WO2002055626A1 - Compositions adhesives enlevables et procede de preparation correspondant - Google Patents

Compositions adhesives enlevables et procede de preparation correspondant Download PDF

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Publication number
WO2002055626A1
WO2002055626A1 PCT/JP2001/008511 JP0108511W WO02055626A1 WO 2002055626 A1 WO2002055626 A1 WO 2002055626A1 JP 0108511 W JP0108511 W JP 0108511W WO 02055626 A1 WO02055626 A1 WO 02055626A1
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Prior art keywords
water
adhesive
weight
parts
adhesive composition
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PCT/JP2001/008511
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English (en)
Japanese (ja)
Inventor
Shigeo Hori
Nobuyuki Uto
Chiaki Sato
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Kaken Tech C0., Ltd.
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Priority to JP2002556681A priority Critical patent/JP4246993B2/ja
Publication of WO2002055626A1 publication Critical patent/WO2002055626A1/fr

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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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • 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
    • C09J2301/412—Additional features of adhesives in the form of films or foils characterized by the presence of essential components presence of microspheres

Definitions

  • the present invention relates to a release-type adhesive composition (including sealant) whose adhesive strength decreases after water absorption or water absorption heating, and in particular, peeling for bonding a plurality of constituent members to form a predetermined structure. It is a type adhesive composition that exhibits a predetermined adhesive strength before water absorption treatment, but the adhesive force is quickly reduced after water absorption or water absorption heating, and can be easily separated into the original components.
  • the present invention relates to a peelable adhesive composition and a method for producing the same. Background art
  • the Recycling Law has been enacted, and it has been required to separate and collect each component of a structure joined by an adhesive composition, and to reuse each component. It is also desirable that the labeling masking film or the masking film or the like affixed to the base material with the adhesive composition can be easily peeled off from the base material when the intended use is completed.
  • the conventional adhesive composition is intended only to strongly adhere each component, label, etc., and is separated into each component as required, or the label, etc., without damaging the base material. It was not easy to peel off.
  • Japanese Patent Application Laid-Open No. 5-173874 discloses an adhesive label in which an acryl-based adhesive layer containing a water-absorbing polymer is formed on a heat-shrinkable sheet.
  • the disclosed pressure-sensitive adhesive label had to use a heat-shrinkable sheet as a base material, and was not only complicated in configuration but also expensive and economically disadvantageous.
  • the water-absorbing polymer is used for adhesives with high cohesion, For example, when simply added to an adhesive composed of a block copolymer, an epoxy resin, or the like, there were cases where the peelability was insufficient.
  • Japanese Patent Application Laid-Open No. H11-112748 discloses a releasable adhesive sheet. More specifically, it is composed of a base film and an adhesive layer formed on the base film, and the adhesive layer has 100 parts by weight of the acrylic adhesive. The polyolefin granules are blended in the range of 1 to 25 parts by weight. However, even with such a removable adhesive sheet, it has been difficult to easily and quickly remove the adhesive sheet from the base material after a long period of time.
  • Japanese Patent Application Laid-Open No. Hei 7-118580 discloses a method for peeling an adhesive, affixed or coated article from a substrate using a peeling sheet. More specifically, a release sheet is constituted by a base material and an adhesive layer formed of an anaerobic adhesive or an anaerobic pressure-sensitive adhesive formed thereon. Then, after the release sheet is attached to the surface of an adhesive, affixed or painted material, the adhesive layer is cured to release these adhesives and the like.
  • a long period of time has elapsed, it has been difficult to uniformly peel the adhesive from the substrate even with such a release sheet.
  • Japanese Unexamined Patent Publication (Kokai) No. 11-92728 discloses a peelable adhesive composition containing a water-soluble filler in a range of 0.1 to 200 parts by weight based on an adhesive base resin. Has already been proposed. When such a peelable adhesive composition is used, an effect that the structure can be peeled in a short time by immersing the structure can be obtained. However, even in such a peelable adhesive composition, a peelable adhesive composition that can be easily peeled in a shorter time depending on the application. was desired. Furthermore, when a hot-melt type adhesive is used as the base resin of the adhesive, it is difficult to disperse uniformly when a relatively large amount of a water-soluble filler is added due to its high viscosity. Case was seen.
  • Japanese Patent Application Laid-Open Nos. Sho 56-61467, Sho 56-61468, Sho 60-252681, Sho 63-17981, Hei 6-33025, Kaihei 6-184504, JP-A-112-18921, JP-2000-868994, and JP-A-2000-239620 disclose an adhesive or a photocurable resin comprising an acrylic resin or the like.
  • a heat-peelable adhesive to which a predetermined amount of thermally expandable particles is added is disclosed.
  • all of these heat-peelable adhesives are intended only for heat-peeling, and are not intended for rapid self-peeling by combining heat-expandable particles with a water-absorbent crosslinked polymer. Did not.
  • the inventors of the present invention used a hot-melt type adhesive or the like as a base resin of an adhesive by containing a water-absorbent crosslinked polymer and further heat-expandable particles in a predetermined amount range. Even in this case, the inventors have found that an adhesive composition that can be uniformly dispersed and that can be peeled off in a shorter time can be obtained, and the present invention has been completed.
  • an object of the present invention is that even when a relatively large amount of a water-absorbent crosslinked polymer is added, the water-absorbent crosslinked polymer can be uniformly dispersed in a base resin of various adhesives, and is high before water absorption.
  • An object of the present invention is to provide an adhesive composition that can obtain adhesive strength and can be peeled off in a short time after absorbing water, and a production method that can efficiently obtain such a peelable adhesive composition.
  • Another object of the present invention is to provide a release-type adhesive composition that combines heat-expandable particles and a water-absorbent crosslinked polymer to self-peel (natural release) after water absorption and heating, and such a release.
  • An object of the present invention is to provide a production method capable of efficiently obtaining a mold adhesive composition. Disclosure of the invention
  • a peelable adhesive composition having a reduced adhesive strength after absorbing water.
  • a peelable adhesive composition containing the water-absorbent crosslinked polymer in the range of 1 to 200 parts by weight with respect to 100 parts by weight of the base resin of the adhesive, and solves the above-mentioned problems. be able to.
  • a peelable adhesive composition by combining an adhesive base resin and a predetermined range of a water-absorbing crosslinked polymer, a structural article bonded using such a peelable adhesive composition
  • a component different from the component
  • the water-absorbent cross-linked polymer swells moderately, the adhesive strength between the components decreases quickly, and each component is separated and collected. Can be.
  • the water-absorbing crosslinked polymer When the water-absorbing crosslinked polymer is used and the amount of addition is within such a range, it can be uniformly dispersed in the base resin of the adhesive.
