (A) were measured according to the method described above.
- Cypomer H manufactured by Solvay Nikka Co., Ltd. was used as a mixture of the above components (a3) and (a4). Cypomer H is a mixture containing 75% CAO (a3) and 25% acrylic acid (a4).
- the viscosity of the resulting acrylic resin (A-1) resin solution was 3500 mPa ⁇ s / 25 ° C., the weight average molecular weight was 570,000, the degree of dispersion was 4.3, and the glass transition temperature was ⁇ 60 ° C.
- the acrylic resin (A-1) was produced in the same manner except that the blending amounts shown in Tables 1 and 2 were changed, and acrylic resins (A-2) to (A-14) and (A'-1) ) To (A′-3) were obtained.
- Tables 1 and 2 below also show the viscosity, weight average molecular weight, degree of dispersion, and glass transition temperature of acrylic resins (A-1) to (A-14) and (A'-1) to (A'-3). Also shown.
- ⁇ Crosslinking agent (B)> The following were prepared as a crosslinking agent (B).
- ⁇ Tackifier (C)> The following were prepared as a tackifier (C).
- the pressure-sensitive adhesive composition solution prepared as described above was applied to a flat yarn (manufactured by Diatex Co., Ltd., thickness 130 ⁇ m) using an applicator so that the thickness after drying was 100 ⁇ m, and the coating was performed at 90 ° C. for 3 minutes. After drying, the release surface of a paper release liner (manufactured by Sanei Kaken Co., Ltd., K-80H-S (F)) was attached. Then, the heat aging process was performed for 7 days in the 40 degreeC drying machine, and the adhesive tape was produced.
- a paper release liner manufactured by Sanei Kaken Co., Ltd., K-80H-S (F)
- test pieces were prepared by cutting the adhesive tapes of Examples 18 to 21 and Comparative Example 4 into a width of 25 mm and a length of 150 mm.
- a test plate of EPDM manufactured by Nippon Test Panel Co., Ltd., standard test plate
- Crimping was performed by reciprocating twice at a crimping speed of 10 mm / s.
- Test pieces were prepared by cutting the adhesive tapes of Examples 1 to 17 and Comparative Examples 1 to 3 to a width of 25 mm and a length of 150 mm. Next, a commercially available Tyvek house wrap sheet and an OSB test plate were used as the adherend, and the adhesive layer of the test piece from which the paper release liner was peeled was applied to the surface of this test plate with a weight of 2 kg. The sheet was reciprocated twice by a roller (pressure bonding speed: 10 mm / s).
- Tyvek house wrap sheet is a commercially available Tyvek® house wrap, OSB (Oriented Strand Board: a wooden board obtained by orienting and stacking thin pieces of wood into high-pressure compression with an adhesive) Ainsworth's product was used.
- Test pieces were prepared by cutting the adhesive tapes of Examples 1 to 17 and Comparative Examples 1 to 3 to a width of 25 mm and a length of 150 mm. Next, a test plate made of SUS304 steel was used as an adherend, and the contact area between the pressure-sensitive adhesive layer of the test piece from which the paper release liner was peeled off and the test plate was 25 mm wide ⁇ 25 mm long. The test piece was reciprocated twice with a roller having a weight of 2 kg (crimping speed: 10 mm / s). The part of the test piece where the adhesive was exposed was folded. After crimping, the sample was left in an environment of 23 ° C.
- Test pieces were prepared by cutting the adhesive tapes of Examples 1 to 17 and Comparative Examples 1 to 3 to a width of 25 mm and a length of 150 mm. Next, a test plate made of SUS304 steel was used as the adherend, and the adhesive layer of the test piece from which the paper release liner was peeled was reciprocated twice on this test plate with a roller weighing 2 kg at a pressing speed of 10 mm / s. And crimped. After crimping, leave it for 30 minutes, expose it in an environment of 60 ° C. and 90% RH for 7 days, return it to an environment of 23 ° C. and 50% RH, leave it for 1 hour, and then fold the play part of the test piece 180 °.
