WO2008010453A1 - Composition de résine, adhésif pour la protection temporaire d'une surface, film adhésif et procédé servant à produire un film adhésif - Google Patents

Composition de résine, adhésif pour la protection temporaire d'une surface, film adhésif et procédé servant à produire un film adhésif Download PDF

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Publication number
WO2008010453A1
WO2008010453A1 PCT/JP2007/063958 JP2007063958W WO2008010453A1 WO 2008010453 A1 WO2008010453 A1 WO 2008010453A1 JP 2007063958 W JP2007063958 W JP 2007063958W WO 2008010453 A1 WO2008010453 A1 WO 2008010453A1
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WIPO (PCT)
Prior art keywords
acrylic resin
sensitive adhesive
pressure
ethylenically unsaturated
temporary surface
Prior art date
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PCT/JP2007/063958
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English (en)
Japanese (ja)
Inventor
Akira Yamabayashi
Toshifumi Akui
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The Nippon Synthetic Chemical Industry Co., Ltd.
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Application filed by The Nippon Synthetic Chemical Industry Co., Ltd. filed Critical The Nippon Synthetic Chemical Industry Co., Ltd.
Publication of WO2008010453A1 publication Critical patent/WO2008010453A1/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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/08—Homopolymers or copolymers of acrylic acid esters
    • 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
    • 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
    • C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation

Definitions

  • Resin composition Resin composition, temporary surface protecting adhesive, adhesive sheet, and method for producing adhesive sheet
  • the present invention relates to a pressure-sensitive adhesive for a temporary surface protective film, which is suitable for protecting plastic products, metal products, etc., and has an excellent adhesive force and peelability.
  • Adhesive for temporary surface protecting adhesive sheet used for building materials, packaging materials, electronics, metal plates, glass plates, synthetic resin plates, laminated steel plates, etc., and further, a method for producing the adhesive sheet and the adhesive sheet It is about.
  • Adhesive films for temporary surface protection are particularly applied to the surface of adherends such as metal plates such as stainless steel plates, aluminum plates and color steel plates, optical members such as glass plates and polarizing films, and resin plates such as plastic plates. Attached and used for the purpose of preventing the surface of the adherend from being contaminated or scratched during transportation, storage, processing, etc.
  • acrylic adhesives are often used as adhesives for temporary surface protective films for protecting plastic plates, metal products, and the like in terms of weather resistance and transparency.
  • An acrylic pressure-sensitive adhesive includes a pressure-sensitive adhesive composition obtained by copolymerizing a (meth) acrylic acid alkyl ester monomer and a monomer containing a functional group such as a carboxyl group, a hydroxyl group, or an epoxy group. Cross-linked with a cross-linking agent such as isocyanate compound, melamine resin, epoxy resin, metal chelate compound or the like is used.
  • a cross-linking agent such as isocyanate compound, melamine resin, epoxy resin, metal chelate compound or the like is used.
  • it is common to increase the cohesion by using a large amount of a cross-linking agent in order to improve re-peelability and to eliminate contamination on the adherend surface after peeling.
  • Patent Document 1 a monomer mixture containing up to 40% by weight of a functional group-containing monomer that can be copolymerized during solution polymerization is polymerized to a polymerization rate of 20% by weight or more, and further copolymerizable A method for producing a pressure-sensitive adhesive composition in which a base monomer is divided into two or more times and polymerized has been proposed.
  • Patent Document 2 contains a alicyclic structure containing an alicyclic structure in the molecule, and has a specific gel fraction and elastic modulus. Peeling adhesive, Patent Document 3, proposes an acrylic polymer re-peeling adhesive having a specific gel fraction by copolymerizing N, N-disubstituted (meth) acrylamide.
  • Patent Document 1 Japanese Patent Laid-Open No. 5-132657
  • Patent Document 2 JP-A-8-143842
  • Patent Document 3 Japanese Patent Laid-Open No. 8-143843
  • a resin composition for forming a shortened temporary adhesive for surface protection and the same The purpose is to provide an adhesive for temporary surface protection, an adhesive sheet, and a production method thereof.
  • an acrylic resin (A) that does not contain an ethylenically unsaturated group or an acrylic resin that does not contain an ethylenically unsaturated group Surprisingly, by irradiating an active energy ray to an acrylic resin composition [I] mainly containing resin (A), which is unlikely to be polymerized, it has an appropriate peel strength. In addition, there is little change in the peel force over time, and there is no contamination of the adherend after peeling, and the curing period is much shorter than conventional acrylic pressure-sensitive adhesives that are crosslinked with a crosslinking agent. And found that a temporary surface-protecting pressure-sensitive adhesive was obtained.
  • a resin composition that does not contain a polymerizable monomer or polymerizable oligomer and contains a resin component and a photopolymerization initiator, and the resin component does not substantially contain an ethylenically unsaturated group.
  • Acrylic rosin An acrylic rosin composition mainly containing (A) and an active energy An adhesive for temporary surface protection obtained by irradiating a line.
  • Acrylic resin that does not contain ethylenically unsaturated groups (A) Strength (meth) Acrylic acid alkyl ester (al) 20-: It is an acrylic resin obtained by polymerizing L00% by weight.