  • the term “after water absorption” in which the adhesive strength is reduced refers to water (which may contain an alcohol or a surfactant, etc .; the same applies hereinafter), hot water (less than 40 to 70 ° C) or It refers to the state of being immersed in hot water (70 to 150 ° C including pressurized conditions) and forcibly absorbing water. Therefore, it does not mean a state in which the water-absorbing crosslinked polymer partially absorbs moisture in the surrounding air.
  • the average particle diameter is set to a value in the range of 1 to 300 m
  • the average fiber length is preferably in the range of 2 to 60 mm.
  • the water-absorbent crosslinked polymer By limiting the average particle size of the water-absorbent crosslinked polymer to the average fiber length to such a range, the water-absorbent crosslinked polymer can be more uniformly dispersed in the base resin of the adhesive. Moreover, a water-absorbent crosslinked polymer having such an average particle diameter / average fiber length can effectively prevent problems such as variation or reduction in adhesive strength before water absorption.
  • the water absorption ratio of the water-absorbing bridge polymer is set to a value within a range of 5 to 1,000 times.
  • the water-absorbing bridge polymer is a crosslinked product of a hydrolyzate of a starch-acrylic nitrile graft polymer, and a starch-acrylic acid graft polymer.
  • such a water-absorbing crosslinked polymer can be more uniformly dispersed in the base resin of the adhesive.
  • the surfactant is added in the range of 0.001 to 20 parts by weight with respect to 100 parts by weight of the base resin of the adhesive. It is preferred to include.
  • the base resin of the adhesive is a rubber-based resin
  • the tackifier is added to 100 parts by weight of the base resin of the adhesive. Is preferably contained in the range of 1 to 800 parts by weight.
  • the base resin of the adhesive is a hot melt type resin.
  • a hot-melt resin such as S 02 0
  • a hot-melt resin can be adjusted to an appropriate viscosity simply by heating without using a solvent, so that it can be uniformly mixed and dispersed without deteriorating the water-absorbent crosslinked polymer. Can be.
  • the base resin of the adhesive is a thermosetting resin.
  • thermosetting resin By using such a thermosetting resin, the initial adhesive strength is high, and excellent mechanical properties and heat resistance can be obtained, so that it can be used as a structural adhesive.
  • thermosetting resin has a low molecular weight before curing and has a relatively low viscosity, so that it can be easily handled as an adhesive.
  • the thermally expandable particles are contained in an amount of 1 to 300 parts by weight based on 100 parts by weight of the base resin of the adhesive. Is preferred.
  • the water-absorbent cross-linked polymer absorbs water and the heat-expandable particles also expand, so they are separated from the adherend in a very short time.
  • self-peeling can also be performed.
  • Another embodiment of the present invention relates to a method for producing a peelable adhesive composition in which the adhesive strength is reduced after water absorption
  • a release adhesive composition can be produced using the adhesive in a molten state. Accordingly, the water-absorbing crosslinked polymer can be uniformly dispersed in the base resin of the adhesive even without solvent. Therefore, a high adhesive strength can be obtained before water absorption, while a water-absorbent cross-linked polymer swells moderately after water absorption, and a peelable adhesive composition in which the adhesive force quickly decreases can be effectively obtained. .
  • Another aspect of the present invention is a method for producing a peelable adhesive composition in which the adhesive strength is reduced after water absorption
  • thermosetting resin as a base resin of the adhesive; and adding 1 to 200 parts by weight of a water-absorbing crosslinked polymer to 100 parts by weight of the base resin of the adhesive.
  • thermosetting resin By producing a peelable adhesive composition using a thermosetting resin in this way, it is possible to uniformly disperse the water-absorbent crosslinked polymer even in the absence of a solvent in the base resin of the adhesive. it can. Accordingly, it is possible to obtain an extremely high adhesive strength before water absorption, but it is possible to effectively obtain a peelable adhesive composition in which, after water absorption, the water-absorbent crosslinked polymer swells appropriately and the adhesive strength decreases promptly. it can.
  • the heat-expandable particles are added in an amount of 1 to 300 parts by weight based on 100 parts by weight of the base resin of the adhesive. It is preferable to further include a step of adding in a range of parts by weight.
  • FIG. 1 is a diagram showing an example of the effect of the amount of water-absorbent crosslinked polymer added.
  • FIG. 2 is a diagram showing an example of a change in adhesive force under different water absorption conditions.
  • FIG. 3 is a diagram showing an example of the effect of the amount of the thermally expandable particles added.
  • FIG. 4 is a cross-sectional view of a film adhesive made of the heat-adhesive peelable adhesive composition of the present invention.
  • a first embodiment of the present invention is a release adhesive composition containing the following components (A) to (D) (hereinafter sometimes referred to as a water release adhesive composition).
  • a water release adhesive composition containing the following components (A) to (D) (hereinafter sometimes referred to as a water release adhesive composition).
  • the components (A) and (B) are essential components, and the components (C) and (D) are optional components.
  • the base resin of the adhesive used in the present invention includes a hot melt adhesive, a solvent-based adhesive, a photo-curable adhesive, a one-part type thermosetting adhesive, and a two-part type thermosetting adhesive.
  • Adhesives such as adhesives and pressure-sensitive adhesives (adhesives) can be used.
  • hot-melt adhesives include (meth) acrylic acid-based polymers, polyvinyl chloride resins, polyurethane resins, cellulose acetate resins, Ethylene vinyl acetate copolymer, polyvinyl acetate resin, olefin resin, polyvinyl acetal resin, polyvinyl alcohol derivative, silicone resin, natural rubber, acryl rubber, chloroprene rubber, nitrile rubber, butadiene rubber, butyl rubber, acrylic Nitrile butadiene rubber (NBR), ethylene vinyl acetate copolymer (EVA) resin, styrene-butadiene-styrene (SBS) block copolymer, styrene-isoprene-styrene (SIS) block copolymer, styrene Ethylenebutylene-styrene (S EBS) block Polymers
  • Epoxy resins, oxetane resins, reactive acrylic resins (SGA), silicone resins, urethane resins, polyester resins, cyanoacrylate adhesives are also used as photo-curing adhesives and thermosetting adhesives.
  • I Examples include an aldehyde adhesive, a melamine aldehyde adhesive, and a urea aldehyde adhesive.
  • an epoxy resin it is preferable to use a bisphenol A-type epoxy resin, an alicyclic epoxy resin, or the like as a main agent, and to use a combination of polyamine dimidazole or the like as a curing agent.
  • a reactive acrylic resin it is preferable to use a combination of an acryl monomer and a radical generator as a main component, and to use a combination of an acryl monomer and a reducing agent as a curing accelerator.
  • the type of the water-absorbent crosslinked polymer is not particularly limited as long as it is particles or fibers obtained by reacting the water-absorbent resin with a crosslinking agent. It is preferable to use a starch-based resin, a polyacrylic acid-based resin, a polyvinyl alcohol-based resin, a polyacrylamide-based resin, and a polyoxymethylene-based resin.
