WO2019130822A1 - Composition de résine, couche de résine, et feuille stratifiée - Google Patents

Composition de résine, couche de résine, et feuille stratifiée Download PDF

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Publication number
WO2019130822A1
WO2019130822A1 PCT/JP2018/040971 JP2018040971W WO2019130822A1 WO 2019130822 A1 WO2019130822 A1 WO 2019130822A1 JP 2018040971 W JP2018040971 W JP 2018040971W WO 2019130822 A1 WO2019130822 A1 WO 2019130822A1
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meth
weight
acrylate
monomer
resin layer
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PCT/JP2018/040971
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English (en)
Japanese (ja)
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昌嗣 東
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日東電工株式会社
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Priority claimed from JP2018194150A external-priority patent/JP7185479B2/ja
Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Priority to CN201880082614.5A priority Critical patent/CN111492007A/zh
Publication of WO2019130822A1 publication Critical patent/WO2019130822A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/06—Polystyrene
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L57/00—Compositions of unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C08L57/02—Copolymers of mineral oil hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L93/00—Compositions of natural resins; Compositions of derivatives thereof
    • C08L93/04—Rosin
    • 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
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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]

Definitions

  • the present invention relates to a resin composition, a resin layer, and a laminated sheet.
  • the present application claims priority based on Japanese Patent Application No. 2017-254900 filed on December 28, 2017 and Japanese Patent Application No. 2018-194150 filed on October 15, 2018. , The entire contents of that application being incorporated herein by reference.
  • a pressure-sensitive adhesive (also referred to as a pressure-sensitive adhesive, hereinafter the same) exhibits a soft solid (viscoelastic) state in a temperature range around room temperature, and has a property of adhering to an adherend by pressure.
  • the pressure-sensitive adhesive is, for example, in the form of a pressure-sensitive adhesive sheet (laminated sheet) having a laminated structure having a resin layer capable of functioning as a pressure-sensitive adhesive on one side or both sides of a support. It is widely used in various industrial fields.
  • Patent documents 1 and 2 are mentioned as technical documents about an adhesive or a pressure sensitive adhesive sheet.
  • the conventional laminated sheet having an adhesive is a rough surface (surface having a concavo-convex shape) such as concrete, mortar, gypsum board, softwood plywood, wood based cement board, calcium silicate board, tile, and fiber reinforced cement board etc.
  • Adhesion to an adherend having the above and a plastic adherend such as polypropylene, which is generally recognized as a low-polar adherend has a high degree of difficulty and tends to lack adhesion. For this reason, not a pressure-sensitive adhesive but an adhesive is often used for adherends having these rough surfaces.
  • measures such as primer treatment have often been required.
  • a laminated sheet such as an adhesive sheet can be used for the purpose of bonding an adherend or a plastic member having a rough surface as described above.
  • a laminated sheet such as a pressure-sensitive adhesive sheet used for an adherend having a rough surface or a plastic member also needs a holding power from the viewpoint of holding a heavy material fixed to the adherend in a fixed state for a long time It is assumed.
  • the bonding operation of the adherend having a rough surface can be performed also in a low temperature environment such as in the winter outdoors, the laminated sheet such as an adhesive sheet has good adhesiveness to the rough surface even at a low temperature. It is desirable to show.
  • the present invention can strongly adhere to both rough surfaces and plastics while strongly adhering to adherends generally easy to adhere, such as glass, metals such as stainless steel and aluminum, etc. It is an object of the present invention to provide a resin layer that has high holding power and exhibits good adhesion even at low temperatures, and a resin composition suitable for forming the resin layer. Another related objective is to provide a laminated sheet including the above resin layer.
  • a (meth) acrylic polymer having a glass transition temperature (Tg) of -40 ° C. or less and an adhesion of 5 to 40 parts by weight with respect to 100 parts by weight of the (meth) acrylic polymer
  • a resin composition containing the application resin.
  • the (meth) acrylic polymer has a homopolymer Tg of ⁇ 50 ° C. or less and an alkyl (meth) acrylate (A1) having a branched alkyl group having 8 to 18 carbon atoms at the end of the ester group and a homopolymer It is a polymer of a monomer component including (meth) acrylate (A2) having a Tg of ⁇ 40 ° C.
  • the monomer component contains 50 to 97% by weight of the alkyl (meth) acrylate (A1) and 3 to 50% by weight of the (meth) acrylate (A2) having the ether bond.
  • alkyl (meth) acrylate (A1) may be described with “monomer A1” below.
  • (meth) acrylate (A2) which has the said ether bond may be described with “monomer A2.”
  • the adhesive force with respect to a to-be-adhered body can be improved by containing the tackifying resin of a specific amount with respect to the said (meth) acrylic-type polymer.
  • the (meth) acrylic polymer is a polymer of a monomer component containing the monomer A1 and the monomer A2 in a specific ratio, a resin layer exhibiting high surface tension and good surface adhesion even at low temperature can be obtained. Easy to form. Therefore, by combining and using the (meth) acrylic polymer and the tackifying resin in the specific amount, high adhesiveness and high holding power to rough surfaces, plastics, etc., and adhesiveness at low temperatures are suitably achieved. be able to.
  • the total proportion of the monomer A1 and the monomer A2 may be 75% by weight or more of the total monomer components forming the (meth) acrylic polymer.
  • the resin composition disclosed herein can be suitably carried out using a (meth) acrylic polymer which is a polymer of monomer components of such composition.
  • R 1 is a hydrogen atom or a methyl group.
  • AO is an alkyleneoxy group having 2 to 3 carbon atoms.
  • n is a number indicating the average added mole number of the above alkyleneoxy group, and may be, for example, 1 to 10.
  • R 2 is an aromatic ring or a linear, branched or alicyclic alkyl group. According to the monomer A2 having such a structure, a resin layer having good adhesion even at low temperature and having appropriate adhesion and holding power in a well-balanced manner is easily formed due to appropriate cohesion.
  • the tackifying resin may include at least one selected from the group consisting of rosin-based tackifying resins, terpene-based tackifying resins, petroleum-based tackifying resins, and styrene-based tackifying resins.
  • the techniques disclosed herein can be suitably practiced using such tackifying resins.
  • the resin composition disclosed herein may include at least one tackifying resin having a softening point of 90 ° C. or higher and 160 ° C.
  • the monomer component constituting the (meth) acrylic polymer may include at least one functional group-containing monomer selected from the group consisting of a monomer having a hydroxyl group, a monomer having a carboxyl group, and a monomer having an epoxy group.
  • a functional group-containing monomer can help to adjust the cohesiveness of the resin layer and the storage elastic modulus G '.
  • the weight average molecular weight (Mw) of the (meth) acrylic polymer is preferably 350,000 or more. According to the (meth) acrylic polymer having such Mw, it is easy to obtain a resin layer having well-balanced adhesion and cohesion to the rough surface and the plastic member.
  • the resin composition can contain a crosslinking agent.
  • the crosslinking agent can help to adjust the cohesiveness of the resin layer and the storage elastic modulus G '.
  • the content of the crosslinking agent can be, for example, 0.01 parts by weight or more and 5 parts by weight or less with respect to 100 parts by weight of the (meth) acrylic polymer.
  • an isocyanate type crosslinking agent and an epoxy type crosslinking agent may be used preferably.
  • a resin layer formed from any of the resin compositions disclosed herein is provided.
  • Such a resin layer exhibits good adhesion to adherends such as rough surfaces and plastics, and has adequate cohesion so that it has high retention and good adhesion even at low temperatures. It can be something shown.
  • the resin layer has a storage elastic modulus G ′ at 23 ° C. of 1.0 ⁇ 10 4 Pa or more and 5.0 ⁇ 10 4 Pa or less, and a storage elastic modulus G ′ at ⁇ 10 ° C. Is 3.0 ⁇ 10 4 Pa or more and 7.0 ⁇ 10 5 Pa or less.
  • a resin layer having such properties is preferable because it has a good balance between adhesion and holding power in a room temperature range and tends to exhibit good adhesion even in a low temperature range.
  • storage-elastic-modulus G 'in 23 degreeC may be described with “storage-elastic-modulus G' (23 degreeC).”
  • storage elastic modulus G 'at -10.degree. C. may be expressed as “storage elastic modulus G' (-10.degree. C.)”.
  • the polymer gel fraction of the resin layer may range from 20% to 95% by weight. According to the resin layer having the polymer gel fraction in the above-mentioned range, it is possible to easily achieve both the adhesiveness (for example, the adhesiveness at low temperature) to the rough surface and the cohesion.