- test plate After peeling off 30 mm, the test plate is fixed to the lower chuck and the end of the test piece is fixed to the upper chuck, and the adhesive tape is peeled off from the adherend at a peeling angle of 180 ° and a speed of 300 mm / min. Was measured.
- the measurement results are shown in Tables 3 and 4 below.
- all of the examples of the present invention are adherends having a relatively high polarity such as SUS, adherends having a relatively low polarity such as polyethylene, and OSB. It has been found that even an adherend having such a rough surface adheres firmly, has a high holding power, and is excellent in adhesiveness even in a high temperature and high humidity environment.
- the comparative example 1 product is inferior in adhesiveness to an adherend having a relatively high polarity such as SUS, and in particular, an adherend having a relatively low polarity such as polyethylene. was found to be inferior in adhesion to SUS, low in holding power, and weak in moisture and heat resistance.
- Comparative Example 3 had low adhesion and holding power to adherends having relatively high polarity, adherends having low polarity, and adherends having rough surfaces. Moreover, from the results of Table 5 above, it was found that all of the examples of the present invention adhered firmly to EPDM. On the other hand, it was found that Comparative Example 4 had poor adhesion to EPDM.
- the pressure-sensitive adhesive composition of the present invention has high adhesion to a highly polar adherend, a low polarity adherend, a hardly adherent adherend such as ethylene propylene diene rubber (EPDM), and a rough surface.
- a pressure-sensitive adhesive composition with excellent holding power, excellent adhesiveness even in high-temperature and high-humidity environments, and reduced adhesive deterioration over time, and packaging tapes such as craft tape, OPP tape, and cloth adhesive tape Cellophane adhesive tape for light packaging, foam tape for