  • the temporary surface protecting adhesive according to any one of the above (2) to (3), wherein
  • the acrylic resin (A) has a weight average molecular weight of 200,000 to 2,000,000.
  • An adhesive for temporary surface protection as described above.
  • a pressure-sensitive adhesive sheet comprising a base material and the temporary surface protecting pressure-sensitive adhesive according to any one of (2) to (10) above.
  • a method of using a pressure-sensitive adhesive sheet comprising: attaching the pressure-sensitive adhesive sheet according to (11) above to an adherend surface, protecting the adherend surface, and then peeling the pressure-sensitive adhesive sheet.
  • An acrylic resin composition mainly containing an acrylic resin (A) [ I] is provided on a base material and includes a step of forming a laminate, and a step of irradiating the laminate with active energy rays.
  • the acrylic resin composition [I] is preferable because it contains a photopolymerization initiator in that the reaction at the time of active energy ray irradiation can be stabilized.
  • the photopolymerization initiator is disadvantageous for curing due to oxygen hindrance on the surface, but is a self-cleaving photopolymerization initiator that is advantageous for internal cross-linking, and is less affected by oxygen hindrance. It is preferable to use both hydrogen abstraction type photopolymerization initiators, which are advantageous for curing at low temperatures, because the entire coating film has good balance and can be crosslinked!
  • “for temporary surface protection” includes not only one-time use but also repeatedly applying and removing a plurality of times.
  • the present invention has an appropriate peel strength and changes with time in peel strength (initial adhesive strength and A resin composition for forming a temporary surface-protective pressure-sensitive adhesive having a reduced curing period and a temporary surface using the same.
  • a protective adhesive can be obtained.
  • the pressure-sensitive adhesive for temporary surface protection according to the present invention does not contain an ethylenically unsaturated group! ⁇
  • Acrylic resin (A) or an acrylic resin (A) that does not contain an ethylenically unsaturated group is mainly used. It is obtained by irradiating an active energy ray to the resin composition [I] containing.
  • the acrylic resin (A) used in the present invention is not particularly limited as long as it is an acrylic resin that does not contain an ethylenically unsaturated group.
  • (meth) Acrylic acid alkyl ester (a1) is preferably used, preferably as a main component, and if necessary, a copolymer obtained by using other copolymerizable monomer (a2).
  • the (meth) acrylic acid alkyl ester (al) includes methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl.
  • the alkyl group has 3 carbon atoms.
  • the following (meth) acrylic acid alkyl esters can be used in combination as appropriate.
  • a copolymerizable monomer having one ethylenically unsaturated group and containing a functional group other than the ethylenically unsaturated group (a2-1) (hereinafter referred to as a functional group-containing copolymer).
  • a functional group-containing copolymer a copolymerizable monomer having one ethylenically unsaturated group and containing a functional group other than the ethylenically unsaturated group (a2-1) (hereinafter referred to as a functional group-containing copolymer).
  • Compatible monomer (a2-1) and copolymerizable monomer (a2-2) other than (al) and (a2-1) (hereinafter referred to as copolymerizable monomer (a2-2)) May be omitted).
  • Examples of the functional group-containing copolymerizable monomer (a2-1) include a carboxyl group-containing monomer, a hydroxyl group-containing monomer, an amino group-containing monomer, a acetoacetyl group-containing monomer, an amide group-containing monomer, and a glycidyl group-containing monomer.
  • carboxyl group-containing monomers and hydroxyl group-containing monomers are preferably used.
  • Examples of the carboxyl group-containing monomer include (meth) acrylic acid, crotonic acid, maleic acid, maleic anhydride, fumaric acid, citraconic acid, glutaconic acid, itaconic acid, acrylic amide N glycolic acid, and cinnamate. And (meth) acrylic acid Michael adducts (for example, alicyclic dimer, methacrylic acid dimer, acrylic acid trimer, methacrylic acid trimer, acrylic acid tetramer, methacrylic acid tetramer, etc.). Methacrylic acid is preferably used.
  • Examples of the hydroxyl group-containing monomer include 2 hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3 black 2 hydroxypropyl (meth) acrylate, tetrahydrofurfuryl (meth).
  • 2-hydroxy-3 phenoxypropyl (meth) acrylate diethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, N-methylol (meta) ) Acrylamide, ethyl carbitol acrylate, tripropylene glycol mono (meth) acrylate, 1,4-butylene glycol mono (meth) acrylate, glycerol mono (meth) acrylate, 2 hydroxyethyl allyloyl phos Fate 4 Butylhydroxiatalylate, force prolatatone modified 2-hydroxyethyl talylate, 2-atallyloyloxychetyl succinic acid, allylic alcohol, etc.
  • 2-hydroxyethyl (meth) acrylate, 4 (Meth) acrylate having a hydroxyalkyl group having 1 to 4 carbon atoms such as but
  • the amino group-containing monomer is preferably a primary or secondary amino group-containing monomer.
  • examples thereof include t-butylaminoethyl (meth) acrylate and ethylaminoethyl (meth) acrylate.
  • Examples of the acetoacetyl group-containing monomer include 2- (acetoacetoxy) ethyl (meth) acrylate and allylacetate acetate.