  • a laminated sheet having any of the resin layers disclosed herein on at least one side of a support.
  • the laminated sheet can be suitably used for bonding or fixing the adherend, for example, in a mode in which the resin layer is attached to the adherend.
  • the adherend include adherends having rough surfaces as described above and various plastic materials.
  • grain containing sheet can be used preferably, for example.
  • the resin layer may have a 180 ° peel adhesion of 10 N / 20 mm or more measured at a peel rate of 300 mm / min in a 23 ° C. environment.
  • the 180 ° peel adhesion at 23 ° C. may be referred to as “room temperature adhesion”.
  • the above room temperature adhesion can be suitably achieved by using the above (meth) acrylic polymer and a specific amount of tackifying resin in combination.
  • the resin layer may have a 180 ° peel adhesion of 5 N / 20 mm or more measured at a peel rate of 300 mm / min in an environment of ⁇ 10 ° C.
  • the 180 ° peel adhesion at ⁇ 10 ° C. may be referred to as “low temperature adhesion”.
  • the (meth) acrylic polymer is a polymer of a monomer component containing the monomer A1 and the monomer A2 in a specific ratio, and therefore, is excellent in flexibility even in a low temperature range. Therefore, according to the technology disclosed herein, the low temperature adhesion can be suitably achieved by using the (meth) acrylic polymer and the specific amount of the tackifying resin in combination.
  • the resin composition, resin layer and laminate sheet disclosed herein can be used, for example, as a pressure-sensitive adhesive composition, a pressure-sensitive adhesive layer and a pressure-sensitive adhesive sheet.
  • (meth) acrylate is a meaning which generally refers to acrylate and methacrylate.
  • (meth) acrylic acid means acrylic acid and methacrylic acid
  • (meth) acryloyl group generically refers to an acryloyl group and a methacryloyl group, respectively.
  • the resin composition disclosed herein is a polymer of a monomer component containing 50 to 97% by weight of monomer A1 and 3 to 50% by weight of monomer A2 and has a Tg of -40 ° C or less (meth) acrylic It contains a polymer and 5 parts by weight or more and 40 parts by weight or less of a tackifier resin with respect to 100 parts by weight of the (meth) acrylic polymer.
  • the above (meth) acrylic polymer is a specific amount of alkyl (meth) acrylate (monomer A1) having a branched alkyl group having 8 to 18 carbon atoms and a specific amount of (meth) acrylate (monomer A2) having an ether bond And are obtained by polymerizing a monomer component containing In addition, each homopolymer of the monomer A1 and the monomer A2 has a low Tg, and the obtained (meth) acrylic polymer also has a low Tg. According to the resin composition containing such (meth) acrylic polymer, high adhesion and high holding power can be expressed to the adherend having a rough surface by the action of the monomer A1 and the monomer A2.
  • Monomer A1 has low Tg and suitable cohesion and tackiness.
  • the monomer A2 has a low Tg and a suitable polarity, and has a suitable interaction with the adherend surface.
  • the resin composition containing the (meth) acrylic polymer has an adequate softness and cohesion, and an interaction with the interface, and has high adhesion and high adhesion to an adherend having a rough surface. It is presumed that the holding power can be exhibited.
  • the resin composition disclosed herein improves the wettability with respect to the low-polar adherend and the interaction with the adherend interface by including the tackifying resin, and further, it is possible to use the adhesive bulk.
  • the elastic modulus By increasing the elastic modulus, appropriate cohesion can be imparted to the resin layer. This can exhibit high adhesion to various adherends such as rough surfaces and plastics.
  • the use of a tackifying resin is particularly effective for low polarity adherends such as polyolefin resins. And by using a specific amount of the tackifying resin in combination with the (meth) acrylic polymer, it is possible to suppress the decrease in adhesiveness at a low temperature while enjoying the effect by the use of the tackifying resin. It is estimated to be.
  • an alkyl (meth) acrylate having a homopolymer Tg of ⁇ 50 ° C. or less and having a branched alkyl group having 8 to 18 carbon atoms at the end of the ester group is used.
  • the Tg of the homopolymer of the monomer A1 is preferably ⁇ 55 ° C. or less, more preferably ⁇ 60 ° C. or less, from the viewpoint of enhancing the adhesion to an adherend having a rough surface.
  • the Tg of the homopolymer of the monomer A1 is preferably ⁇ 80 ° C. or higher, more preferably ⁇ 75 ° C. or higher, from the viewpoint of enhancing the holding power.
  • the carbon number of the alkyl group of the monomer A1 is preferably 8 to 16, and more preferably 8 to 14 from the viewpoint of imparting appropriate softness to the resin layer and from the viewpoint of enhancing the cohesion of the resin layer. preferable.
  • the Tg of the homopolymer of each monomer is the numerical value described in “Polymer Handbook” (Third Edition, John Wiley & Sons, Inc., 1989).
  • the value of conventional is adopted.
  • the catalog values of the monomer manufacturing companies are adopted.
  • a value obtained by the following measuring method is used. That is, in a reactor equipped with a thermometer, a stirrer, a nitrogen introducing pipe and a reflux condenser, 100 parts by weight of the monomer to be measured, 0.1 parts by weight of 2,2'-azobisisobutyronitrile and acetic acid as a polymerization solvent Charge 200 parts by weight of ethyl, and stir for 1 hour while introducing nitrogen gas. After oxygen in the polymerization system is removed in this manner, the temperature is raised to 60 ° C.
  • test sample sheet-like homopolymer having a thickness of about 50 ⁇ m.
  • a 2-3 mg sample is taken from the obtained test sample, placed in an aluminum container, crimped and subjected to DSC measurement (Q-2000 manufactured by TA Instruments).
  • the temperature program is ⁇ 80 ° C. to 150 ° C. (measurement rate 10 ° C./min), and measurement is performed under nitrogen (50 ml / min) atmosphere gas.
  • Tmg mid-point glass transition temperature
  • the monomers A1 can be used alone or in combination of two or more. From the viewpoint of enhancing
  • (meth) acrylate having a homopolymer Tg of ⁇ 40 ° C. or less and having an ether bond in the molecular skeleton is used.
  • the Tg of the homopolymer of the monomer A2 is preferably ⁇ 45 ° C. or less, more preferably ⁇ 50 ° C. or less, from the viewpoint of enhancing the adhesion to an adherend having a rough surface.
  • the Tg of the homopolymer of the monomer A2 is preferably ⁇ 90 ° C. or higher, and more preferably ⁇ 80 ° C. or higher, from the viewpoint of enhancing the adhesion and retention to an adherend having a rough surface.
  • the said ether bond which monomer A2 has in a molecular skeleton means a chain
  • a monomer having an unsaturated double bond of (meth) acryloyl group and having a linear ether bond can be used without particular limitation.
  • Examples of the monomer A2 include monomers represented by general formula (1): CH 2 CRCR 1 -COO- (AO) n -R 2 ;
  • R 1 in the above general formula (1) is a hydrogen atom or a methyl group.
  • AO is an alkyleneoxy group having 2 to 3 carbon atoms.
  • n is a number indicating the average added mole number of the alkyleneoxy group.
  • R 2 is a monovalent organic group which does not contain an ether bond, and is preferably a hydrocarbon group.
  • Monomer A2 can be used individually by 1 type or in combination of 2 or more types.
  • N in the above general formula (1) may be, for example, 1 to 10. From the viewpoint of polarity level and polymerization reactivity, in some embodiments, n in the general formula (1) is preferably 2 to 8, more preferably 2 to 5.
  • R 2 in the above general formula (1) is preferably a non-substituted aromatic ring or a linear, branched or alicyclic alkyl group.
  • aromatic ring of R 2 include a phenyl group and the like.
  • linear alkyl group of R 2 and branched alkyl groups include an isopropyl group, an ethyl group, a methyl group and the like.
  • alicyclic alkyl group of R 2 include a cyclohexyl group and the like.
  • R 2 is preferably a linear alkyl group or a branched alkyl group, and particularly preferably a linear alkyl group, since it tends to be a linear ether bond-containing (meth) acrylate having a low Tg of a homopolymer.
  • the carbon number of R 2 is preferably 1 to 6, more preferably 1 to 5, and even 1 to 4 or 1 to 3 because it tends to be a monomer A2 having appropriate polarity.
  • alkyleneoxy having an AO of 2 carbon atoms such as methoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, propoxypolyethylene glycol (meth) acrylate, etc.