  • water-absorbent crosslinked resins include, for example, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, crotonic acid, itaconic acid, iS-hydroxyacrylic acid, It is preferably a crosslinked resin obtained by polymerizing at least one monomer component selected from ⁇ -acryloxypropionic acid and a neutralized product thereof together with a crosslinking agent.
  • unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, crotonic acid, itaconic acid, iS-hydroxyacrylic acid
  • Preferred crosslinking agents include, for example,
  • Diethylene glycol diethylene glycol, glycerin, propylene glycol, 1,4-butanediol, polypropylene glycol, etc.
  • Polyhydric alcohol
  • Polyglycinolone such as ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin triglycidyl ether;
  • Haloepoxy compounds such as epichlorohydrin and monomethylchlorohydrin;
  • the amount of the cross-linking agent used is preferably determined in consideration of the amount of water absorption in the water-absorbent cross-linked polymer.
  • preferred water-absorbent crosslinked polymers include a crosslinked product of a hydrolyzate of a starch-acrylonitrile graft polymer, a crosslinked product of a neutralized product of a starch-acrylic acid graft polymer, and a vinyl acetate-acrylic acid ester copolymer
  • Cross-linked saponified product cross-linked hydrolyzate of acrylonitrile copolymer, cross-linked hydrolyzate of acrylamide copolymer, partially neutralized cross-linked polyacrylic acid, containing carboxyl group
  • Examples include cross-linked polyvinyl alcohol modified products, cross-linked isobutylene-maleic anhydride copolymers, cross-linked polyethylene oxide products, cross-linked urethane modified products, and the like.
  • the water absorption ratio of the water-absorbing resin is preferably set to a value within a range of 5 to 1,000 times.
  • the reason for this is that if the water absorption ratio is less than 5 times, the adhesive strength after water absorption may not be sufficiently reduced, or it may be necessary to add a large amount of water absorbent resin. It is.
  • the water absorption capacity of the water-absorbent resin is more preferably set to a value in the range of 10 to 500 times, and further preferably to a value in the range of 50 to 300 times.
  • the water absorption capacity of the water-absorbent resin can be measured as a volume increase ratio after immersing the water-absorbent resin in excess water for 24 hours.
  • the average particle size of the water-absorbent crosslinked polymer is less than 0.1, it may be difficult to uniformly mix and disperse, or the adhesive force after water absorption may not be sufficiently reduced. Because there is.
  • the average particle diameter of the water-absorbent crosslinked polymer is set to a value in the range of 0.5 to 500 ⁇ m, and to a value in the range of 10 to "! Is more preferable.
  • the average fiber length is preferably in the range of 2 to 6 Omm.
  • the average fiber length of the water-absorbent crosslinked polymer is less than 2 mm, it may be difficult to mix and disperse it uniformly, or the adhesive strength after water absorption may not be sufficiently reduced. Because there is. Meanwhile, such water absorption If the average fiber length of the cross-linked polymer exceeds 6 Omm, it may be difficult to mix and disperse it uniformly in the base resin of the adhesive, or the initial adhesive strength may decrease. That's why.
  • the average fiber length of the water-absorbent crosslinked polymer is more preferably set to a value in the range of 3 to 5 Omm, and further preferably to a value in the range of 5 to 40 mm.
  • the average particle size / average fiber length of the water-absorbent crosslinked polymer can be determined by actually measuring the particle size / fiber length from an electron micrograph and calculating the average value from the measured value.
  • the shape of the water-absorbent crosslinked polymer is not limited to a particle shape or a fibrous shape, and may be a polygon, an irregular shape, or a combination thereof.
  • the amount of the water-absorbing crosslinked polymer to be added is preferably set to a value within the range of 1 to 200 parts by weight based on 100 parts by weight of the base resin of the adhesive.
  • the amount of the water-absorbing cross-linked polymer is in the range of 100 to 100 parts by weight with respect to 100 parts by weight of the base resin of the adhesive. More preferably, the value is in the range of up to 80 parts by weight.c
  • FIG. 1 the horizontal axis shows the amount (parts by weight) of the water-absorbent cross-linked polymer with respect to 100 parts by weight of the adhesive base resin, and the vertical axis shows the adhesive force (MPa). Is shown.
  • Line A changes the amount of the water-absorbing crosslinked polymer added in the surfactant-free formulation of Example 1.
  • Line A shows the adhesion after immersion in warm water (60 ° C) for 6 hours.
  • Line B shows the initial adhesive force measured by changing the amount of the water-absorbent crosslinked polymer in the formulation containing a predetermined amount of the surfactant of Example 1, and line B 'shows hot water (60%). (° C) for 6 hours.
  • the addition amount of the water-absorbent crosslinked polymer hardly affects the initial adhesive strength of both lines A and B
  • the addition amount of the water-absorbent crosslinked polymer for example, When the amount exceeds 25 parts by weight, the adhesive strength after immersion in hot water (60 ° C) for 6 hours is remarkably reduced as compared with the initial adhesive strength. The tendency of the adhesive strength to decrease is more remarkable in the line B ′ containing a surfactant.
  • the addition amount of the water-absorbing cross-linked polymer is set to a value of 10 parts by weight or more, and an adhesive composition containing no surfactant is used.
  • the amount of the water-absorbing cross-linked polymer is set to a value of 30 parts by weight or more, it is possible to sufficiently reduce the adhesive strength after water absorption.
  • the adhesive force change curve shown in FIG. 1 varies not only with the type of the adhesive base resin but also with the type of the water-absorbing cross-linked polymer and tackifier. .
  • the water-absorbent crosslinked polymer when added to the base resin of the adhesive, it is preferable to heat and melt the base resin. For this reason, due to such heat melting, the water-absorbent crosslinked polymer may be thermally decomposed or aggregated, making it difficult to uniformly mix and disperse the water-absorbent crosslinked polymer. Therefore, it is preferable to improve the heat resistance and the mixing and dispersibility in advance by performing a surface treatment on the water-absorbent crosslinked polymer.
  • the surface of the water-absorbent crosslinked polymer is treated with a coupling agent, added with inorganic particles, metal plating, metal deposition, inorganic deposition, or a polymer having a higher glass transition point than the water-absorbent crosslinked polymer. It is preferable to use and coat.
  • a coupling agent added with inorganic particles, metal plating, metal deposition, inorganic deposition, or a polymer having a higher glass transition point than the water-absorbent crosslinked polymer. It is preferable to use and coat.
  • a thixotropy agent in the water-absorbent crosslinked polymer, a thixotropy agent, a viscosity modifier, a plasticizer, a coloring agent, a pigment, a weathering agent, an ultraviolet absorber, a discoloration inhibitor, an oxidation agent may be contained within a range not departing from the object of the present invention. It is also preferable to add one kind or a combination of two or more kinds of inhibitors, inorganic particles, carbon particles, carbon fibers, conductive particles, extenders, fungicides, antibacterial agents, and bactericides.