automobiles, damping sheet, flame retardant adhesive tape, residential curing tape, soundproof seal, double-sided tape for fixing carpet, vinyl tape for electrical insulation, outdoor anticorrosion tape, indoor display tape , Anti-slip tape, airtight waterproof adhesive tape, medical adhesive bandage, surgical tape, adhesive bandage, electrical / electronic tape, optical double-sided tape, semiconductor adhesive Sing tape, thermally conductive tape, heat tape, as the conductive tape or the like, can be used in a wide range of applications, among
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Abstract
Description
ここで、R1は水素またはメチル基、R2は飽和脂肪族、不飽和脂肪族、芳香族、飽和脂環族、または2価の不飽和脂環族炭化水素、nは1以上の正数を示す。
〔式〕 CH2=CR1-CO-O-(R2-COO-)nH ・・・(1)
ここで、R1は水素またはメチル基、R2は飽和脂肪族、不飽和脂肪族、芳香族、飽和脂環族、または2価の不飽和脂環族炭化水素、nは1以上の正数を示す。
なお、本発明において、(メタ)アクリルとはアクリルあるいはメタクリルを、(メタ)アクリロイルとはアクリロイルあるいはメタクリロイルを、(メタ)アクリレートとはアクリレートあるいはメタクリレートをそれぞれ意味するものである。また、アクリル系樹脂とは、少なくとも1種の(メタ)アクリレート系モノマーを含む重合成分を重合して得られる樹脂である。
本発明で用いられるアクリル系樹脂(A)は、炭素数1~3のアルキル基を有する(メタ)アクリレート、t-ブチル(メタ)アクリレート、環状構造含有モノマー及び炭素数3~10のビニルエステル系モノマーからなる群から選ばれる少なくとも1種(a1)、t-ブチル(メタ)アクリレートを除く、炭素数4~24のアルキル基を有する(メタ)アクリレート(a2)、後記一般式(1)で示される末端カルボキシル基含有モノマー(a3)及び(メタ)アクリル酸(a4)を特定量含む共重合成分(a)を共重合してなるものである。
さらに、共重合成分として、必要に応じて、水酸基含有モノマー(a5)やその他の重合性モノマー(a6)を含有してなるものである。以下、各共重合成分(a)を順に説明する。
上記(a1)成分は、炭素数1~3のアルキル基を有する(メタ)アクリレート、t-ブチル(メタ)アクリレート、環状構造含有モノマー及び炭素数3~10のビニルエステル系モノマーからなる群から選ばれる少なくとも1種である。中でも、炭素数1~3のアルキル基を有する(メタ)アクリレートであることが好ましい。
上記(a2)は、共重合成分(a)の主成分となるものであり、t-ブチル(メタ)アクリレートを除く、炭素数4~24、好ましくは炭素数4~12のアルキル基を有する(メタ)アクリレートである。
上記(a3)成分は、下記一般式(1)で示される末端カルボキシル基含有モノマーである。
ここで、R1は水素またはメチル基、R2は飽和脂肪族、不飽和脂肪族、芳香族、飽和脂環族、または2価の不飽和脂環族炭化水素、nは1以上の正数を示す。
(メタ)アクリル酸(a4)の含有割合としては、共重合成分(a)全体の通常0.1~5重量%、特には0.5~4.5重量%、さらには1~4重量%であることが好ましい。含有割合が少なすぎると各種被着体に対する接着性が低下する傾向があり、多すぎると低極性の被着体に対する接着性が低下する傾向がある。