  • monomers which are groups; and monomers wherein AO is an alkyleneoxy group having 3 carbon atoms such as methoxypolypropylene glycol (meth) acrylate, ethoxypolypropylene glycol (meth) acrylate, propoxypolypropylene glycol (meth) acrylate and the like.
  • the monomer A2 in which R 1 in the general formula (1) is a hydrogen atom is preferable. That is, the monomer A2 is preferably an acrylate.
  • AO in the above general formula (1) is preferably an alkyleneoxy group having 2 carbon atoms, that is, an oxyethylene group, from the viewpoint of having a suitable polar balance.
  • the amount of monomer A1 used is suitably 50 to 97% by weight of the total monomer components forming the (meth) acrylic polymer.
  • the amount of monomer A1 used is preferably 55% by weight or more, more preferably 58% by weight or more, and still more preferably 59% by weight or more, from the viewpoint of enhancing adhesion to a rough surface and holding power. is there.
  • the amount of monomer A1 used is preferably 95% by weight or less, more preferably 93% by weight or less, still more preferably 91% by weight, from the viewpoint of enhancing adhesion to a rough surface and holding power. It is below.
  • the amount of monomer A2 used is suitably 3 to 50% by weight of the total monomer components forming the (meth) acrylic polymer.
  • the amount of monomer A2 used is preferably 3.5% by weight or more, more preferably 4% by weight or more, of the monomer component from the viewpoint of enhancing the adhesion to a rough surface and holding power. More preferably, it is at least weight percent.
  • the amount of monomer A2 used is preferably 48% by weight or less, more preferably 45% by weight or less, and still more preferably 40% by weight, from the viewpoint of enhancing adhesion to a rough surface and holding power. It is below.
  • the total proportion of monomer A1 and monomer A2 may be, for example, 75% by weight or more of the total monomer components. From the viewpoint of further enhancing the adhesion and retention to an adherend having a rough surface, the proportion of the total of the monomer A1 and the monomer A2 is preferably 80% by weight or more of all monomer components, and is 85% by weight or more Is more preferably 90% by weight or more.
  • the monomer component forming the (meth) acrylic polymer may include at least one functional group-containing monomer selected from the group consisting of a monomer having a hydroxyl group, a monomer having a carboxyl group, and a monomer having an epoxy group. .
  • a functional group-containing monomer By including such a functional group-containing monomer, it becomes possible to control the crosslink network formation and the intermolecular interaction while maintaining the softness of the resin layer, and it is possible to enhance the cohesion of the resin layer and express a higher holding power. can do.
  • the monomer component may contain, for example, a combination of a monomer having a hydroxyl group and a monomer having a carboxyl group.
  • the monomer having a hydroxyl group (hydroxyl group-containing monomer) those having a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group and having a hydroxyl group are particularly preferable. It can be used without limitation.
  • hydroxyl group-containing monomer for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl ( Hydroxyalkyl (meth) acrylates such as meta) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxy lauryl (meth) acrylate; (4-hydroxymethylcyclohexyl) methyl And hydroxyalkyl cycloalkane (meth) acrylates such as meta) acrylate; and the like.
  • hydroxyl group-containing monomers examples include hydroxyethyl (meth) acrylamide, allyl alcohol, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, and diethylene glycol monovinyl ether.
  • the hydroxyl group-containing monomers can be used alone or in combination of two or more. Among them, hydroxyalkyl (meth) acrylate is preferable, and 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate are particularly preferable.
  • the monomer having a carboxyl group those having a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group and having a carboxyl group are particularly limited. It can be used without.
  • the carboxyl group-containing monomer include (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid and the like.
  • the carboxyl group-containing monomers can be used alone or in combination of two or more. Among these, acrylic acid and methacrylic acid are preferable, and acrylic acid is particularly preferable.
  • the monomer having an epoxy group examples include those having a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group and having an epoxy group are particularly limited. It can be used without.
  • the epoxy group-containing monomer examples include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether and the like.
  • the epoxy group-containing monomers can be used singly or in combination of two or more.
  • the amount used in the case of using a hydroxyl group-containing monomer is preferably 0.01% by weight or more of all monomer components forming the (meth) acrylic polymer, from the viewpoint of enhancing the cohesion, and 0.03% by weight or more It is more preferable that The amount of the hydroxyl group-containing monomer used is suitably 20% by weight or less, preferably 15% by weight or less, from the viewpoint of suppressing excessive increase in viscosity and gelation, preferably 10% by weight or less. % Or less is more preferable, 5% by weight or less is further preferable, 3% by weight or less is further more preferable, and 2% by weight or less is particularly preferable.
  • the amount used is that of all the monomer components forming the (meth) acrylic polymer from the viewpoint of enhancing the cohesion and from the viewpoint of imparting molecular level interaction with the adherend surface. It is preferable that it is 0.1 weight% or more, and it is more preferable that it is 0.2 weight% or more.
  • the amount of the carboxyl group-containing monomer used is preferably 5% by weight or less, and 3% by weight or less, from the viewpoint of enhancing followability to a rough surface and maintaining high adhesive strength at low temperature. Some are more preferable, 2.6% by weight or less is further preferable, and 2.2% by weight or less is particularly preferable.
  • the amount used in the case of using an epoxy group-containing monomer is preferably 0.1% by weight or more of all monomer components forming the (meth) acrylic polymer, from the viewpoint of enhancing the cohesion, 0.2% by weight or more It is more preferable that The amount of the epoxy group-containing monomer used is preferably 1% by weight or less of the above-mentioned monomer component, and more preferably 0.5% by weight or less, from the viewpoint of suppressing gelation and viscosity increase.
  • a (meth) acrylic-type polymer is a graft polymer, it is not this limitation.
  • the weight ratio of the hydroxyl group-containing monomer to the carboxyl group-containing monomer (hydroxyl group-containing monomer / carboxyl group-containing monomer) From the viewpoint of enhancing the adhesive strength to the adherend, it is preferably 0.01 or more, more preferably 0.02 or more, and preferably 1.0 or less, more preferably 0.50 or less.
  • the monomer component forming the (meth) acrylic polymer is, in addition to the above-mentioned monomer A1 and monomer A2, if necessary, a copolymerizable monomer other than the above functional group-containing monomer (corresponding to monomer A1 or monomer A2 May be included).
  • the copolymerizable monomers can be used singly or in combination of two or more.
  • copolymerization monomer for example, a monomer represented by the general formula (2): CH 2 CRCR 3 -COO-R 4 ;
  • R 3 in the above general formula (2) is a hydrogen atom or a methyl group.
  • R 4 is a C 1-24 unsubstituted alkyl group or a substituted alkyl group.
  • the unsubstituted alkyl group having 1 to 24 carbon atoms (more preferably 1 to 18 carbon atoms) or a substituted alkyl group as R 4 in the general formula (2) is a linear or branched alkyl group. Or a cyclic cycloalkyl group.
  • R 4 may be a linear alkyl group having 1 to 18 carbon atoms, a branched alkyl group having 3 to 7 carbon atoms, a cyclic alkyl group, or the like.
  • R 4 is a substituted alkyl group
  • preferable examples of the substituent include an aryl group having 3 to 7 carbon atoms and an aryloxy group having 3 to 7 carbon atoms.
  • the aryl group is not particularly limited, but is preferably, for example, a phenyl group.
  • Examples of the monomer represented by the above general formula (2) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, s-butyl (meth) acrylate and t-butyl (meth) Acrylate, isobutyl (meth) acrylate, n-pentyl (meth) acrylate, isopentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, isoamyl (meth) acrylate, n-octyl (meth) acrylate, n Nonyl (meth) acrylate, phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, 3,3,5-trimethylcyclohexyl (meth) acrylate, isobornyl
  • vinyl monomers such as vinyl acetate, vinyl propionate, styrene, ⁇ -methylstyrene, N-vinylcaprolactam, N-vinylpyrrolidone and the like; tetrahydrofurfuryl (meth) acrylate, fluorine (Meth) acrylate monomers such as (meth) acrylates, silicone (meth) acrylates and 2-methoxyethyl acrylate; cyano group-containing monomers such as (meth) acrylonitrile; other, amide group-containing monomers, amino group-containing monomers, Imide group-containing monomers, N-acryloyl morpholine, vinyl ether monomers and the like can also be used.
  • vinyl monomers such as vinyl acetate, vinyl propionate, styrene, ⁇ -methylstyrene, N-vinylcaprolactam, N-vinylpyrrolidone and the like
  • silane type monomer containing a silicon atom and the like can be mentioned.