  • the tackifier is added to improve the initial adhesive strength and to effectively reduce the adhesive strength when absorbing water. Further, by adding a tackifier, a function as a dispersant can be exhibited when the water-absorbing crosslinked polymer is added to the base resin of the adhesive.
  • aliphatic petroleum resins aromatic petroleum resins, and aliphatic and aromatic Polymerized petroleum resin, alicyclic hydrogenated petroleum resin, alkyl phenol resin, xylene resin, coumarone indene resin, terpene resin, terpene; c-nor resin, aromatic modified terpene resin, hydrogenated terpene resin, rosin resin,
  • One type of hydrogenated rosin-based resin, disproportionated rosin-based resin, dimerized rosin-based resin, esterified rosin-based resin and the like may be used alone or in combination of two or more.
  • tackifiers it is particularly preferable to use an aliphatic petroleum resin or an aromatic petroleum resin.
  • an aliphatic petroleum resin or an aromatic petroleum resin it is particularly preferable to use an aliphatic petroleum resin or an aromatic petroleum resin. The reason for this is that by using such a tackifier, the addition of a small amount can effectively improve the adhesive force when absorbing water. This is because such a tackifier is economical and economical.
  • the amount of the tackifier to be added is preferably in the range of 1 to 800 parts by weight per 100 parts by weight of the base resin of the adhesive.
  • the reason for this is that if the amount of the tackifier is less than 1 part by weight, the adhesive strength after water absorption may not be sufficiently reduced, or the initial adhesive strength may be reduced. On the other hand, if the added amount of the tackifier exceeds 800 parts by weight, it becomes difficult to uniformly mix and disperse the adhesive in the base resin, or the creep resistance of the obtained adhesive becomes poor. This is because it may decrease.
  • the amount of the tackifier is more preferably in the range of 5 to 500 parts by weight, and even more preferably in the range of 30 to 300 parts by weight.
  • Surfactants are preferably used when rapidly absorbing water to reduce the adhesive strength, but the type thereof is not particularly limited. Anionic surfactants, cationic surfactants, and nonionic surfactants are used. Any of a surfactant and a polymer surfactant may be used.
  • fatty acids fatty acid esters, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, sorbitol fatty acid esters, sorbitan fatty acid ester ethers, sorbitol fatty acid ester ethers, glycerin fatty acid esters, sucrose fatty acid esters, etc. Combinations of more than one species are included.
  • the use of relay, sucrose distearate, sucrose monodistearate, etc. can significantly reduce the adhesive strength after water absorption with a small amount of addition, while effectively reducing the initial adhesive strength. It is preferable because it can be prevented.
  • the amount of the surfactant added is preferably set to a value within the range of 0.001 to 20 parts by weight based on 100 parts by weight of the base resin.
  • the reason for this is that if the amount of the surfactant is less than 0.001 parts by weight, the effect of addition is not exhibited, and when the adhesive composition absorbs water, the adhesive force is rapidly reduced. This is because it may not decrease. On the other hand, if the amount of the surfactant exceeds 20 parts by weight, it may be difficult to uniformly mix and disperse the surfactant, or the initial adhesive strength may decrease.
  • the amount of the surfactant added is more preferably set to a value within the range of 0.5 to 10 parts by weight, and even more preferably set to a value within the range of 1 to 5 parts by weight.
  • water-soluble filler examples include inorganic salts, chelates, polysaccharides, urine resins, sodium bicarbonate, etc., alone or in combination of two or more.
  • the amount of the water-soluble filler should be within a range of 5 to 50 parts by weight per 100 parts by weight of the base resin of the adhesive. Is preferred.
  • At least one force coupling agent selected from the group consisting of a silane coupling agent, an aluminum force coupling agent, and a titanium coupling agent is added to the base resin of the adhesive.
  • a coupling agent selected from the group consisting of a silane coupling agent, an aluminum force coupling agent, and a titanium coupling agent
  • Such coupling agents include r-aminopropyltriethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, r-mercaptopropyltriethoxysilane, r-aminopropyltriethoxyaluminum, and r-aminopropyltriethoxysilane.
  • Aminopropyltrimethoxytitanium and the like can be mentioned.
  • the amount of the coupling agent is preferably set to a value within the range of 0.1 to 20 parts by weight per 100 parts by weight of the base resin of the adhesive.
  • the value is more preferably in the range of 5 to 10 parts by weight, and even more preferably in the range of 1 to 5 parts by weight.
  • Such organic solvents include methyl ethyl ketone, methyl isobutyl ketone, toluene, ethyl ether, ethyl acetate, tetrahydrofuran,
  • N.N-Dimethylformamide, methanol, 1-butanol, etc. may be used alone or in combination of two or more.
  • the same additives as the additives to the water-absorbing cross-linked polymer for example, thixotropic agents, viscosity modifiers, plasticizers, coloring agents, pigments, weathering agents, discoloration inhibitors, curing It is also preferable to add one kind or a combination of two or more kinds of agents, antioxidants, inorganic particles, carbon particles, carbon fibers, conductive particles and the like within a range not departing from the object of the present invention.
  • the method for producing the water-peelable adhesive composition is not particularly limited, For example, it is preferable to include the following steps.
  • (B) A water-absorbent crosslinked polymer having an average particle diameter of 1 to 800 ⁇ m and a water-absorbent crosslinked polymer having an average fiber length of 2 to 6 Omm, based on 100 parts by weight of the base resin of the adhesive. Or one of the two water-absorbent crosslinked polymers is added in an amount of 1 to 200 parts by weight.
  • a thermoplastic resin such as a SISS block copolymer or a SBS block copolymer because of easy handling.
  • a molten adhesive can be used by using a latent curing adhesive or by using a two-pack adhesive consisting of a main agent and a curing agent.
  • a thermosetting epoxy adhesive composed of a bisphenol A resin and an amine-based curing agent
  • only the bisphenol A resin is heated and melted.
  • the amine-based curing agent is preferably added at the time of use after the dry blending step or the dry blending step.
  • the mixing ratio of the water-absorbing crosslinked polymer is preferably set to a value within the range of 1 to 200 parts by weight, based on 100 parts by weight of the base resin of the adhesive in a molten state, and 100 to 1 part by weight.
  • the value is more preferably in the range of 100 parts by weight, and even more preferably in the range of 20 to 80 parts by weight.
  • the amount of the water-absorbent crosslinked polymer exceeds 200 parts by weight, it may be difficult to uniformly mix and disperse the polymer.
  • the temperature at which the water-absorbent crosslinked polymer or the like is mixed into the base resin of the adhesive may be set to a value within a range of 100 to 250 ° C. preferable. The reason for this is that if the mixing temperature is lower than 100 ° C., it may be difficult to uniformly mix and disperse the water-absorbent crosslinked polymer. If the temperature exceeds ° C, the water-absorbent crosslinked polymer may be thermally decomposed or aggregated.