  • amide group-containing monomer examples include diacetone acrylamide, (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-jetyl (meth) acrylamide, N-methylol acrylamide, and the like.
  • glycidyl group-containing monomer examples include glycidyl (meth) acrylate and allylic glycidyl ether.
  • These functional group-containing copolymerizable monomers (a2-1) are used alone or in combination of two or more.
  • the copolymerizable monomer (a2-2) includes, for example, acrylonitrile, meta-tali-tolyl, styrene, OC-methylstyrene, vinyl acetate, butyl propionate, vinyl chloride, vinylidene chloride, alkyl butyl ether, Ether bonds such as 2-methoxyethyl (meth) acrylate, 2-methoxy cetyl (meth) acrylate, butoxy cetyl (meth) acrylate, etc. (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, etc.
  • ethylene glycol di (meth) acrylate for the purpose of increasing the molecular weight, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) Polyfunctional monomers such as attalylate, propylene glycol di (meth) acrylate, and dibutylbenzene can be used in combination.
  • the content of the copolymerizable monomer component (al) and (a2) constituting the acrylic resin (A) does not contain an ethylenically unsaturated group! whole by pair, 20 is (meth) acrylic acid alkyl ester (al): LOO weight 0/0, preferably other copolymerizable monomer (a2) is 0-80 wt%, more preferably ( (Meth) acrylic acid ester (al) is 50 to 100 weight.
  • other copolymerizable monomer (a2) is 0 to 50% by weight
  • a 70 is (meth) acrylic acid ester (al): LOO wt%
  • other copolymerizable mono mer (a2) is 0 to 30 weight 0/0.
  • (meth) acrylic acid alkyl ester (al) as a main component as a copolymerizable monomer component of acrylic resin (A) from the viewpoint of suppressing the increase in adhesive strength over time.
  • the functional group-containing copolymerizable monomer (a2-1) is contained as the other copolymerizable monomer (a2)
  • the functional group-containing copolymer is added to the entire copolymerizable monomer component. It is preferable that the amount of the monomer (a2-l) is 0.1 to 20% by weight, more preferably 0.3 to 18% by weight, and particularly preferably 0.5 to 15% by weight.
  • the acrylic resin (A) containing no ethylenically unsaturated group used in the present invention is produced by a method well known to those skilled in the art, such as radical polymerization in an organic solvent.
  • organic solvent used for intensive polymerization examples include aromatic hydrocarbons such as toluene and xylene, esters such as ethyl acetate and butyl acetate, aliphatic alcohols such as n-propyl alcohol and iso-propyl alcohol, and methyl ether.
  • aromatic hydrocarbons such as toluene and xylene
  • esters such as ethyl acetate and butyl acetate
  • aliphatic alcohols such as n-propyl alcohol and iso-propyl alcohol
  • methyl ether examples thereof include ketones such as tilketone, methylisobutylketone, and cyclohexanone.
  • polymerization initiators used for intensive radical polymerization 2,2'-azobisisobutyryl-tolyl, 2,2'-azobis-2-methylbutyryl-tolyl, which is a normal radical polymerization initiator, 4 , 4, azobis (4-cyananovaleric acid), 2, 2, azobis (methylpropionic acid) and other azo initiators, benzoyl peroxide, lauryl peroxide, di-t-butyl peroxide, tamenno, id And organic peroxides such as oral peroxide.
  • the weight average molecular weight of the acrylic resin (A) that does not contain the ethylenically unsaturated group obtained by force is not particularly limited, but is usually 200,000 to 2,000,000, preferably 300,000 to 1.5 million. If the weight average molecular weight is too small, the removability tends to be difficult to obtain, and if it is too large, a large amount of diluent solvent is required, and the coating property and cost tend to be inferior.
  • the above weight average molecular weight is a weight average molecular weight in terms of standard polystyrene molecular weight, and can be measured by high performance liquid chromatography (Waters 2695 (main unit) and Waters 2414 (detector)).
  • the glass transition temperature (Tg) of the acrylic resin (A) that does not contain an ethylenically unsaturated group is not particularly limited, but is usually 0 ° C or lower, preferably -20 °. C or less. If the glass transition temperature is too high, initial adhesion cannot be obtained, and the adhesive strength tends to increase with time.
  • Tg is obtained from the following formula using Tg of a homopolymer of each monomer component constituting the copolymer.
  • Tg is the glass transition temperature of the copolymer
  • Tgl, Tg2, and Tgk are the Tg of the homopolymer of each monomer component
  • the present invention contains only the acrylic resin (A) that does not contain the ethylenically unsaturated group, and is obtained by irradiating the acrylic resin (A) with active energy rays.
  • “substantially contains only acrylic resin (A)” means that acrylic resin (A) usually contains less than 5% of other ingredients, preferably less than 3%. It also means that it is contained. Examples of such other components include residual monomer components and initiators during the production of acrylic resin (A).
  • the acrylic resin composition [I] mainly containing the acrylic resin (A) that does not contain the ethylenically unsaturated group of the present invention is irradiated with active energy rays.