  • silane monomers include 3-acryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 4-vinylbutyltrimethoxysilane, 4-vinylbutyltriethoxysilane, 8-vinyloctyltrimethoxysilane 8-vinyloctyl triethoxysilane, 10-methacryloyloxydecyl trimethoxysilane, 10-acryloyloxydecyl trimethoxysilane, 10-methacryloyloxydecyl triethoxysilane, 10-acryloyloxydecyl triethoxysilane, and the like.
  • the amount of the copolymerizable monomer used is preferably 20% by weight or less, and more preferably 15% by weight or less, of all the monomer components forming the (meth) acrylic polymer.
  • the content of the copolymerizable monomer exceeds 20% by weight, for example, the adhesion to a rough surface may be reduced.
  • the monomer component which forms the said (meth) acrylic-type polymer can contain a polyfunctional monomer as needed for the purpose of preparation of cohesion force etc.
  • a polyfunctional monomer can be used individually by 1 type or in combination of 2 or more types.
  • the above-mentioned polyfunctional monomer is a monomer having at least two polymerizable functional groups ((meth) acryloyl group, vinyl group etc.) having unsaturated double bond, and, for example, (poly) ethylene glycol di (meth) acrylate , (Poly) propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,2- Ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,12-dodecanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethane tri (meth
  • the said polyfunctional monomer can be used by 5 weight% or less with respect to all the monomer components which form a (meth) acrylic-type polymer.
  • the above-mentioned polyfunctional monomer varies depending on the molecular weight, the number of functional groups, etc., it is preferably 3% by weight or less, more preferably 2% by weight or less, based on all the monomer components forming the (meth) acrylic polymer. If the content of the polyfunctional monomer is too large, for example, the modulus of elasticity of the resin composition may be too high, and the adhesion to a rough surface (particularly, the adhesion in a low temperature range) may be reduced.
  • the Tg of the (meth) acrylic polymer is ⁇ 40 ° C. or less.
  • the Tg of the (meth) acrylic polymer is preferably ⁇ 45 ° C. or less, more preferably ⁇ 50 ° C. or less, from the viewpoint of enhancing the adhesion to an adherend having a rough surface.
  • the Tg of the (meth) acrylic polymer is, for example, preferably ⁇ 55 ° C. or less, more preferably ⁇ 57 ° C. or less, and still more preferably ⁇ 60 ° C. or less, from the viewpoint of enhancing adhesion at low temperatures.
  • the Tg of the (meth) acrylic polymer is preferably ⁇ 85 ° C. or higher, and more preferably ⁇ 80 ° C. or higher, from the viewpoint of enhancing the adhesion and retention to an adherend having a rough surface. preferable.
  • the Tg of the (meth) acrylic polymer is a theoretical value calculated from the following Fox equation based on the composition of the monomer component constituting the (meth) acrylic polymer.
  • Fox's formula: 1 / Tg W 1 / Tg 1 + W 2 / Tg 2 +... + W n / Tg n
  • Tg is the glass transition temperature (unit: K) of the (meth) acrylic polymer
  • the manufacturing method of the said (meth) acrylic-type polymer is not specifically limited, A well-known manufacturing method can be selected suitably.
  • various radical polymerization methods such as solution polymerization, radiation polymerization by irradiation with electron beam and ultraviolet light (UV), bulk polymerization, emulsion polymerization and the like can be used.
  • the (meth) acrylic polymer to be obtained may be any of a random copolymer, a block copolymer, a graft copolymer and the like.
  • Mw of the said (meth) acrylic-type polymer is controllable by a polymerization initiator, a chain transfer agent, reaction conditions, etc., and the use amount is suitably adjusted according to these kind.
  • solution polymerization for example, ethyl acetate, toluene, a mixed solvent of these, and the like may be used as a polymerization solvent.
  • the above-mentioned solution polymerization is carried out, for example, under a stream of an inert gas such as nitrogen, usually with a polymerization initiator at about 50 to 70 ° C., for about 5 to 30 hours.
  • polymerization initiator examples include, for example, 2,2′-azobisisobutyronitrile (AIBN), 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis [2- (5) -Methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis (2-methylpropionamidine) disulfate, 2,2'-azobis (N, N'-dimethyleneisobutylamidine) Azo initiators such as 2,2'-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate (manufactured by Wako Pure Chemical Industries, Ltd., VA-057); potassium persulfate, ammonium persulfate, etc.
  • AIBN 2,2′-azobisisobutyronitrile
  • 2-amidinopropane 2,2′-azobis [2- (5) -Methyl-2-imidazolin-2-
  • the polymerization initiators can be used singly or in combination of two or more.
  • the use amount of the polymerization initiator is usually preferably about 0.005 to 1 part by weight, and more preferably about 0.01 to 0.5 part by weight, with respect to 100 parts by weight of the monomer component. preferable.
  • chain transfer agent examples include lauryl mercaptan, glycidyl mercaptan, mercaptoacetic acid, 2-mercaptoethanol, thioglycolic acid, 2-ethylhexyl thioglycolate, 2,3-dimercapto-1-propanol and the like.
  • the chain transfer agent can be used alone or in combination of two or more.
  • the amount of the chain transfer agent used is usually about 0.1 parts by weight or less based on 100 parts by weight of the total amount of monomer components. Alternatively, chain transfer agents may not be used.
  • Emulsion polymerization is typically carried out using known emulsifiers.
  • the emulsifier include anionic emulsifiers such as sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecyl benzene sulfonate, ammonium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl phenyl ether sulfate, etc .; polyoxyethylene alkyl ether, polyoxyethylene alkyl And nonionic emulsifiers such as phenyl ether, polyoxyethylene fatty acid ester, polyoxyethylene-polyoxypropylene block polymer and the like.
  • emulsifier As said emulsifier, you may use the emulsifier in which radically polymerizable functional groups, such as a propenyl group and allyl ether group, were introduce
  • An emulsifier into which such a polymerizable functional group is introduced is generally referred to as a reactive emulsifier.
  • Specific examples of the reactive emulsifier include Aqualon HS-10, HS-20, KH-10, BC-05, BC-10, BC-20 (all of which are manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), Adekaria Soap SE10 N. (Made by ADEKA company) etc. are mentioned.
  • Reactive emulsifiers are preferred because they are incorporated into the polymer chain after polymerization, which improves the water resistance.
  • An emulsifier can be used individually by 1 type or in combination of 2 or more types.
  • the amount of the emulsifier used is usually about 0.3 to 5 parts by weight with respect to 100 parts by weight of the monomer component, and is about 0.5 to 1 part by weight in view of polymerization stability and mechanical stability. It is preferable to
  • the (meth) acrylic polymer When the (meth) acrylic polymer is produced by radiation polymerization, it can be produced by polymerizing the above-mentioned monomer component by irradiation with radiation such as electron beam and UV.
  • radiation polymerization When the radiation polymerization is performed by an electron beam, it is not particularly necessary to include a photopolymerization initiator in the monomer component.
  • the radiation polymerization is performed by UV polymerization, it is preferable that the monomer component contains a photopolymerization initiator from the viewpoint of shortening the polymerization time and the like.
  • a photoinitiator can be used individually by 1 type or in combination of 2 or more types.
  • the photopolymerization initiator is not particularly limited as long as it can initiate photopolymerization, and can be appropriately selected and used from various known photopolymerization initiators.
  • photopolymerization initiators such as benzoin ether type, acetophenone type, ⁇ -ketol type, photoactive oxime type, benzoin type, benzyl type, benzophenone type, ketal type and thioxanthone type can be used.
  • the amount of the photopolymerization initiator used is 0.05 to 1.5 parts by weight, preferably 0.1 to 1 parts by weight, per 100 parts by weight of the monomer component.
  • the weight average molecular weight (Mw) of the (meth) acrylic polymer is preferably 350,000 or more.
  • the Mw of the (meth) acrylic polymer is more preferably 400,000 or more, and still more preferably 500,000 or more, from the viewpoint of enhancing the durability and cohesion of the resin layer.
  • the Mw of the (meth) acrylic polymer is preferably 3,000,000 or less, more preferably 2,500,000 or less, from the viewpoint of enhancing the adhesiveness at low temperatures and from the viewpoint of suppressing the increase in viscosity of the resin composition. Is more preferably 2,000,000 or less, still more preferably 1.5,000,000 or less, and even more preferably 1.2,000,000 or less.
  • the Mw of the (meth) acrylic polymer can be measured by GPC (gel permeation chromatography) under the following conditions, and calculated in terms of polystyrene.