本発明では上記(a1)~(a4)の各成分を共重合したアクリル系樹脂(A)を用いるが、さらに水酸基含有モノマー(a5)を共重合させることが望ましい。この水酸基含有モノマー(a5)としては、例えば、2-ヒドロキシエチル(メタ)アクリレート、4-ヒドロキシブチル(メタ)アクリレート、5-ヒドロキシペンチル(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(メタ)アクリル酸ヒドロキシアルキルエステル、カプロラクトン変性2-ヒドロキシエチル(メタ)アクリレート等のカプロラクトン変性モノマー、ジエチレングリコール(メタ)アクリレート、ポリエチレングリコール(メタ)アクリレート等のオキシアルキレン変性モノマー、2-アクリロイロキシエチル-2-ヒドロキシエチルフタル酸等の1級水酸基含有モノマー;2-ヒドロキシプロピル(メタ)アクリレート、2-ヒドロキシブチル(メタ)アクリレート、3-クロロ2-ヒドロキシプロピル(メタ)アクリレート等の2級水酸基含有モノマー;2,2-ジメチル2-ヒドロキシエチル(メタ)アクリレート等の3級水酸基含有モノマーをあげることができる。
これらの中でも、架橋剤との反応性に優れる点で1級水酸基含有モノマーが好ましく、特には2-ヒドロキシエチル(メタ)アクリレート、4-ヒドロキシブチル(メタ)アクリレート好ましい。
本発明では必要に応じてその他の重合性モノマー(a6)を用いてもよく、その他の重合性モノマー(a6)としては、例えば、アセトアセチル基含有モノマー、イソシアネート基含有モノマー、グリシジル基含有モノマー、アミノ基含有モノマー、アミド基含有モノマーの官能基含有モノマーやその他の共重合性モノマーがあげられる。
かかる重合にあたっては、溶液重合で製造することが、安全に、安定的に、任意のモノマー組成でアクリル系樹脂(A)を製造できる点で好ましい。
本発明の粘着剤組成物は、上記アクリル系樹脂(A)に加え、架橋剤(B)を含有することが接着性の点から好ましい。
ここで上記架橋剤(B)は、アクリル系樹脂(A)中の官能基と反応し、架橋構造を形成させるものであり、例えば、エポキシ系架橋剤、イソシアネート系架橋剤、アジリジン系架橋剤、メラミン系架橋剤、アルデヒド系架橋剤、アミン系架橋剤、金属キレート系架橋剤があげられる。これらの中でも各種被着体に対する接着性と保持力をバランスよく両立させることができる点から、エポキシ系架橋剤を用いることが好ましく、また、高温・高湿の環境下においても粘着テープとしての経時安定性に優れ、さらに接着性及び耐湿熱性に優れた効果を得るためにはイソシアネート系架橋剤を用いることが好ましい。
粘着付与剤(C)は、アクリル系樹脂(A)の良好な物性をさらに発揮させるために用いられるものであり、本発明の粘着剤組成物に含有されることが好ましい。粘着付与剤(C)としては、アクリル系樹脂(A)に相溶性を示す樹脂、例えば、ロジン系樹脂、テルペン系樹脂、キシレン系樹脂、フェノール系樹脂、クマロン系樹脂、石油系樹脂等があげられる。これらの粘着付与剤(C)は、単独でもしくは2種以上を併せて用いることができる。
上記成分を混合することにより、本発明の粘着剤組成物を得ることができる。また、この粘着剤組成物が架橋されることにより、本発明の粘着剤が得られる。そして、この粘着剤は、本発明の粘着テープの粘着剤層として好適に用いることができる。
本発明の粘着テープは、上記粘着剤組成物を架橋(硬化)することにより得られた粘着剤を、粘着剤層として含有するものである。具体的には、上記粘着剤組成物を、酢酸エチル等の溶媒に溶解させて、固形分濃度が10~70%になるように塗工用の粘着剤組成物溶液を調液し、この溶液を基材に塗工、乾燥することにより粘着テープの粘着剤層とすることができる。
かかる厚みが厚すぎると粘着剤の塗工が困難になる傾向があり、薄すぎると充分な粘着力が得られない傾向がある。
そして、粘着テープが、両面粘着テープの場合、枚葉状態には、2つの粘着剤層の両方の表面にリリースライナーが設けられることが好ましく、ロール状態の場合には、2つの粘着剤層の一方の表面のみにリリースライナーが設けられることが好ましい。
また、ポリマーの屋根シート材料等、例えば、エチレンプロピレンジエンゴム(EPDM)、ブチルゴム(IIR)、クロロプレンゴム(CR)、ポリ塩化ビニル、塩素化ポリエチレン、熱可塑性ポリオレフィンゴムおよび改質アスファルトなどのシートの継ぎ目の気密・防水を目的として用いることもできる。
なお、アクリル系樹脂(A)の粘度、重量平均分子量、分散度及びガラス転移温度に関しては、前述の方法にしたがって測定した。
アクリル系樹脂(A)の製造に先立ち、製造に用いる共重合成分(a)として以下のものを用意した。
(a1)成分
・MA:メチルアクリレート
・MMA:メチルメタクリレート
・EA:エチルアクリレート
・Vac:酢酸ビニル
・t-BA:ターシャリーブチルアクリレート
・ACMO:アクリロイルモルホリン
(a2-1)成分
・BA:ブチルアクリレート