  • “mainly containing acrylic resin (A)” means that the acrylic resin (A) does not contain an ethylenically unsaturated group and the resin composition [ I] is a main component, and preferably contains 60% by weight or more of an acrylic resin containing no ethylenically unsaturated group (A) in the resin composition [I], more preferably 60% by weight or more. 70% by weight or more
  • the resin component in the strong acrylic resin composition [I] substantially does not contain an ethylenically unsaturated group, and only the acrylic resin (A) has power. I prefer that.
  • the coconut resin component is also effective only for the acrylic resin (A) that does not contain an acetylenically unsaturated group” means that 95% by weight or more of the rosin component is ethylenically unsaturated. It means that the acrylic resin (A) does not contain a saturated group, and it is preferable that the acrylic resin (A) 97-: LOO% by weight does not contain an ethylenically unsaturated group. In addition, it is preferable that the resin component other than the acrylic resin (A) does not contain an ethylenically unsaturated group.
  • the acrylic resin composition [I] in the present invention is characterized in that it does not contain a polymerizable monomer or a polymerizable oligomer.
  • the acrylic resin composition [I] in the present invention preferably contains a photopolymerization initiator in order to stabilize the reaction during irradiation with active energy rays.
  • the powerful photopolymerization initiator is not particularly limited as long as it generates radicals by the action of light, and includes an intramolecular self-cleavage photopolymerization initiator and a hydrogen abstraction photopolymerization initiator. Used.
  • Examples of the intramolecular self-cleaving type photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-tert-butyldichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2-phenyl.
  • the hydrogen abstraction type photopolymerization initiator for example, benzophenone, benzoyl ammonium Benzoic acid, Methyl benzoylbenzoate, 4-Phenolpenzophenone, Hydroxybenzophenone, 3,3'-Dimethyl-4-methoxybenzophenone, 2, 4, 6 Trimethylbenzophenone, 4-Methylbenzophenone, Thioxanthone, 2 Chlorthioxanthone, 2-Methylthioxanthone, 2, 4 Dimethylthioxanthone, Isopropylthixanthone, Camphorquinone, Dibenzosuberone, 2 Ethylanthraquinone, 3, 3 ', 4, 4' —Tetra (t-butylperoxycarbol) benzophenone, benzyl, 9,10 phenanthrenequinone, and the like.
  • the use of both a self-cleaving photopolymerization initiator and a hydrogen abstraction photopolymerization initiator provides a good balance between photocrosslinking of the surface portion of the pressure-sensitive adhesive layer and internal photocrosslinking. Therefore, it is preferable in that a tolerance of adhesive force and cohesive force can be obtained.
  • the combination of the self-cleaving type photopolymerization initiator and the hydrogen abstraction type photopolymerization initiator includes a self-cleaving type 1-hydroxycyclohexyl phenol and a hydrogen abstraction type benzophenone, methylbenzophenone, Or a combination of 2, 4, 6 trimethylbenzophenone is preferred.
  • the content of the photopolymerization initiator is not particularly limited !, but acrylic resin having no ethylenically unsaturated groups (A) 0.01 to 20 parts by weight per 100 parts by weight In particular, 0.05 to: L0 parts by weight, and further 0.1 to 4 parts by weight is preferable. If the amount is too small, there is a tendency that variation due to irradiation with active energy line tends to occur, too much. And the crosslink density decreases, and the effect of removability tends to be difficult to obtain.
  • the self-cleaving photopolymerization initiator and the hydrogen abstraction photopolymerization are used in combination as a photopolymerization initiator.
  • the ratio of the initiator is preferably from 70Z30 to LZ99 (weight ratio), especially from 55Z45 to 3Z97 (weight ratio), and more preferably from 45Z55 to 5Z95 (weight ratio). , Photocrosslinking of the surface portion becomes insufficient and adherend contamination tends to occur.
  • the acrylic pressure-sensitive adhesive of the present invention is one that is conventionally performed! Instead of the method of cross-linking glazed acrylic resin using a cross-linking agent, it is cross-linked by irradiation with active energy rays. A smaller amount of a cross-linking agent can also be added compared to the conventional one in that stable physical properties can be obtained with good reproducibility.
  • a reactive crosslinking agent is combined with an acrylic resin (A) that does not contain an ethylenically unsaturated group, and an acrylic resin (A) and a reactive crosslinking agent that do not contain an ethylenically unsaturated group. It is also preferable to use the rosin composition [I].
  • the reactive crosslinking agent when blended, it does not contain an ethylenically unsaturated group! /, And the acrylic resin (A) contains a functional group-containing co-polymer as its constituent component. It is preferable to contain a polymerizable monomer (a2 1).
  • the reactive crosslinking agent that does not contain an ethylenically unsaturated group is not particularly limited as long as it can react with the acrylic resin (A).
  • an isocyanate compound, an epoxy compound examples thereof include compounds, aziridine compounds, and melamine compounds.
  • Examples of the isocyanate compound include 2,4 tolylene diisocyanate, 2,6 tolylene diisocyanate, hydrogenated tolylene diisocyanate, 1,3 xylylene diisocyanate, 1, 4 Xylylene diisocyanate, hexamethylene diisocyanate, diphenol-methane 4,4-diisocyanate, isophorone diisocyanate, 1,3 bis (isocyanatomethyl) cyclohexane, tetramethylxylylene diisocyanate 1, 5 naphthalene diisocyanate, tri-methane methane triisocyanate, and adducts of these polyisocyanate compounds and polyols such as trimethylolpropane, these polyisocyanates. Examples thereof include a burette body and an isocyanurate body of Natoi compound.