  • GPC gel permeation chromatography
  • the sample for GPC the sample is dissolved in tetrahydrofuran (THF) to make a 0.1% by weight solution, which is allowed to stand overnight, and then the filtrate filtered through a 0.45 ⁇ m membrane filter is used.
  • THF tetrahydrofuran
  • the resin composition disclosed herein can optionally contain a crosslinking agent.
  • crosslinking agents include isocyanate crosslinking agents, epoxy crosslinking agents, silicone crosslinking agents, oxazoline crosslinking agents, aziridine crosslinking agents, silane crosslinking agents, alkyl etherified melamine crosslinking agents, metal chelate crosslinking agents
  • Cross-linking agents such as, but not limited to, peroxides.
  • an isocyanate type crosslinking agent and an epoxy-type crosslinking agent are mentioned.
  • An isocyanate crosslinking agent and an epoxy crosslinking agent may be used in combination.
  • the crosslinking agents may be used alone or in combination of two or more.
  • the amount of the crosslinking agent used is preferably in the range of 0.005 parts by weight to 10 parts by weight with respect to 100 parts by weight of the (meth) acrylic polymer.
  • the content of the crosslinking agent relative to 100 parts by weight of the (meth) acrylic polymer is preferably 0.01 parts by weight or more and 4 parts by weight or less, more preferably 0.02 parts by weight or more and 3 parts by weight or less, More preferably, it is 0.05 parts by weight or more and 2 parts by weight or less.
  • the amount of the polyfunctional monomer used is preferably in the range of 0.001 parts by weight to 2 parts by weight with respect to 100 parts by weight of the (meth) acrylic polymer, and is preferably 0.003 parts by weight or more More preferably, it is in the range of 1 part by weight or less.
  • isocyanate type crosslinking agent use is made of a compound having two or more isocyanate groups (which may be isocyanate regenerated functional groups in which an isocyanate group is temporarily protected by a blocking agent or quantification or the like).
  • isocyanate-based crosslinking agent examples include tolylene diisocyanate, aromatic isocyanates such as xylene diisocyanate, alicyclic isocyanates such as isophorone diisocyanate, aliphatic isocyanates such as hexamethylene diisocyanate, and the like.
  • examples of the isocyanate-based crosslinking agent include lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate, cycloaliphatic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate and isophorone diisocyanate, and the like.
  • Aromatic diisocyanates such as 2,4-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, polymethylene polyphenylisocyanate, trimethylolpropane / tolylene diisocyanate trimer adduct (Tosoh Corp., product Name: Coronate L), trimethylolpropane / hexamethylene diisocyanate trimer adduct (made by Tosoh Corp., trade name: Coronate HL), hexamethylole Isocyanate adducts of isocyanurate of diisocyanate (Tosoh Corp., trade name: Coronate HX) etc., trimethylolpropane adduct of xylylene diisocyanate (Mitsui Chemical Co., Ltd., trade name: Takenate D110N), trimethylolose of xylylene diisocyanate Propan
  • An isocyanate type crosslinking agent can be used individually by 1 type or in combination of 2 or more types.
  • the amount of the isocyanate crosslinking agent used can be, for example, 0.01 parts by weight or more and 10 parts by weight or less with respect to 100 parts by weight of the (meth) acrylic polymer, and usually 0.03 parts by weight or more and 8 parts by weight or less It is preferable to set it as 0.05 to 6 parts by weight, or more preferably to 0.08 to 5 parts by weight.
  • the amount of the isocyanate crosslinking agent used can be appropriately set in consideration of cohesion, prevention of peeling in the durability test, and the like.
  • the amount of the isocyanate crosslinking agent used relative to 100 parts by weight of the (meth) acrylic polymer is 5.0 parts by weight from the viewpoint of facilitating exerting good adhesion even at low temperatures in the composition containing the tackifying resin. It may be less than 4.0 parts by weight, preferably less than 3.0 parts by weight, more preferably less than 2.0 parts by weight, and less than 1.5 parts by weight More preferably, it is particularly preferably less than 1.0 part by weight.
  • the amount of the isocyanate crosslinking agent used is preferably, for example, 0.10 parts by weight or more, from the viewpoint of facilitating exerting good holding power in the composition containing the tackifying resin, and is preferably 0 More preferably, it is at least 20 parts by weight.
  • an isocyanate-based crosslinking agent is contained in an aqueous resin composition (for example, a resin composition containing an aqueous dispersion of (meth) acrylic polymer prepared by emulsion polymerization), the isocyanate-based crosslinking agent and water are used.
  • an isocyanate crosslinking agent in which an isocyanate group is temporarily protected by a blocking agent or quantification.
  • an isocyanate crosslinking agent may not be used.
  • epoxy crosslinking agent the polyfunctional epoxy compound which has 2 or more of epoxy groups in 1 molecule can be used.
  • epoxy crosslinking agents include N, N, N ', N'-tetraglycidyl-m-xylenediamine, diglycidyl aniline, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, 1, 6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, sorbitol polyglycidyl ether, glycerol polyglycidyl ether, penta Erythritol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitan polyglycid
  • the epoxy crosslinking agents can be used singly or in combination of two or more.
  • the use amount of the epoxy-based crosslinking agent can be, for example, about 0.005 part by weight or more and about 1 part by weight or less with respect to 100 parts by weight of the (meth) acrylic polymer, and 0.01 part by weight or more and 0.5 parts by weight Or less or about 0.015 parts by weight or more and 0.3 parts by weight or less.
  • the use amount of the epoxy-based crosslinking agent can be appropriately set in consideration of cohesion, durability and the like.
  • any radically active species can be generated by heating to promote crosslinking of the above (meth) acrylic polymer of the resin composition, but it is possible to use appropriately, but it is possible to improve workability and stability.
  • a peroxide having a half-life temperature of 80 ° C. to 160 ° C., and more preferably 90 ° C. to 140 ° C.
  • peroxide examples include di (2-ethylhexyl) peroxydicarbonate (one-minute half-life temperature: 90.6 ° C.), di (4-t-butylcyclohexyl) peroxydicarbonate (one-minute half-life) Temperature: 92.1 ° C), di-sec-butylperoxydicarbonate (one-minute half-life temperature: 92.4 ° C), t-butyl peroxy neodecanoate (one-minute half-life temperature: 103.5 ° C) ), T-Hexyl peroxypivalate (one-minute half-life temperature: 109.1 ° C), t-butylperoxypivalate (one-minute half-life temperature: 110.3 ° C), dilauroyl peroxide (one-minute half-life) Temperature: 116.4 ° C.), di-n-octanoyl peroxide (one-minute half-life temperature: 117.4 ° C.), 1,1,
  • di (4-t-butylcyclohexyl) peroxydicarbonate one-minute half-life temperature: 92.1 ° C.
  • dilauroyl peroxide one-minute half-life temperature: 116. 4 ° C.
  • dibenzoyl peroxide one-minute half-life temperature: 130.0 ° C.
  • the half life of the said peroxide is an index showing the decomposition rate of a peroxide, and means the time until the remaining amount of a peroxide becomes half.
  • the decomposition temperature for obtaining the half life at any time and the half life time at any temperature are described in the manufacturer catalog etc. For example, “Organic peroxide catalog 9th edition of NOF Corporation ( May 2003) and the like.
  • the peroxides may be used alone or in combination of two or more.
  • the amount of the peroxide used is usually about 0.02 to 2 parts by weight, preferably about 0.05 to 1 parts by weight, per 100 parts by weight of the (meth) acrylic polymer. It is preferable to do.
  • the amount of the peroxide used is appropriately selected within this range in order to adjust the processability, reworkability, crosslinking stability, peelability and the like.
  • the amount of peroxide remaining after the reaction treatment can be determined, for example, by measuring the amount of peroxide decomposition by HPLC (high performance liquid chromatography). Specifically, for example, a sample of about 0.2 g is collected from the resin layer after reaction treatment, immersed in 10 ml of ethyl acetate, shaken and extracted at 120 rpm for 3 hours at 25 ° C. with a shaker, and then room temperature Let stand for 3 days. Then, add 10 ml of acetonitrile, shake at 120 rpm for 30 minutes at 25 ° C., filter through a membrane filter (0.45 ⁇ m), inject about 10 ⁇ l of the extract into HPLC and analyze, and after reaction treatment The amount of peroxide can be
  • bonds with the atom in an organic compound or coordination bond can be used.
  • polyvalent metals include Al, Cr, Zr, Co, Cu, Fe, Ni, V, Zn, In, Ca, Mg, Mn, Y, Ce, Sr, Ba, Mo, La, Sn, Ti, etc.