(a2-2)成分
・2EHA:2-エチルヘキシルアクリレート
(a3)成分
・CAO:下記一般式(1)で示される末端カルボキシル基含有モノマー
CH2=CR1-CO-O-(R2-COO-)nH ・・・(1)
上記一般式(1)においてR1は水素、R2はエチレン鎖、nは1~5の化合物(以下、「CAO」と称することがある)
(a4)成分
・AAc:アクリル酸
(a5)成分
・HEMA:2-ヒドロキシエチルメタクリレート
サイポマーHは、CAO(a3)を75%と、アクリル酸(a4)を25%含有する混合物である。
温度計、撹拌機及び還流冷却機を備えた反応器内に、メチルアクリレート(a1)3部、ブチルアクリレート(a2-1)26.7部、2-エチルヘキシルアクリレート(a2-2)65.2部、サイポマーH 5部〔CAO(a3)3.75部、アクリル酸(a4)1.25部〕、2-ヒドロキシエチルメタクリレート(a5)0.1部、酢酸エチル55部、及び重合開始剤としてアゾビスイソブチロニトリル0.15部を仕込み、撹拌しながら昇温し、酢酸エチル還流温度にて7時間重合させた後、酢酸エチルで希釈してアクリル系樹脂(A-1)の51%溶液を得た。
得られたアクリル系樹脂(A-1)の樹脂溶液の粘度は3500mPa・s/25℃、重量平均分子量は57万、分散度4.3、ガラス転移温度は-60℃であった。
アクリル系樹脂(A-1)の製造において、下記表1、2に示す配合量に変更した以外は同様に行い、アクリル系樹脂(A-2)~(A-14)及び(A’-1)~(A’-3)の溶液を得た。また、下記表1、2にアクリル系樹脂(A-1)~(A-14)及び(A’-1)~(A’-3)の粘度、重量平均分子量、分散度及びガラス転移温度も併せて示す。
架橋剤(B)として以下のものを用意した。
・エポキシ系架橋剤:テトラッドC(1,3-ビス(N,N-ジグリシジルアミノメチル)シクロヘキサン)、三菱ガス化学社製
・イソシアネート系架橋剤:コロネートL-55E(トリレンジイソシアネートとトリメチロールプロパンのアダクト体〔固形分55%〕)、東ソー社製
粘着付与剤(C)として以下のものを用意した。
・不均化ロジンエステル:スーパーエステルA-100(不均化ロジンのグリセリンエステル、軟化点95~105℃)、荒川化学工業社製
上記のようにして調製、準備したアクリル系樹脂(A-1)~(A-14)及び(A’-1)~(A’-3)について、その固形分100部に対して、実施例1~14及び比較例1~3は、架橋剤(B)としてエポキシ系架橋剤(テトラッドC)を0.03部、実施例15~17についてはイソシアネート系架橋剤(コロネートL-55E)を固形分に換算して後記の表4記載の量、粘着付与剤(C)として不均化ロジンエステル(スーパーエステルA-100)15部を混合し、酢酸エチルにて固形分濃度を48%になるように調液し、均一になるまで撹拌し、粘着剤組成物溶液を得た。
得られた粘着剤組成物について、以下の通り粘着テープを作製し、以下の評価を行った。評価結果を後記の表3及び4に示す。
上記のようにして調製、準備したアクリル系樹脂(A-1、A-14、A’-1)について、その固形分100部に対して、架橋剤(B)としてエポキシ系架橋剤テトラッドC、または、イソシアネート系架橋剤コロネートL-55Eを固形分に換算して後記の表5記載の量、及び、粘着付与剤(C)を15部混合し、酢酸エチルにて固形分濃度を48%になるように調液し、均一になるまで撹拌し、粘着剤組成物溶液を得た。
得られた粘着剤組成物について、以下の通り粘着テープを作製し、以下の評価を行った。評価結果を後記の表5に示す。
上記のようにして準備した粘着剤組成物溶液をフラットヤーン(ダイヤテックス社製、厚み130μm)に対して乾燥後の厚みが100μmになるようにアプリケーターを用いて塗工し、90℃で3分間乾燥し、紙製リリースライナー(サンエー化研社製、K-80H-S(F))の剥離面を貼り合わせた。その後、40℃の乾燥機中で7日間加熱エージング処理を行い、粘着テープを作製した。
上記実施例1~17、比較例1~3の粘着テープを幅25mm、長さ150mmにカットして試験片を作製した。次いで、被着体としてSUS304鋼(エンジニアリングテストサービス社製、JIS規格適合品)、及びポリエチレン(PE)(日本テストパネル社製、標準試験板)の試験板を使用し、この試験板に、紙製リリースライナーを剥離した試験片の粘着剤層を重さ2kgのローラーを圧着速さ10mm/sで2往復させて圧着させた。圧着後、24時間放置し、試験片の遊び部分を180°折り返し、30mm剥がした後、下部のチャックに試験板を、上部のチャックに試験片の端をそれぞれ固定し、引き剥がし角度180°、300mm/minの速度で被着体から粘着テープを引き剥がし、粘着力を測定した。測定結果を後記表3、4に示す。