  • Examples of the epoxy compound include N, N, ⁇ ', N'-tetraglycidinole m-xylylenediamine, diglycidyl dilin, 1,3 bis (N, N glycidylaminomethyl) cyclohexane.
  • aziridine compounds examples include tetramethylol methane tree ⁇ aziridyl propionate, trimethylol propane-tri- ⁇ -aziridyl propionate, ,, ⁇ '-diphenylmethane-1,4'-bis (1— Aziridinecarboxamide), ⁇ , ⁇ ′-hexamethylene 1,6bis (1 aziridinecarboxyamide) and the like.
  • Examples of the melamine compounds include hexamethoxymethyl melamine, hexaethoxymethylol melamine, hexapropoxymethyl melamine, hexasuboxymethyl melamine, hexapentylmethyl melamine, hexahexyloxymethyl melamine, and the like. It is done.
  • These reactive crosslinking agents may be used alone or in combination of two or more.
  • the content of the reactive crosslinking agent is 0.05 to 20 parts by weight with respect to 100 parts by weight of the acrylic resin having no ethylenically unsaturated group ( ⁇ ). It is preferably 0.1 to 18 parts by weight, more preferably 0.3 to 15 parts by weight. If the content is too small, the effect of adding the reactive cross-linking agent cannot be obtained, and if it is too high, there is a high possibility that the unreacted cross-linking agent will cause contamination.
  • an acid catalyst such as paratoluenesulfonic acid, phosphoric acid, hydrochloric acid, and ammonium chloride can be used in combination in order to promote crosslinking.
  • the addition amount is preferably 10 to 50% by weight based on the crosslinking agent.
  • the resin composition used in the present invention may further include a filler, a pigment, a diluent, an anti-aging agent, an ultraviolet absorber, an ultraviolet stabilizer, and an antistatic agent that are usually blended as necessary.
  • a filler such as may be added in a range without impairing the required physical properties!
  • an ultraviolet absorber such as may be added in a range without impairing the required physical properties!
  • an ultraviolet stabilizer such as may be added in a range without impairing the required physical properties!
  • an antistatic agent such as may be added in a range without impairing the required physical properties!
  • additives such as may be added in a range without impairing the required physical properties!
  • One or more additives can be used. The amount of these additives should be set in a timely manner so that the desired physical properties can be obtained.
  • the resin in addition to the acrylic resin composition [I], the resin does not contain a polymerizable monomer or polymerizable oligomer, and contains a resin component and a photopolymerization initiator.
  • a temporary surface protecting adhesive is formed by an active energy ray, which is a composition, wherein the resin component is substantially only acrylic resin (A) containing no ethylenically unsaturated group.
  • the present invention provides a rosin composition.
  • the photopolymerization initiator is an essential component. Detailed description of each component, the amount thereof, additional components and the like of the resin composition of this embodiment is the same as the description of the acrylic resin composition [I].
  • the acrylic resin (A) containing no ethylenically unsaturated group obtained above, or containing no ethylenically unsaturated group ! acrylic resin ( Acrylic resin composition mainly containing A) [I] (Preferably, an acrylic resin composition containing no ethylenically unsaturated group (A) and a photopolymerization initiator alone or in combination. Adhesive performance can be obtained by irradiating a fat composition [1]) with active energy rays.
  • active energy rays As active energy rays, rays such as far ultraviolet rays, ultraviolet rays, near ultraviolet rays, infrared rays, electromagnetic waves such as X rays and y rays, electron rays, proton rays, neutron rays, etc.
  • rays such as far ultraviolet rays, ultraviolet rays, near ultraviolet rays, infrared rays, electromagnetic waves such as X rays and y rays, electron rays, proton rays, neutron rays, etc.
  • curing by ultraviolet irradiation is advantageous because of the curing speed, the availability of the irradiation device, and the price.
  • UV irradiation use a high-pressure mercury lamp, ultrahigh-pressure mercury lamp, carbon arc lamp, metal halide lamp, xenon lamp, chemical lamp, electrodeless discharge lamp, etc. that emits light in the wavelength range of 150 to 450 nm. Can do.
  • the dose of the active energy ray preferably to be 100 ⁇ 2000MjZcm 2 instrument: g «150 ⁇ 1500mjZcm 2, and particularly preferably from 180 ⁇ 1000nijZcm 2. If the irradiation dose is too small, the cohesive force is insufficient due to insufficient crosslinking, and if it is too much, the substrate tends to deteriorate the release film.
  • a resin composition [I] containing no unsaturated group, acrylic resin (A), or ethylenically unsaturated group and mainly containing acrylic resin (A) has an active energy. Since the irradiation of the line is performed, it is not necessary to carry out in an inert gas atmosphere in order to suppress the inhibition of polymerization by oxygen, or to coat the coating film made of the pressure-sensitive adhesive composition with a cover film.