  • an oxygen atom and the like can be mentioned.
  • the organic compound include alkyl esters, alcohol compounds, carboxylic acid compounds, ether compounds and ketone compounds.
  • the tackifying resin used for the resin composition disclosed herein is not particularly limited, and can be appropriately selected from known tackifying resins.
  • tackifying resins for example, rosin-based tackifying resin, terpene-based tackifying resin, phenol-based tackifying resin, hydrocarbon-based tackifying resin, ketone-based tackifying resin, polyamide-based tackifying resin, epoxy-based tackifying resin, elastomer-based tackifying resin Etc.
  • the tackifying resin can be used singly or in combination of two or more.
  • rosin-based tackifying resins examples include unmodified rosin (raw rosin) such as gum rosin, wood rosin, tall oil rosin, and modified rosin obtained by modifying these unmodified rosins by polymerization, disproportionation, hydrogenation, etc.
  • unmodified rosin raw rosin
  • modified rosin obtained by modifying these unmodified rosins by polymerization, disproportionation, hydrogenation, etc.
  • polymerized rosins stabilized rosins, disproportionated rosins, fully hydrogenated rosins, partially hydrogenated rosins, and other chemically modified rosins
  • various rosin derivatives may be mentioned.
  • rosin derivatives examples include rosin phenol resins obtained by adding phenol to an rosin (unmodified rosin, modified rosin, various rosin derivatives and the like) with an acid catalyst and thermally polymerizing it; Ester compounds of rosin obtained by esterifying unmodified rosin with alcohol (unmodified rosin ester), modified rosin such as polymerized rosin, stabilized rosin, disproportionated rosin, fully hydrogenated rosin, partially hydrogenated rosin, etc.
  • Rosin ester-based resins such as ester compounds of modified rosin esterified by esterification (polymerized rosin ester, stabilized rosin ester, disproportionated rosin ester, fully hydrogenated rosin ester, partially hydrogenated rosin ester, etc.); Unsaturated fatty acid modified rosin based resins modified with unsaturated fatty acids such as unmodified rosins and modified rosins (polymerized rosins, stabilized rosins, disproportionated rosins, fully hydrogenated rosins, partially hydrogenated rosins, etc.); Unsaturated fatty acid modified rosin ester resin modified from rosin ester resin with unsaturated fatty acid; Carboxyl group in unmodified rosin, modified rosin (polymerized rosin, stabilized rosin, disproportionated rosin, completely hydrogenated rosin, partially hydrogenated rosin, etc.), unsaturated fatty acid modified rosin resin and
  • terpene-based tackifying resins include terpene-based resins such as ⁇ -pinene polymers, ⁇ -pinene polymers and dipentene polymers, and those terpene-based resins modified (phenol modification, aromatic modification, hydrogenation modification And modified terpene resins (eg, terpene phenol resins, styrene modified terpene resins, aromatic modified terpene resins, hydrogenated terpene resins, etc.) and the like.
  • terpene-based resins such as ⁇ -pinene polymers, ⁇ -pinene polymers and dipentene polymers
  • those terpene-based resins modified phenol modification, aromatic modification, hydrogenation modification And modified terpene resins (eg, terpene phenol resins, styrene modified terpene resins, aromatic modified terpene resins, hydrogenated terpene resins, etc.) and the like.
  • phenol-based tackifying resins include condensates of various phenols (eg, phenol, m-cresol, 3,5-xylenol, p-alkylphenol, resorcin etc.) with formaldehyde (eg, alkylphenol-based resin, xylene formaldehyde) And resins such as resoles obtained by subjecting the above-mentioned phenols and formaldehyde to an addition reaction with an alkali catalyst, and novolaks obtained by subjecting the above-mentioned phenols and formaldehyde to a condensation reaction with an acid catalyst.
  • phenols eg, phenol, m-cresol, 3,5-xylenol, p-alkylphenol, resorcin etc.
  • formaldehyde eg, alkylphenol-based resin, xylene formaldehyde
  • resins such as resoles obtained by subjecting the above-mentioned
  • hydrocarbon-based tackifying resins examples include petroleum-based tackifying resins and styrene-based tackifying resins. More specifically, aliphatic hydrocarbon resins, aromatic hydrocarbon resins, aliphatic cyclic hydrocarbon resins, aliphatic / aromatic petroleum resins (such as styrene-olefin copolymers), aliphatic Aliphatic petroleum resins, hydrogenated hydrocarbon resins, coumarone resins, coumarone indene resins and the like can be mentioned.
  • rosin-based tackifying resins that can be preferably used include Pencel series, which are rosin ester-based tackifying resins manufactured by Arakawa Chemical Industries, Ltd., such as “Pencel AZ”, “Pencel D-125”, and “Pencel D- 135 ",” Pencel D-160 “,” Pencel KK “,” Pencel C "and the like, but not limited thereto.
  • the tackifying resin is suitably used in a range of 5 parts by weight to 40 parts by weight with respect to 100 parts by weight of the (meth) acrylic polymer.
  • the amount of tackifier resin used is preferably, for example, 7 parts by weight or more, and more preferably 10 parts by weight or more with respect to 100 parts by weight of the (meth) acrylic polymer.
  • the amount of tackifier resin used is preferably, for example, 38 parts by weight or less, and more preferably 35 parts by weight or less with respect to 100 parts by weight of the (meth) acrylic polymer.
  • the softening point (softening temperature) of the tackifying resin is not particularly limited.
  • the softening point of the tackifying resin is preferably 180 ° C. or less, more preferably 160 ° C. or less, and 150 ° C. or less, 140 ° C. or less from the viewpoint of facilitating exerting good adhesion even at low temperature. Or 135 ° C. or less.
  • the softening point of the tackifying resin is suitably 60 ° C. or more, and is 80 ° C. or more It is preferable that it is 90 degreeC or more.
  • tackifying resin having a softening point in the range of 90 ° C. to 160 ° C., 90 ° C. to 150 ° C., or 90 ° C. to 140 ° C.
  • at least one type of tackifying resin has the above-mentioned softening point.
  • 50% by weight or more, 70% by weight or more, 90% by weight or more or 100% by weight of the total amount of the tackifying resin has the above-mentioned softening point.
  • the softening point of tackifying resin can employ
  • the resin composition disclosed herein may contain (meth) acrylic oligomers.
  • a (meth) acrylic oligomer refers to a polymer containing a monomer unit derived from a monomer having a (meth) acryloyl group (that is, a (meth) acrylic monomer) in a polymer structure, and typically It refers to a polymer containing the monomer unit in a proportion of more than 50% by weight.
  • Tg is higher than said (meth) acrylic-type polymer, and a polymer with small Mw can be used preferably.
  • the (meth) acrylic oligomer may help to improve the adhesion to adherends such as rough surfaces and plastics.
  • the (meth) acrylic oligomer preferably has a Tg of about 0 ° C. to 300 ° C., preferably about 20 ° C. to 300 ° C., and more preferably about 40 ° C. to 300 ° C. If the Tg is less than about 0 ° C., the cohesion of the resin layer may be reduced in a temperature range of room temperature or higher, and the retention characteristics and the adhesiveness at high temperature may be reduced.
  • Tg of a (meth) acrylic-type oligomer is a theoretical value calculated based on the formula of Fox similarly to Tg of a (meth) acrylic-type polymer.
  • the Mw of the (meth) acrylic oligomer may be, for example, 1,000 or more and less than 30,000, preferably 1,500 or more and less than 20,000, and more preferably 2,000 or more and less than 10,000. If the Mw is 30000 or more, the effect of improving the adhesion may not be obtained sufficiently. Moreover, since it becomes low molecular weight as Mw is less than 1000, it may cause the fall of adhesive force and a retention characteristic. Mw of a (meth) acrylic-type oligomer can be calculated
  • methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth), for example is mentioned.
  • the above (meth) acrylic oligomers are alkyl (meth) acrylates having a branched alkyl group such as isobutyl (meth) acrylate and t-butyl (meth) acrylate; cyclohexyl (meth) acrylate and isobornyl (meth)
  • a cyclic structure of an ester of (meth) acrylic acid such as acrylate dicyclopentanyl (meth) acrylate with an alicyclic alcohol, or an aryl (meth) acrylate such as phenyl (meth) acrylate or benzyl (meth) acrylate
  • UV is used for synthesis of (meth) acrylic oligomers and preparation of a resin layer
  • it is an ester of an alcohol and (meth) acrylic acid which does not contain an unsaturated bond in that polymerization inhibition is unlikely to occur.