上記実施例1~17、比較例1~3の粘着テープを幅25mm、長さ150mmにカットして試験片を作製した。次いで、被着体として市販品のタイベック・ハウスラップシート、及びOSBの試験板を使用し、この試験板の表面に対し、紙製リリースライナーを剥離した試験片の粘着剤層を重さ2kgのローラー(圧着速さ10mm/s)で2往復させて圧着させた。圧着後、24時間放置し、試験片の遊び部分を180°折り返し、30mm剥がした後、試験板を治具に固定し、試験機のチャックに試験片の端を固定し、引き剥がし角度90°、300mm/minの速度で被着体から粘着テープを引き剥がし、粘着力を測定した。測定結果を後記表3、4に示す。
なお、タイベック・ハウスラップシートは市販品のタイベック(R)・ハウスラップを、OSB(Oriented Strand Board:薄い削片状にした木片を配向させて積層させ接着剤で高温圧縮した木質板)はカナダのエインズワース社製のものを使用した。
上記実施例1~17、比較例1~3の粘着テープを幅25mm、長さ150mmにカットして試験片を作製した。次いで、被着体としてSUS304鋼の試験板を使用し、この試験板に、紙製リリースライナーを剥離した試験片の粘着剤層と試験板との接触面積が幅25mm×長さ25mmになるように上記試験片を重さ2kgのローラー(圧着速さ10mm/s)で2往復させて圧着させた。試験片の粘着剤が露出する部分は折り返した。圧着後23℃、50%RHの環境にて30分間放置し、40℃の環境に移し20分間静置した。試験板及び試験片が鉛直に垂れ下がるように1kgの錘を取り付け、その後40℃の環境にて試験片が落下する時間、または、24時間後に試験片が試験板からずれた距離を測定した。なお、24時間以内に試験片が落下しなかった場合は、値を1440(min)とした。測定結果を後記表3、4に示す。
上記実施例1~17、比較例1~3の粘着テープを幅25mm、長さ150mmにカットして試験片を作製した。次いで、被着体としてSUS304鋼の試験板を使用し、この試験板に、紙製リリースライナーを剥離した試験片の粘着剤層を重さ2kgのローラーを圧着速さ10mm/sで2往復させて圧着させた。圧着後、30分間放置し、60℃、90%RHの環境にて7日間暴露し、23℃、50%RHの環境に戻し、1時間放置した後、試験片の遊び部分を180°折り返し、30mm剥がした後、下部のチャックに試験板を、上部のチャックに試験片の端をそれぞれ固定し、引き剥がし角度180°、300mm/minの速度で被着体から粘着テープを引き剥がし、粘着力を測定した。測定結果を後記表3、4に示す。
これに対し、比較例1品はSUSのような比較的極性が高い被着体や、特にポリエチレンのように比較的極性が低い被着体に対する接着性に劣る結果となり、また、比較例2品はSUSに対する接着力に劣るとともに、保持力も低く、さらには、耐湿熱性に弱いことが分かった。更に、比較例3品は極性の比較的高い被着体や低い被着体、粗面を有する被着体に対して接着性や保持力の低いものであった。
また上記表5の結果より、本発明の実施例品はいずれも、EPDMに対して強固に接着することが分かった。
これに対し、比較例4品はEPDMに対する接着性が弱いことが分かった。
Claims (8)
- 炭素数1~3のアルキル基を有する(メタ)アクリレート、t-ブチル(メタ)アクリレート、環状構造含有モノマー及び炭素数3~10のビニルエステル系モノマーからなる群から選ばれる少なくとも1種(a1)1~20重量%、
t-ブチル(メタ)アクリレートを除く、炭素数4~24のアルキル基を有する(メタ)アクリレート(a2)55~97重量%、
下記一般式(1)で示される末端カルボキシル基含有モノマー(a3)1~20重量%、
及び(メタ)アクリル酸(a4)0.1~5重量%、
を含む共重合成分(a)を共重合してなるアクリル系樹脂(A)を含有することを特徴とする粘着剤組成物。
〔式〕 CH2=CR1-CO-O-(R2-COO-)nH ・・・(1)
ここで、R1は水素またはメチル基、R2は飽和脂肪族、不飽和脂肪族、芳香族、飽和脂環族、または2価の不飽和脂環族炭化水素、nは1以上の正数を示す。 - 上記炭素数4~24のアルキル基を有する(メタ)アクリレート(a2)として、炭素数4~7のアルキル基を有する(メタ)アクリレート(a2-1)及び炭素数8~24のアルキル基を有する(メタ)アクリレート(a2-2)を含有することを特徴とする請求項1記載の粘着剤組成物。