  • the irradiation with active energy rays in the present invention is preferably carried out in the presence of oxygen, and particularly in the atmosphere.
  • the irradiation amount of active energy is usually less than lOOOmjZcm 2 because the number of reaction points is reduced when the polymer of the present invention is crosslinked as compared with the case of using a polymerizable monomer or polymerizable oligomer. An irradiation dose is sufficient.
  • the temporary surface-protecting pressure-sensitive adhesive after being crosslinked by irradiation with active energy rays preferably has a gel fractional power of 0 to LOO wt%, particularly 50 to LOO wt%. Is preferred. When the gel fraction is too small, the re-peelability tends to decrease due to insufficient cohesive force.
  • the gel fraction is a measure of the degree of crosslinking, and is calculated by the following method.
  • an adhesive sheet (without a separator) obtained as described below is wrapped in 200 mesh SUS wire mesh, immersed in toluene at 23 ° C for 24 hours, and the insoluble adhesive component remaining in the wire mesh
  • the weight percentage is defined as the gel fraction. Subtract the weight of the base material.
  • the irradiation amount and irradiation intensity of the active energy line are adjusted, and the photopolymerization initiator is divided into a self-cleavage type and a hydrogen abstraction type.
  • the photopolymerization initiator is divided into a self-cleavage type and a hydrogen abstraction type.
  • the irradiation amount and irradiation intensity of the active energy rays, the composition ratio of the photopolymerization initiator, and the addition amount need to be balanced because the gel fraction changes due to their interaction. .
  • Temporary surface by irradiating with active energy ray using cryl-based rosin composition [I] Although it has adhesive performance as a protective pressure-sensitive adhesive, specifically, for example, it does not contain such an ethylenically unsaturated group, but does not contain an acrylic resin (A) or an ethylenically unsaturated group.
  • Acrylic greaves (A) The acrylic greaves composition [I], which contains mainly, is applied to the substrate, and then an active energy ray is irradiated to form an adhesive sheet. It is bonded to the adherend.
  • sheet is described as including a film that is not particularly distinguished from “film”.
  • the material for the base material is not particularly limited as long as it is a material for forming a sheet.
  • Polyester resin such as boribylene terephthalate, polyethylene terephthalate Z isophthalate copolymer, polyolefin resin such as polyethylene, polypropylene, polymethylpentene, polyfluoride bure, polyvinylidene fluoride, polyfluorinated styrene, etc.
  • Polyfluorinated styrene resin nylon 6, nylon 6, nylon 6 and other polyamides, polyvinyl chloride, polychlorinated bur Z acetate acetate copolymer, ethylene-butyl acetate copolymer, ethylene-vinyl alcohol copolymer Butyl polymers such as polybulal alcohol and vinylon, cellulose-based resins such as cellulose triacetate and cellophane, acrylic resins such as polymethyl methacrylate, polyethyl methacrylate, polyethyl ethyl and polybutyl acrylate, Polystyrene, polycarbonate, poly Relate, synthetic resin sheet such as polyimide, fine paper, Gurashi down paper such as paper, glass fibers, natural fibers, single-layer, or multi-layer material such as synthetic fibers.
  • a sheet of polyethylene terephthalate, polyethylene, polypropylene or the like is preferably used.
  • the surface of the base material is known for easy adhesion such as corona discharge treatment, plasma treatment, primer coating, degreasing treatment, and surface roughening treatment.
  • a treatment for improving the resistance may be applied, or an antistatic layer may be provided to prevent the charge.
  • the thickness of the substrate is not particularly limited, but is generally 500 ⁇ m or less, preferably 5 to 30.
  • a thickness of about 0 m, more preferably about 10 to 200 ⁇ m can be exemplified.
  • the pressure-sensitive adhesive for temporary resurface protection of the present invention is provided as a pressure-sensitive adhesive sheet.
  • the thickness of the pressure-sensitive adhesive layer is not particularly limited, but is generally 1 to: LOO / zm, preferably 2 to 50; If the pressure-sensitive adhesive layer is too thick, the adhesive of the temporary surface protecting adhesive sheet tends to remain on the adherend surface when it is peeled off. It tends to be difficult to perform the function as a pressure-sensitive adhesive sheet for surface protection, for example, the adhesive strength to the adherend is reduced and peeling occurs.
  • a separator can be stacked on the surface of the pressure-sensitive adhesive sheet for the purpose of protecting the temporary surface-protective pressure-sensitive adhesive layer from contamination until the pressure-sensitive adhesive sheet for temporary surface protection of the present invention is bonded to an adherend.
  • the separator those obtained by releasing the synthetic resin sheet, paper, cloth, nonwoven fabric and the like exemplified in the base material can be used.
  • the pressure-sensitive adhesive sheet using the temporary surface protecting pressure-sensitive adhesive of the present invention does not contain an ethylenically unsaturated group on the base material, and is an acrylic resin (A), or ethylene. It is obtained by coating and drying an acrylic resin composition [I] mainly containing an acrylic resin (A) that does not contain an unsaturated group, and irradiating with active energy rays. When the acrylic resin (A) or the acrylic resin composition [I] does not contain such an ethylenically unsaturated group and is in a solution state, it does not contain a solution-like ethylenically unsaturated group.