  • Certain (meth) acrylates are preferred.
  • an alkyl (meth) acrylate in which the alkyl group has a branched structure, or an ester of an alicyclic alcohol and (meth) acrylic acid can be suitably used as a monomer constituting the (meth) acrylic oligomer.
  • suitable (meth) acrylic oligomers include, for example, cyclohexyl methacrylate (CHMA), dicyclopentanyl acrylate (DCPA), dicyclopentanyl methacrylate (DCPMA), isobornyl acrylate (IBXA) And homopolymers such as isobornyl methacrylate (IBXMA) 1-adamantyl acrylate (ADA), 1-adamantyl methacrylate (ADMA), etc .; copolymer of CHMA and isobutyl methacrylate (IBMA), co-polymerization of CHMA and IBXMA Polymer, copolymer of CHMA and acryloyl morpholine (ACMO), copolymer of CHMA and diethyl acrylamide (DEAA), copolymer of ADA and methyl methacrylate (MMA), DCPMA and IBX Copolymers of A, a copolymer of DCPMA and MMA; and
  • the amount thereof to be used is not particularly limited.
  • the amount of the (meth) acrylic oligomer used is preferably 70 parts by weight or less, for example 1 to 70 parts by weight, with respect to 100 parts by weight of the (meth) acrylic polymer, more preferably Is 2 to 50 parts by weight, more preferably 3 to 40 parts by weight.
  • the addition amount of the (meth) acrylic oligomer is too large, the elastic modulus may be too high, and the rough surface adhesion at low temperature may be lowered.
  • the effect of improving the adhesive strength can be suitably exhibited.
  • the technology disclosed herein can be preferably practiced in a form not using (meth) acrylic oligomers.
  • the resin composition disclosed herein may contain a silane coupling agent for the purpose of improving the adhesion reliability at the interface with the adherend, and the like.
  • a silane coupling agent for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4 epoxycyclohexyl) ethyl Epoxy group-containing silane coupling agents such as trimethoxysilane, 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-triethoxysilyl-N- (1,3 Amino-containing silane coupling agents such as -dimethylbutylidene) propylamine, N-phenyl- ⁇ -aminopropyltrimethoxysilane, 3-acryloxy
  • the amount of the silane coupling agent to be used is preferably 1 part by weight or less, for example 0.01 to 1 part by weight, more preferably 0.02 to 0.6, per 100 parts by weight of the (meth) acrylic polymer. It is a weight part.
  • the amount of the silane coupling agent used is too large, the crosslinking may be inhibited or the adhesion properties may be impaired.
  • the technology disclosed herein can be preferably practiced even in a form that does not use a silane coupling agent.
  • the resin composition disclosed herein may contain other known additives as needed.
  • powders such as colorants and pigments, dyes, surfactants, plasticizers, surface lubricants, leveling agents, softeners, antioxidants, antioxidants, light stabilizers, ultraviolet light absorbers, polymerization inhibitors, Inorganic or organic fillers, metal powders, particles, foils and the like can be added as appropriate depending on the application.
  • a resin layer formed from any of the resin compositions disclosed herein is provided.
  • the thickness of the resin layer is not particularly limited.
  • the thickness of the resin layer may be, for example, about 1 ⁇ m to 1000 ⁇ m, preferably about 2 ⁇ m to 500 ⁇ m, and more preferably 2 ⁇ m to 300 ⁇ m.
  • the thickness of the resin layer may be, for example, 5 ⁇ m or more, 10 ⁇ m or more, 25 ⁇ m or more, 35 ⁇ m or more in some aspects, from the viewpoint of improving adhesion and adhesion to rough asperities. It may be 50 ⁇ m or more or 70 ⁇ m or more.
  • the thickness of the resin layer may be, for example, 200 ⁇ m or less, 150 ⁇ m or less, or 100 ⁇ m or less.
  • the resin layer disclosed herein may have a single layer structure or a multilayer structure of two or more layers.
  • the polymer gel fraction of the resin layer is not particularly limited. From the viewpoint of adhesion to rough surfaces, usually 20 to 98% by weight is suitable. In some embodiments, the polymer gel fraction of the resin layer may be, for example, 20 to 95% by weight.
  • the polymer gel fraction of the resin layer is in the above range, high adhesion and high holding power tend to be suitably developed. It is presumed that when the polymer gel fraction of the resin layer is in the above-mentioned range, the softness of the resin layer can be maintained, and cohesion can be imparted by formation of a suitable crosslinked network. .
  • the polymer gel fraction of the resin layer is, for example, preferably 22% by weight or more, more preferably 25% by weight or more, and more preferably 30% by weight or more from the viewpoint of enhancing the cohesion and retention of the resin layer. It is further preferred that Further, from the viewpoint of enhancing the rough surface adhesion at a low temperature, the polymer gel fraction of the resin layer is, for example, preferably 90% by weight or less, more preferably 85% by weight or less, and 80% by weight or less Is more preferably 75% by weight or less, still more preferably 70% by weight or less.
  • the said resin composition contains a crosslinking agent
  • the influence of a crosslinking process temperature and crosslinking process time is considered, and a gel fraction is controlled. it can.
  • the polymer gel fraction of a resin layer is measured by the method as described in the Example mentioned later.
  • the resin layer disclosed herein preferably has a storage modulus G ′ (23 ° C.) of 1.0 ⁇ 10 4 Pa or more and 5.0 ⁇ 10 4 Pa or less.
  • a storage modulus G ′ (23 ° C.) of the resin layer is lowered, the adhesion of the resin layer to the unevenness of the rough surface (followability to the unevenness shape) tends to be high.
  • the adhesion becomes high the contact area between the resin layer and the rough surface becomes large, and the adhesion becomes easy to improve.
  • the storage elastic modulus G ′ (23 ° C.) of the resin layer is, for example, preferably 4.8 ⁇ 10 4 Pa or less, and 4.6 ⁇ 10 4 Pa or less Is more preferred.
  • the storage elastic modulus G ′ (23 ° C.) of the resin layer may be, for example, 1.2 ⁇ 10 4 Pa or more. Or 1.5 ⁇ 10 4 Pa or more.
  • the storage elastic modulus G ′ (23 ° C.) of the resin layer can be measured using a commercially available dynamic viscoelasticity measuring device, and more specifically, it is measured by the method described in the examples described later.
  • the storage elastic modulus G ′ (23 ° C.) of the resin layer can be adjusted by the composition of the monomer component constituting the acrylic polymer, the use of a crosslinking agent, the use of a tackifying resin, and the like. For example, by increasing the weight fraction of monomer A2 in the monomer component or by decreasing the weight ratio of monomer A1 to monomer A2 (ie, by using more monomer A2 to monomer A1) ), The storage modulus G ′ (23 ° C.) of the resin layer can be reduced.
  • An example of the monomer A2 having a high effect of reducing the storage elastic modulus G ′ (23 ° C.) is a linear ether bond-containing (meth) acrylate represented by the above general formula (1), and the Tg of homopolymer is ⁇ 40 C. or less (more preferably -45.degree. C. or less, more preferably -50.degree. C. or less, for example -55.degree. C. or less) can be mentioned.
  • the resin layer disclosed herein preferably has a storage modulus G ′ ( ⁇ 10 ° C.) of 3.0 ⁇ 10 4 Pa or more and 7.0 ⁇ 10 5 Pa or less.
  • the low storage elastic modulus G ′ ( ⁇ 10 ° C.) of the resin layer is advantageous from the viewpoint of facilitating good adhesion of the resin layer to the irregularities of the rough surface even at low temperatures and enhancing the rough surface adhesion at low temperatures. It is. From such a viewpoint, in some embodiments, the storage elastic modulus G ′ ( ⁇ 10 ° C.) of the resin layer is, for example, preferably 6.5 ⁇ 10 5 Pa or less, and 6.0 ⁇ 10 5 Pa or less Is more preferred.
  • the storage elastic modulus G ′ ( ⁇ 10 ° C.) of the resin layer may be, for example, 5.0 ⁇ 10 4 Pa or more. It may be 7.0 ⁇ 10 4 Pa or more.
  • the storage elastic modulus G ′ ( ⁇ 10 ° C.) of the resin layer can be measured using a commercially available dynamic viscoelasticity measuring apparatus, as with the storage elastic modulus G ′ (23 ° C.), and more specifically, it will be described later It measures by the method as described in the Example which The storage elastic modulus G ′ ( ⁇ 10 ° C.) of the resin layer can be adjusted by the composition of the monomer component constituting the acrylic polymer, the use of a crosslinking agent, the use of a tackifying resin, and the like.