  • the mixing temperature of the water-absorbent crosslinked polymer is more preferably set to a value in the range of 120 to 200 ° C, and more preferably to a value in the range of 150 to 180 ° C. Is more preferred.
  • the mixer for mixing the water-absorbent crosslinked polymer and the like into the base resin of the adhesive is not particularly limited.
  • the water-absorbent crosslinked polymer When mixing the water-absorbent crosslinked polymer into the base resin of the adhesive, it is preferable to dry blend without using an aqueous solvent so that the water-absorbent crosslinked polymer does not swell. However, it is also preferable to use an organic solvent as long as the water-absorbent crosslinked polymer does not excessively swell.
  • a well-known adhesive application means for example, a roll coater, a bar coater, a brush coating It is preferable to apply the adhesive composition by a spatula or a spatula.
  • the water-peelable adhesive composition is a solution-based adhesive or a one-part adhesive
  • a dispenser in the case of a hot-melt adhesive, an applicator is used. Is preferred.
  • the adhesive strength of the water-peelable adhesive composition is not prevented from decreasing, but the adhesive strength is not decreased by moisture in the air or the like. Since it is possible to further improve the initial adhesive strength, it is preferable to apply a silane coupling agent to the coated surface of the adhesive with a primer.
  • the form of the water-peelable adhesive composition of the present invention is not particularly limited, and examples thereof include hot melt adhesives, film adhesives, solvent adhesives, and spray adhesives. And other various forms.
  • the water-peelable adhesive composition of the present invention is laminated on a substrate, and is formed into a form such as an adhesive tape, a masking tape (coating tape), a marking film, a temporary fixing tape, a plating tape, and a process tape. It is also preferable that In this case, it is preferable that a polyester film, a vinyl chloride film, a polypropylene film, a fluororesin film, or the like is used as a base material, and an adhesive layer having a thickness of 100 to 500 im is formed thereon. .
  • the peeling conditions for peeling the water-peelable adhesive composition are not particularly limited as long as the water-absorbing adhesive composition reduces the adhesive strength by absorbing water. Soak in water at 10 ° C (including hot water under pressurized conditions; the same applies hereinafter) for 10 minutes to 24 hours, or add water at 10 ° C to 150 ° C for 1 minute. It is preferable to shower from 0 minutes to 24 hours. The reason for this is that under such a water absorbing condition, such as a simple condition, water, hot water or hot water can be used as it is, and if such a water absorbing time or a showering time is used, the adherend can be effectively used. Can be decomposed.
  • alcohol or a surfactant (including a dispersant and a detergent) is added to water 10. It is also preferable to add 0.1 to 20 parts by weight of water per 0 parts by weight.
  • a fluorine-based / silicone-based inert liquid instead of the above-mentioned water, hot water or hot water, and in addition to the above-mentioned water, hot water or hot water.
  • an adhesive having the composition shown in Example 3 was prepared, and was set to each condition of 25 ° C ⁇ 80% RH, water (25 ° C), 60 ° C hot water, and 90 ° C hot water. It shows a change in adhesive strength when left for a long time.
  • Fig. 2 when water is not absorbed basically (25 ° C x 80% RH), the adhesive force is hardly changed, but the more it is immersed in high-temperature hot water or hot water. The decline is significant. Therefore, it is possible to set a desired stripping time by adjusting the temperature of the water.
  • the surrounding pressure is set to a value in the range of 0 to 1 MPa (about 1 to 10 atm), It is more preferable that the value be in the range of 0 to 0.5 MPa (about 1 to 5 atm), and it is preferable that the value be in the range of 0.1 to 0.3 MPa (about 1 to 3 atm). More preferred.
  • the second embodiment of the present invention is a release adhesive composition containing the following components (A) to (E) (hereinafter sometimes referred to as a combined heat release adhesive composition). It is characterized by adding (B) a water-absorbent crosslinked polymer and (E) thermally expandable particles to (A) a base resin of an adhesive. Therefore, the components (A), (B) and (E) are essential components, and the components (C) and (D) are optional components in the hot-release adhesive composition of the second embodiment. is there. The contents of the components (A) to (D) are the same as in the first embodiment. The description can be omitted here.
  • the heat-expandable particles can be suitably used as long as the particles increase in volume upon heating.
  • the outer shell is a vinylidene chloride-acrylonitrile copolymer resin or vinyl acetate. It is composed of one type or a combination of two or more types of luacrylonitrile copolymer resin, methyl methacrylate-acrylonitrile copolymer resin, acrylonitrile resin, phenolic resin, epoxy resin, etc. It is preferable that the inside contains a heat-foamable gas or liquid.
  • the average particle size of the thermally expandable particles be a value within a range of 1 to 300 m.
  • the reason for this is that if the average particle size of the thermally expandable particles is less than 1 jwm, the releasability of the adhesive may decrease.
  • the average particle size of the thermally expandable particles exceeds 300 jum, it may be difficult to uniformly mix the adhesive into the base resin. Therefore, the average particle diameter of the thermally expandable particles is more preferably set to a value within a range of 3 to 200 Um, and even more preferably to a value within a range of 5 to 150 jUm. Better.
  • the average particle size of the hollow microspheres can be easily calculated from an optical micrograph using an image processing device.
  • the amount of the heat-expandable particles is in the range of 1 to 300 parts by weight based on 100 parts by weight of the base resin of the adhesive.
  • the reason for this is that if the amount of such thermally expandable particles is less than 1 part by weight, the effect of adding This is because the peelability of the adhesive may decrease.
  • the amount of the heat-expandable particles exceeds 300 parts by weight, the adhesive strength before peeling is reduced, or it is difficult to uniformly mix the adhesive into the base resin. This is because it may be.
  • the amount of the heat-expandable particles is more preferably set to a value within the range of 10 to 150 parts by weight, based on 100 parts by weight of the base resin of the adhesive, and 30 to 1 part by weight. More preferably, the value is in the range of 100 parts by weight.
  • the amount of the heat-expandable particles to be added in consideration of the peeling conditions described later. For example, in order to prevent self-exfoliation only by heat treatment at 105 ° C or more, the amount of the heat-expandable particles should be adjusted based on 100 parts by weight of the adhesive base resin. It is preferred that the value be in the range of 1 to 40 parts by weight. Also, in order to adjust so as not to be self-peeled only by a heat treatment at 120 ° C. or more, the amount of the heat-expandable particles should be 1 to 3 with respect to 100 parts by weight of the base resin of the adhesive. The value is preferably within the range of 0 parts by weight.