  • a direct coating method in which an acrylic resin (A) or an acrylic resin composition [I] is applied directly to a substrate, or an acrylic resin (not containing a solution-like ethylenically unsaturated group) ( A) or the acrylic resin composition [I] is applied to a separator and then laminated on the substrate by a transfer coating method for bonding to the substrate.
  • Coating is carried out by conventional methods such as roll coating, die coating, gravure coating, comma coating, and screen printing.
  • the acrylic resin (A) or the acrylic resin composition [I] is applied to the separator, dried by heating, and then bonded to the substrate.
  • the same method as direct coating can be used.
  • the pressure-sensitive adhesive sheet using the temporary surface-protecting pressure-sensitive adhesive of the present invention is attached to the surface of the adherend, and even if the adherend and the pressure-sensitive adhesive sheet are exposed to a high temperature, the temporary sheet of the present invention is used. Surface protection It is possible to peel off the adherend strength of the adhesive.
  • adherend there are no particular limitations on the type of adherend that can be used for the temporary surface protecting adhesive of the present invention.
  • adherend aluminum, copper, iron metal foil, polyethylene naphthalate, polyethylene terephthalate, boribylene terephthalate, Polyethylene terephthalate Z isophthalate Copolymers and other polyester resins, polyethylene, polypropylene, polymethylpentene and other polyolefin resins, polyfluorinated bures, polyvinylidene fluoride, polyfluorinated styrene resins , Nylon 6, nylon 6, 6, etc.
  • Polyamide polysalt vinyl, polyvinyl chloride Z vinyl acetate copolymer, ethylene vinyl acetate copolymer, ethylene-bule alcohol copolymer, polybulu alcohol , Vinyl polymers such as vinylon, cellulose triacetate, cellophane, etc.
  • cellulose resins acrylic resins such as polymethyl methacrylate, polyethyl methacrylate, polyethyl acrylate, and polybutyl acrylate
  • synthetic resin sheets or plates such as polystyrene, polycarbonate, polyarylate, and polyimide. It is done.
  • the adhesive for temporary surface protection of the present invention is applied to metal plates, glass plates, synthetic resin plates, laminated steel plates, etc. for label sheets, tapes, building materials, packaging materials, and electronics. Used as a temporary surface protecting adhesive.
  • the pressure-sensitive adhesive sheet obtained from the temporary surface-protecting pressure-sensitive adhesive can be temporarily protected on the surface of the adherend by being affixed to the surface of the adherend, and after the purpose of protection has ended.
  • the pressure-sensitive adhesive sheet is peeled off from the adherend.
  • Hexamethylene diisocyanate compound (Nippon Polyurethane, Coronate HX)
  • a resin composition solution was prepared with the formulation shown in Table 1.
  • the obtained rosin composition solution was applied using a polyethylene terephthalate (PET) sheet (thickness 38 m) as a base material so that the thickness after drying was 25 / zm. Dried for minutes. After that, UV irradiation with the high-pressure mercury lamp (irradiation amount shown in Table 1) is performed, and a PET sheet that has been subjected to release treatment is attached to the surface of the pressure-sensitive adhesive layer, which is a powerful resin composition. An adhesive sheet with an adhesive was obtained.
  • PET polyethylene terephthalate
  • the gel fraction (%) was measured in the same manner as in the above method except that a sample obtained from the pressure-sensitive adhesive sheet after 1 week had been used.
  • Adhesive strength was measured in the same manner as described above, except that a sample obtained from a pressure-sensitive adhesive sheet after one week was used.
  • the peelability (contamination resistance to the adherend) was determined by allowing the adhesive sheet obtained above to stand for 1 day, and then preparing a test piece of 25 mm x 100 mm from the adhesive sheet.
  • a 2kg roller is reciprocated twice on the adherend (SUS304BA plate), left at 70 ° C for 5 days, and then peeled 180 ° under 23 ° C, 50% RH atmosphere (peeling speed 300mmZmin) The state of each adherend surface was observed. As a result, no contamination was confirmed on all sheets.
  • Table 2 shows the evaluation results of Examples and Comparative Examples.
  • Example 2 (%) (N / 25mm) (%) (N / 25mm) Example "! 90. 2 0. 26 91 0. 28 Example 2 90. 6 0. 28 96. 8 0. 23 Example 3 90. 7 0. 19 97. 7 0. 12 Example 4 90. 8 0. 09 91. 5 0. 1 Comparative Example 1 72. 8 0. 9 98. 9 0. 12
  • the present invention provides a coated film after peeling that has an appropriate peel strength and has little change over time in the peel force.