- 上記炭素数4~7のアルキル基を有する(メタ)アクリレート(a2-1)の炭素数8~24のアルキル基を有する(メタ)アクリレート(a2-2)に対する含有割合が、重量比で、(a2-1)/(a2-2)=1/99~85/15であることを特徴とする請求項2記載の粘着剤組成物。
- 上記一般式(1)で示される末端カルボキシル基含有モノマー(a3)100重量部に対する上記(メタ)アクリル酸(a4)の含有量が10~400重量部であることを特徴とする請求項1~3のいずれか一項に記載の粘着剤組成物。
- 上記共重合成分(a)として、さらに水酸基含有モノマー(a5)を含有することを特徴とする請求項1~4のいずれか一項に記載の粘着剤組成物。
- 請求項1~5のいずれか一項に記載の粘着剤組成物が架橋されてなることを特徴とする粘着剤。
- 基材と、上記基材上に形成された請求項6記載の粘着剤とを備えることを特徴とする粘着テープ。
- 請求項7記載の粘着テープからなることを特徴とする気密防水用粘着テープ。
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WO2020189652A1 (ja) * | 2019-03-19 | 2020-09-24 | 三菱ケミカル株式会社 | 粘着剤組成物、粘着剤および粘着テープ |
KR20200136155A (ko) * | 2019-05-27 | 2020-12-07 | 주식회사 엘지화학 | 점착제 조성물, 이를 포함하는 점착 필름, 점착 필름의 제조 방법 및 이를 포함하는 플라스틱 유기 발광 디스플레이 |
JP2021070744A (ja) * | 2019-10-30 | 2021-05-06 | 綜研化学株式会社 | 粘着剤組成物および粘着シート |
TWI759029B (zh) * | 2019-12-27 | 2022-03-21 | 日商有澤製作所股份有限公司 | 黏著帶 |
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WO2020082318A1 (en) * | 2018-10-26 | 2020-04-30 | Henkel Ag & Co. Kgaa | Reworkable adhesive composition |
EP4130185A4 (en) * | 2020-03-27 | 2024-02-14 | Mitsubishi Chemical Corporation | ADHESIVE COMPOSITION, ADHESIVE, TAPE AND TAPE FOR AIR-TIGHT AND WATER-TIGHT SEALS |
TWI827251B (zh) * | 2022-09-13 | 2023-12-21 | 碁達科技股份有限公司 | 防水黏著劑 |
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KR20200136155A (ko) * | 2019-05-27 | 2020-12-07 | 주식회사 엘지화학 | 점착제 조성물, 이를 포함하는 점착 필름, 점착 필름의 제조 방법 및 이를 포함하는 플라스틱 유기 발광 디스플레이 |
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TWI759029B (zh) * | 2019-12-27 | 2022-03-21 | 日商有澤製作所股份有限公司 | 黏著帶 |
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US20200002579A1 (en) | 2020-01-02 |
JP7147559B2 (ja) | 2022-10-05 |
EP3597716A1 (en) | 2020-01-22 |
EP3597716A4 (en) | 2020-03-18 |
JPWO2018168678A1 (ja) | 2020-01-16 |
US11286323B2 (en) | 2022-03-29 |
EP3597716A8 (en) | 2020-05-20 |
EP3597716B8 (en) | 2021-08-18 |
EP3597716B1 (en) | 2021-06-16 |
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