  • the amount of the heat-expandable particles must be added to the base resin of the adhesive. It is preferable that the value be in the range of 45 to 100 parts by weight with respect to 100 parts by weight of the fat. Further, in order to be able to self-peel at a temperature of 105 ° C. or more and a heat treatment time of 15 minutes or less, the amount of the heat-expandable particles must be adjusted by adding 100 parts by weight of the base resin of the adhesive. On the other hand, the value is preferably in the range of more than 100 parts by weight to 300 parts by weight.
  • the abscissa indicates the amount (parts by weight) of the heat-expandable particles added to 100 parts by weight of the base resin of the adhesive, and the ordinate indicates the adhesive force (MPa).
  • the left axis shows the self-peeling time (immersion in hot water at 90 ° C) measured by changing the amount of the thermally expandable particles in the adhesive composition of Example 14; Shows the initial adhesive strength.
  • the amount of the thermally expandable particles hardly affects the initial adhesive strength, but when the amount of the thermally expandable particles exceeds, for example, 20 parts by weight.
  • the self-peeling time is significantly shorter.
  • the self-peeling time (immersion in hot water at 90 ° C) can be shortened to within 10 hours by setting the amount of the thermally expandable particles to a value of 25 parts by weight or more. It is possible to It is known that the change curve of the self-peeling time shown in FIG. 3 changes depending on not only the type of the base resin of the adhesive but also the type of the water-absorbing crosslinked polymer.
  • the coating method and the form of the peelable adhesive composition combined with heat of the second embodiment can be the same as those of the first embodiment, and within a predetermined range, for example, as shown in FIG. As shown, it is also possible to change the form of the combined heat and release adhesive composition.
  • FIG. 4 (a) shows that the heat-releasing adhesive composition contains a film-forming resin and the thickness of the heat-releasing adhesive composition is, for example, in the range of 10 to 200 m. It is an example in which the value is set to the value within the range.
  • FIG. 4 (b) shows that one side (B side in the figure) of the film-form and heat-peelable adhesive composition (sometimes referred to as a first adhesive layer) has organic thermally expandable particles on one side.
  • an adhesive layer comprising a thermosetting adhesive component containing no organic heat-expandable particles and a water-absorbent cross-linked polymer in a smaller amount than the first adhesive layer. This may be referred to as a second adhesive layer.).
  • FIG. 4 (c) shows whether the organic heat-expandable particles and the water-absorbent cross-linked polymer are not contained between the two heat-peelable adhesive compositions (first adhesive layer), or An adhesive layer composed of a thermosetting adhesive component containing a smaller amount of organic heat-expandable particles and a water-absorbing bridging polymer than the first adhesive layer (may be referred to as a third adhesive layer). This is an example in which is provided.
  • the peeling conditions can be the same as those in the first embodiment.
  • the use of hot water with additional heating conditions makes it possible to more quickly exfoliate using the expansion of the thermally expandable particles. Therefore, for example, when 1 to 40 parts by weight of the heat-expandable particles are added to 100 parts by weight of the base resin of the adhesive, self-peeling when simply heated at a temperature of 105 ° C or more is prevented.
  • self-peeling can be performed within an immersion time of 12 hours or less.
  • the method for producing the heat-release adhesive composition is not particularly limited, but preferably includes, for example, the following steps.
  • thermosetting resin as base resin for adhesive
  • thermosetting resin for example, an epoxy resin is prepared, but it is preferable to sufficiently deaerate the adhesive so that the adhesive strength does not vary.
  • a reactive diluent or a solvent In order to adjust the viscosity of the thermosetting resin, it is preferable to add a reactive diluent or a solvent.
  • the viscosity of the thermosetting resin for example, 1 00 ⁇ 1 00, 00 Om P a ⁇ s is preferably set to a value within the range of (measurement temperature 25 ° C) (Further, the thermosetting resin
  • thermosetting resin As a base resin of the adhesive. And when using thermosetting resin. Due to the relatively low viscosity, it is not necessary to dry blend the water-absorbing cross-linked polymer with the adhesive resin heated to a molten state. It is also preferable to do so.
  • the environmental temperature at the time of addition it is preferable to set the environmental temperature at the time of addition to be equal to or lower than the foaming temperature so that the thermally expandable particles do not foam on the way, and to be 10 ° C. or higher than the foaming temperature. More preferably, the temperature is low.
  • SIS block copolymer as a base resin and 0.2 parts by weight of a phenolic antioxidant were contained, and a planetary mixer was used. The mixture was stirred for 3 hours to uniformly dissolve. Next, 30 parts by weight of a C5-based hydrogenated petroleum resin and a KI gel 201 K-F2 (Kuraray) comprising a crosslinked isobutylene-monomaleic anhydride copolymer were used.
  • Example 1 35 parts by weight, average particle size 15 m, water absorption magnification 200 times), 7 parts by weight of polyethylene glycol monostearyl ether (HLB: 15.7) as a surfactant, plasticizer as a plasticizer Liquid paraffin (flash point: 256 ° C., density: 0.865 g Z cm 3 ) was contained in a melting pot at a ratio of 5 parts by weight. Further, the mixture was stirred for 1 hour using a planetary mixer, and it was confirmed that each component was uniformly melted and mixed. Thus, a water-peelable adhesive composition of Example 1 was obtained.
  • Table 1 the SIS block copolymer used in Example 1 was used.
  • the body is represented by A1
  • the water-absorbent crosslinked polymer is represented by B1
  • the tackifier C5 hydrogenated petroleum resin, softening point: 100 ° C, average molecular weight: 650
  • the activator is denoted by D1.
  • Example 2 As shown in Table 1, in Example 2, the effect of reducing the amount of the surfactant used in Example 1 was examined, and in Example 3, a water-absorbent crosslinked polymer and adhesive which were different from Example 1 were used. The amount of the tackifier and the surfactant used was examined.In Example 4, the effect of changing the type of the surfactant in Example 3 was examined.In Example 5, the tackifier and the surfactant in Example 1 were used. The effects of not using an activator were examined separately. As can be understood from the results in Table 1, in Example 2, since the amount of the surfactant used was lower than that in Example 1, the initial adhesive strength increased, but the adhesive strength after water absorption tended to decrease. Has decreased.
  • Example 3 while the amount of the water-absorbent crosslinked polymer used in Example 1 was increased, the initial adhesive force was further increased because the amount of the tackifier and the surfactant was smaller than the amount used. At the same time, the tendency of the adhesive strength to decrease after water absorption became larger.
  • Example 4 it is considered that the type of the surfactant in Example 3 was changed, but the initial adhesive strength was slightly lower than that in Example 3, but the adhesive strength after water absorption was higher. The tendency of the decline in the number has increased. Also, in Example 5, it seems that the surfactant in Example 1 was not used, but the initial adhesive strength was slightly increased compared to Example 1, but the adhesive strength after water absorption decreased. It has become small.