  • the present invention provides a resin composition for forming a temporary surface-protective pressure-sensitive adhesive that is free from contamination of the body and further shortens the curing time, and a temporary surface-protective pressure-sensitive adhesive using the composition. It is very useful as an adhesive for temporary surface protection used for metal plates, glass plates, synthetic resin plates, laminated steel plates, etc. for sheets, tapes, building materials, packaging materials, and electronics.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention concerne une composition de résine servant à former un adhésif pour la protection temporaire d'une surface lequel a une force d'adhérence et une aptitude à se décoller adéquates qui ne varient pas au cours du temps, tout en ne laissant aucune contamination sur l'objet dont il est séparé. Cette composition de résine a une durée de durcissement réduite. L'invention concerne également un adhésif pour la protection temporaire d'une surface lequel utilise une telle composition. L'invention concerne précisément une composition de résine servant à former un adhésif pour la protection temporaire d'une surface par irradiation d'un rayonnement d'énergie active, laquelle contient un composant résine et un initiateur de photopolymérisation sans contenir un monomère polymérisable ou un oligomère polymérisable. Dans cette composition de résine, le composant résine est composé presque intégralement d'une résine acrylique (A) ne contenant pas de groupe à insaturation éthylénique. L'invention concerne également précisément un adhésif pour la protection temporaire d'une surface lequel ne contient essentiellement qu'une résine acrylique (A) ne contenant pas de groupe à insaturation éthylénique et lequel est obtenu par irradiation avec un rayonnement d'énergie active. L'invention concerne en outre précisément un adhésif pour la protection temporaire d'une surface lequel est obtenu en irradiant avec un rayonnement d'énergie active une composition de résine acrylique [I] contenant principalement une résine acrylique (A), laquelle ne contient pas de groupe à insaturation éthylénique.
PCT/JP2007/063958 2006-07-18 2007-07-13 Composition de résine, adhésif pour la protection temporaire d'une surface, film adhésif et procédé servant à produire un film adhésif WO2008010453A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2006195568 2006-07-18
JP2006-195568 2006-07-18
JP2006-195567 2006-07-18
JP2006195567 2006-07-18

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WO2008010453A1 true WO2008010453A1 (fr) 2008-01-24

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KR (1) KR20090031907A (fr)
TW (1) TW200815551A (fr)
WO (1) WO2008010453A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104592913A (zh) * 2015-01-30 2015-05-06 日东电工（上海松江）有限公司 丙烯酸类粘合剂的制备方法、粘合剂及其用途
WO2020054745A1 (fr) * 2018-09-12 2020-03-19 王子ホールディングス株式会社 Feuille adhésive, produit en couches et procédé de production d'un produit en couches

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JPH07502558A (ja) * 1991-12-31 1995-03-16 ミネソタ　マイニング　アンド　マニュファクチャリング　カンパニー 再剥離型低溶融粘度アクリル系感圧接着剤
JP2000109771A (ja) * 1998-10-07 2000-04-18 Lintec Corp 粘着シート
JP2001064612A (ja) * 1999-08-30 2001-03-13 Mitsubishi Rayon Co Ltd 紫外線硬化型粘着剤組成物
JP2004262957A (ja) * 2003-01-30 2004-09-24 Mitsubishi Plastics Ind Ltd ホットメルト型紫外線架橋透明粘着剤、透明粘着シート及び積層体
JP2005290357A (ja) * 2004-03-08 2005-10-20 Nitto Denko Corp 粘着剤組成物、粘着シート類及び表面保護フィルム
WO2006088099A1 (fr) * 2005-02-16 2006-08-24 The Nippon Synthetic Chemical Industry Co., Ltd. Adhésif pour élément optique et procédé de fabrication d’adhésif pour élément optique

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Publication number Priority date Publication date Assignee Title
JPH07502558A (ja) * 1991-12-31 1995-03-16 ミネソタ　マイニング　アンド　マニュファクチャリング　カンパニー 再剥離型低溶融粘度アクリル系感圧接着剤
JP2000109771A (ja) * 1998-10-07 2000-04-18 Lintec Corp 粘着シート
JP2001064612A (ja) * 1999-08-30 2001-03-13 Mitsubishi Rayon Co Ltd 紫外線硬化型粘着剤組成物
JP2004262957A (ja) * 2003-01-30 2004-09-24 Mitsubishi Plastics Ind Ltd ホットメルト型紫外線架橋透明粘着剤、透明粘着シート及び積層体
JP2005290357A (ja) * 2004-03-08 2005-10-20 Nitto Denko Corp 粘着剤組成物、粘着シート類及び表面保護フィルム
WO2006088099A1 (fr) * 2005-02-16 2006-08-24 The Nippon Synthetic Chemical Industry Co., Ltd. Adhésif pour élément optique et procédé de fabrication d’adhésif pour élément optique

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104592913A (zh) * 2015-01-30 2015-05-06 日东电工（上海松江）有限公司 丙烯酸类粘合剂的制备方法、粘合剂及其用途
CN104592913B (zh) * 2015-01-30 2016-11-02 日东电工（上海松江）有限公司 丙烯酸类粘合剂的制备方法、粘合剂及其用途
WO2020054745A1 (fr) * 2018-09-12 2020-03-19 王子ホールディングス株式会社 Feuille adhésive, produit en couches et procédé de production d'un produit en couches
JP2020041069A (ja) * 2018-09-12 2020-03-19 王子ホールディングス株式会社 粘着シート、積層体及び積層体の製造方法
JP7305939B2 (ja) 2018-09-12 2023-07-11 王子ホールディングス株式会社 粘着シート、積層体及び積層体の製造方法

Also Published As

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KR20090031907A (ko) 2009-03-30
TW200815551A (en) 2008-04-01

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