  • Comparative Example 1 As shown in Table 1, in Comparative Example 1, the change in adhesion after water absorption was examined without using the tackifier and surfactant in Example 1 and without adding a water-absorbing crosslinked polymer or the like. As can be understood from the results in Table 1, in Comparative Example 1, there was no significant difference between the initial adhesive strength and the adhesive strength after water absorption because no water-absorbing crosslinked polymer was added. I could't see it.
  • B 1 crosslinked isobutylene maleic anhydride copolymer
  • Example 6 50 parts by weight of C5 hydrogenated petroleum resin, K201-F2 as a water-absorbing cross-linked polymer (average particle diameter 30 ⁇ m, water absorption magnification 200 times, in Table 2 , B2)) in a melting pot with 21 parts by weight of liquid paraffin (flash point: 256 ° density: 0.865 cm 3 ) as a plasticizer at a ratio of 5 parts by weight. Housed. Further, the mixture was stirred for 1 hour using a planetary mixer, and it was confirmed that each component was uniformly melted and mixed. Thus, a water-peelable adhesive composition of Example 6 was obtained.
  • Adhesive strength after water absorption 1 and Adhesive strength after water absorption 2 were measured and evaluated. As a result, it is considered that the tackifier was added in a relatively large amount. After immersion in water for 6 hours, no remarkable decrease in the adhesive strength was observed, but the temperature was not reduced by warm water (60 ° C). It was confirmed that the adhesive strength was reduced to about 1 Z3 of the initial adhesive strength when using.
  • Example 7 no significant decrease in adhesive strength was observed after immersion in water for 6 hours, but almost no adhesive strength was exhibited when hot water (60 ° C) was used. Confirmed that it will not be. Also in Example 8, no significant decrease in adhesive strength was observed after immersion in water for 6 hours, but almost no adhesive strength was exhibited when warm water (60 ° C) was used. Make sure it ’s gone Was. Also, in Example 9, although no remarkable decrease in adhesive strength was observed after immersion in water for 6 hours, when hot water (60 ° C.) was used, the adhesive strength was almost zero. It was confirmed that expression did not occur.
  • Example 9 although it seems that the water-absorbent crosslinked polymer having a large average particle size was used, the initial adhesive strength tended to be low. Also, in Examples 10 and 11, although no remarkable decrease in the adhesive strength was observed after immersion in water for 6 hours, hot water was used.
  • Comparative Example 3 an adhesive composition was prepared and evaluated in the same manner as in Example 6, except that the water-absorbent crosslinked polymer in Example 6 was not added. As a result, in Comparative Example 3, since no water-absorbent crosslinked polymer was added, no decrease in adhesive strength was observed even after immersion in water and warm water for 6 hours.
  • B 2 Crosslinked isobutylene maleic anhydride copolymer, average particle size 30 jUm
  • B 3 Crosslinked isobutylene maleic anhydride copolymer, average particle size 150 ⁇ m
  • B 4 Crosslinked isobutylene maleic anhydride copolymer, average particle size 1400 m
  • B 5 polyacrylate polymer, average particle size 30 im
  • B 6 polyacrylate polymer, average particle size 150 ju m
  • the water-peelable adhesive composition obtained in Example 1 was applied from a hot melt applicator under the conditions of 180 ° C and 0.98 MPa (1 O kgf / cm2). Then, a screen mesh for screen printing (made of polyamide, 30 cm x 30 cm) and a metal frame (made of aluminum) were bonded and fixed. In this state, no screen mesh was peeled off from the metal frame where screen printing was performed 50,000 times. Next, when the screen mesh was immersed in warm water at 60 ° C for 10 minutes, it was confirmed that the screen mesh was naturally separated from the metal frame. Therefore, according to the present embodiment, since no organic solvent is used, there is no effect on the human body and there is no flammability problem.
  • the screen mesh peeling operation after screen printing can be performed easily and in a short time. Now you can do it. If a conventional hot melt adhesive is used, it must be immersed in methyl ethyl ketone at 60 ° C for at least one hour, and then scraped off using a metal spatula, which damages the metal frame. Many cases were seen.
  • the water-peelable adhesive composition obtained in Example 1 was applied from a hot melt applicator at 180 ° C. and 0.98 MPa (1 O kgf / cm 2). Then, the heat insulating material (hard urethane rubber) used for the refrigerator and the metal housing (made of painted aluminum) were bonded and fixed. In this state, the refrigerator was assembled, and a continuous test was performed for 500,000 hours at an ambient temperature of 60 ° C. However, no detachment of the heat insulating material from the metal casing was observed. Next, the refrigerator was disassembled, and the components consisting of the heat insulating material and the metal casing were taken out. After hot water at 95 ° C was showered at the junction for 10 minutes, the metal casing was removed.
  • the heat insulating material hard urethane rubber
  • the heat insulation material was separated from nature. Therefore, according to the present embodiment, the heat insulating material can be easily and quickly peeled off from the metal housing. ⁇ Also, since the metal housing has no risk of being damaged, it can be reused as it is. Now you can. When a conventional adhesive was used, it was necessary to use a metal spatula to peel off the heat insulating material from the metal housing, and the metal housing was often damaged.
  • the type of adhesive base resin was studied. That is, in a container, 100 £ of Epikoto 828 (manufactured by Japan Epoxy Resin Co., Ltd.), 75 g of 1 gel 201 K-F2 (manufactured by Kuraray Co., Ltd.), and 75 g of thermally expandable particles After adding 25 g of Matsumoto Microsphere F-30D (manufactured by Matsumoto Yushi Seiyaku Co., Ltd.), the mixture was stirred for 1 hour using a mixer to uniformly mix the components. Next, after adding 5 Og of epomate B002 (manufactured by Japan Epoxy Resin Co., Ltd.) as a curing agent, the mixture was further stirred for 5 minutes to obtain a peelable adhesive composition combined with heat.
  • Epikoto 828 manufactured by Japan Epoxy Resin Co., Ltd.
  • 1 gel 201 K-F2 manufactured by Kuraray Co., Ltd.
  • thermally expandable particles After adding 25 g of Matsumoto Microsphere
  • Example 2 As in Example 1, after the measurement sample was prepared, the initial adhesive force was measured, and the measurement sample was placed in hot water (90 ° C) and a heating oven (105 ° C, 120 ° C). Was placed, and the self-peeling time was measured. As a result, as shown in Table 3, an extremely high initial adhesive strength of 7.5 MPa was obtained. -On the other hand, it was difficult to self-peel within 12 hours by heat treatment, but it was possible to self-peel in about 7 to 9 hours when using hot water It was confirmed.
  • the effect of the amount of thermally expandable particles added on the initial adhesive strength, self-peeling time in hot water and a heating oven, the effect of the type of water-absorbent resin, and the thermosetting resin (reactive acrylic) The effects of the type of resin) and the effects of adding surfactants and coupling agents were studied.
  • the X mark means that self-peeling does not occur even after being left for 12 hours under the condition of water absorption Z heating.
  • the added amount of the heat-expandable particles is 40 parts by weight or less, the initial adhesive strength is high. It was confirmed that a heat-releasing adhesive composition was obtained.
  • the base resin of the adhesive contains the water-absorbing crosslinked polymer in a predetermined amount, and
  • the initial adhesive strength is as strong as before, but when immersed in water, warm water or even hot water, the water-absorbent crosslinked polymer absorbs water and swells, It has become possible to easily separate an adherend, for example, glass and an accessory.
  • thermosetting adhesive a high initial adhesive strength is obtained by including the water-absorbent crosslinked polymer and the heat-expandable particles in the thermosetting adhesive in a predetermined amount range, respectively.
  • self-exfoliation does not occur by heat treatment at about 120 ° C, and only when hot water is used, the water-absorbing cross-linked polymer absorbs water and the thermal expansion of the heat-expandable particles. As a result, self-peeling became possible within 12 hours.
  • a cosmetic container a medicine container, an aromatic container, a beverage container, a seasoning container, an article storage container, a gas storage container, a liquid crystal storage container (including an LCD panel) ), And circuit board storage container (including the housing for electrical components). It is expected to be used for joining composite containers where collection of each component is particularly desired.
  • an adhesive for screen fixing for screen printing an adhesive for temporary fixing when transporting semiconductor components
  • a masking tape Adhesives bolts (screw) adhesives to prevent loosening
  • wallpaper adhesives decorative films (marking film) adhesives
  • glass fixing adhesives magnet fixing adhesives
  • metal fixing adhesives tiles
  • the type of the base resin is considered. It can also be used as a molding resin by taking into account or adding inorganic particles.For example, it can be suitably used as a resin for semiconductor encapsulation, an electrically insulating resin, a resin for forming a circuit board, and the like. Be expected.
  • the base resin of the adhesive contains the water-absorbing crosslinked polymer and further the heat-expandable particles in a predetermined amount range, so that the water-absorbing property is improved.
  • the cross-linkable polymer and the heat-expandable particles can be uniformly mixed and dispersed, and a peelable adhesive composition having a reduced adhesive strength after water absorption can be obtained effectively.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention concerne des compositions adhésives enlevables dont la force adhésive décroît lors d'absorption d'eau (une composition adhésive enlevable à l'aide d'eau et une composition adhésive enlevable à l'aide d'eau et de chaleur). Les compositions adhésives enlevables comprennent 100 parties en poids d'une résine adhésive de base, telle qu'une résine thermofusible ou une résine thermodurcissable, 1 à 200 parties en poids d'un polymère réticulé hydrophile, 1 à 300 parties en poids de particules expansibles à la chaleur, et 0,001 à 20 parties en poids d'un tensioactif.
PCT/JP2001/008511 2001-01-10 2001-09-28 Compositions adhesives enlevables et procede de preparation correspondant WO2002055626A1 (fr)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005085383A1 (fr) * 2004-03-03 2005-09-15 Nippon Kayaku Kabushiki Kaisha Adhésif à base d’eau pour éléments de polarisation et polarisateur obtenu a l’aide dudit adhesif
KR100886680B1 (ko) * 2006-03-02 2009-03-04 주식회사 엘지화학 아크릴계 점착제 조성물 및 이를 포함하는 점착제 물품
CN102120918A (zh) * 2010-01-09 2011-07-13 爱克工业株式会社 粘着剂组成物
CN102844395A (zh) * 2010-03-05 2012-12-26 3M创新有限公司 粘合剂组合物
JP2014091774A (ja) * 2012-11-02 2014-05-19 Denki Kagaku Kogyo Kk （メタ）アクリル系樹脂組成物及び接着・解体方法
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6044569A (ja) * 1983-08-22 1985-03-09 Dainichi Seika Kogyo Kk 接着剤組成物
EP0252739A2 (fr) * 1986-07-09 1988-01-13 LINTEC Corporation Feuilles adhésives pour fixer des plaquettes
JPS63298274A (ja) * 1987-05-29 1988-12-06 株式会社日本触媒 水剥離性粘着ラベル及び粘着テ−プ
JPH0792914A (ja) * 1993-09-21 1995-04-07 Toppan Printing Co Ltd 感熱性粘着ラベル
JPH07173445A (ja) * 1993-10-29 1995-07-11 Nitto Denko Corp 水膨潤性の感圧接着剤組成物
JPH07242860A (ja) * 1994-03-03 1995-09-19 Nitto Denko Corp 半導体ウエハの保護部材

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6044569A (ja) * 1983-08-22 1985-03-09 Dainichi Seika Kogyo Kk 接着剤組成物
EP0252739A2 (fr) * 1986-07-09 1988-01-13 LINTEC Corporation Feuilles adhésives pour fixer des plaquettes
JPS63298274A (ja) * 1987-05-29 1988-12-06 株式会社日本触媒 水剥離性粘着ラベル及び粘着テ−プ
JPH0792914A (ja) * 1993-09-21 1995-04-07 Toppan Printing Co Ltd 感熱性粘着ラベル
JPH07173445A (ja) * 1993-10-29 1995-07-11 Nitto Denko Corp 水膨潤性の感圧接着剤組成物
JPH07242860A (ja) * 1994-03-03 1995-09-19 Nitto Denko Corp 半導体ウエハの保護部材

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005085383A1 (fr) * 2004-03-03 2005-09-15 Nippon Kayaku Kabushiki Kaisha Adhésif à base d’eau pour éléments de polarisation et polarisateur obtenu a l’aide dudit adhesif
US7740949B2 (en) 2004-03-03 2010-06-22 Nippon Kayaku Kabushiki Kaisha Water-based adhesive for polarizing element and polarizer obtained with the same
KR100886680B1 (ko) * 2006-03-02 2009-03-04 주식회사 엘지화학 아크릴계 점착제 조성물 및 이를 포함하는 점착제 물품
CN102120918A (zh) * 2010-01-09 2011-07-13 爱克工业株式会社 粘着剂组成物
CN102844395A (zh) * 2010-03-05 2012-12-26 3M创新有限公司 粘合剂组合物
US9333723B2 (en) 2010-03-05 2016-05-10 3M Innovative Properties Company Adhesive composition
JP2014091774A (ja) * 2012-11-02 2014-05-19 Denki Kagaku Kogyo Kk （メタ）アクリル系樹脂組成物及び接着・解体方法
CN114479680A (zh) * 2022-02-10 2022-05-13 珠海华萃科技有限公司 一种软膜显示屏用上墙混合膜及其使用方法
CN114479680B (zh) * 2022-02-10 2024-03-29 珠海华萃科技有限公司 一种软膜显示屏用上墙混合膜及其使用方法
CN116987315A (zh) * 2023-07-04 2023-11-03 中国海洋大学 多孔碳纤维复合材料及其制备方法和应用

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