  • the haze value of the resin layer disclosed herein is not particularly limited.
  • the embodiment can be carried out in a mode in which the haze value of the resin layer is 10% or less when the thickness of the resin layer is 85 ⁇ m.
  • the haze value of the resin layer at a thickness of 85 ⁇ m is 1.9% or less.
  • the laminate sheet having the highly transparent resin layer has an application that requires high light transmittance in a configuration having or not having a support, and a performance that allows the adherend to be visually recognized well through the laminate sheet.
  • it is suitable for the use by which the property which can visually recognize the external appearance of the said support body through a resin layer is calculated
  • the haze value of the resin layer at a thickness of 85 ⁇ m is more preferably 1.5% or less, still more preferably 1% or less, and still more preferably 0.7% or less.
  • the lower limit of the haze value of the resin layer is not particularly limited. For example, it can be carried out in an embodiment in which the haze value of the resin layer with a thickness of 85 ⁇ m is 0% or more (for example, 0.05% or more).
  • the haze value of the laminated sheet is not particularly limited. For example, it can carry out in the aspect which is 15% or less in the haze value of a lamination sheet with a base material.
  • the laminated sheet with a substrate having high transparency is suitable for applications in which high light transmittance is required, and applications in which performance capable of favorably visually recognizing an adherend through the laminate sheet is required.
  • the haze value of the base material-laminated sheet is 5% or less, more preferably 1.9% or less, and still more preferably 1.5% or less (e.g. 1% or less).
  • the lower limit of the haze value of the laminated sheet with a substrate is not particularly limited.
  • it can be implemented in the aspect whose haze value of a lamination sheet with a base material is 0% or more (for example, 0.05% or more).
  • the “haze value” refers to the ratio of diffuse transmission light to total transmission light when the measurement target is irradiated with visible light. It is also called cloudy price.
  • the resin layer can be formed, for example, as a laminated sheet by applying the resin composition on one side or both sides of a support and removing the polymerization solvent or the like by heat drying or the like.
  • the support constituting the laminated sheet may be a releasable support (that is, a support capable of releasing the resin layer constituting the laminated sheet) or a non-removable support.
  • a resin layer from the resin composition apply
  • one or more solvents other than the polymerization solvent may be appropriately added, as appropriate, for the purpose of improving the coatability and adjusting the thickness.
  • Various methods can be used as a method of applying the above-mentioned resin composition. Specifically, for example, roll coat, kiss roll coat, gravure coat, reverse coat, roll brush, spray coat, dip roll coat, bar coat, knife coat, air knife coat, curtain coat, lip coat, die coater etc. Methods such as extrusion coating may be mentioned.
  • the heating and drying temperature is preferably 40 to 200 ° C., more preferably 50 to 180 ° C., and particularly preferably 70 to 170 ° C. By making heating temperature into said range, the resin layer which has the outstanding adhesion characteristic can be obtained.
  • the heating and drying time is preferably 5 seconds to 20 minutes, more preferably 5 seconds to 15 minutes, and particularly preferably 10 seconds to 10 minutes.
  • a resin layer can be formed.
  • materials that can be blended into the above-mentioned resin composition such as a crosslinking agent can be appropriately blended.
  • the above monomer components may be used in the form of syrup by polymerizing a part thereof in advance of ultraviolet irradiation.
  • a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp or the like can be used.
  • a polyolefin film mainly composed of polyolefin such as polyethylene (PE), polypropylene (PP) and ethylene-propylene copolymer, and a polyester mainly composed of polyethylene terephthalate (PET) and polybutylene terephthalate etc.
  • Polyester film polyvinyl chloride film containing polyvinyl chloride as a main component, others, polyethersulfone film, polystyrene film, polyacrylic film, polyurethane film, polyimide film, polyamide film, polyamideimide film, cycloolefin film, ethylene- Plastic film such as vinyl alcohol copolymer film; Porous material such as paper, cloth, non-woven fabric, etc .; Net; Air such as polyethylene foam or acrylic foam Containing sheet; metal foil; and can include these complexes, various support film and the like.
  • the composite include, but are not limited to, a laminate of a metal foil and a plastic film, and a plastic film reinforced with an inorganic fiber such as glass fiber and carbon fiber.
  • the concept of air bubbles in the air bubble-containing sheet includes air bubbles not having a solid outer shell and air bubbles having a solid outer shell (for example, by containing hollow particles). Therefore, in this application, the above-mentioned bubble-containing sheet may be referred to as "bubble or particle-containing sheet".
  • the bubble or particle-containing sheet may include one or both of a bubble having no solid shell and a bubble having a solid shell.
  • the thickness of the support film is usually about 5 ⁇ m to about 3000 ⁇ m, preferably about 10 ⁇ m to about 2500 ⁇ m, and more preferably about 20 ⁇ m to about 2000 ⁇ m. In some embodiments, the thickness of the support film may be, for example, 1000 ⁇ m or less, 500 ⁇ m or less, 300 ⁇ m or less, 100 ⁇ m or less, or 50 ⁇ m or less.
  • the support film may be subjected to release treatment and antifouling treatment with a silicone-based, fluorine-based, long-chain alkyl-based or fatty acid amide-based release agent, silica powder, or the like, as necessary.
  • the support film may be subjected to antistatic treatment such as application of an antistatic agent, kneading, deposition, and the like.
  • the laminated sheet 1 includes a support film 10 having a first surface 10A and a second surface 10B, and an adhesive layer 21 which is a resin layer provided on the first surface 10A side.
  • the first surface 10A is non-peelable, whereby the laminate sheet 1 is configured as a single-sided adhesive sheet with a substrate.
  • the laminated sheet 1 before use may further include a release liner 31 for protecting the surface (adhesive surface) 21A of the pressure-sensitive adhesive layer 21, as shown in FIG. .
  • At least the side of the release liner 31 in contact with the adhesive surface 21A is a release surface (release surface). In practical use, the release liner 31 is released from the adhesive surface 21A.
  • the structural example of the lamination sheet which concerns on other one Embodiment is typically shown in FIG.
  • the laminated sheet 2 is provided on the second surface 10B side, the support film 10 having the first surface 10A and the second surface 10B, the pressure-sensitive adhesive layer 21 which is a resin layer provided on the first surface 10A side. And an adhesive layer 22 which is a resin layer.
  • the first surface 10A and the second surface 10B are both non-peelable, whereby the laminate sheet 2 is configured as a double-sided pressure-sensitive adhesive sheet with a substrate.
  • the pressure-sensitive adhesive sheet 2 before use is, as shown in FIG. 2, a release liner 31, 32 for protecting the surface (first adhesive surface) 21A of the adhesive layer 21 and the surface (second adhesive surface) 22A of the adhesive layer 22. May be further included.
  • the release liners 31 and 32 have at least the side in contact with the adhesive surfaces 21A and 22A as the release surfaces, and are peeled off from the adhesive surfaces 21A and 22A in practical use.
  • the laminated sheet 3 includes a pressure-sensitive adhesive layer 21 which is a resin layer, a release liner 31 which protects one surface (first pressure-sensitive adhesive surface) 21A of the pressure-sensitive adhesive layer 21, and the other surface of the pressure-sensitive adhesive layer 21 (second Adhesive surface) a release liner 32 for protecting 21B.
  • the release liners 31, 32 are peeled off from the adhesive surfaces 21A, 21B.
  • the pressure-sensitive adhesive layer 21 of this embodiment can also be grasped as a pressure-sensitive adhesive sheet not having a non-peelable support, that is, a substrate-less pressure-sensitive adhesive sheet.
  • plastic film such as polyethylene, polypropylene, polyethylene terephthalate, polyester film, porous material such as paper, cloth, non-woven fabric, net, bubble-containing sheet, metal foil, laminate of these, etc. And the like.
  • a plastic film can be used suitably from the point which is excellent in surface smoothness.
  • the plastic film is not particularly limited as long as it can protect the resin layer.
  • polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer examples include coalesced films, polyethylene terephthalate films, polybutylene terephthalate films, polyurethane films, ethylene-vinyl acetate copolymer films and the like.
  • the thickness of the release liner is usually about 5 to 300 ⁇ m, preferably about 5 to 200 ⁇ m.
  • the above release liner may, if necessary, be a releasing agent of silicone type, fluorine type, long chain alkyl type or fatty acid amide type, release by silica powder etc., antifouling treatment, coating type, kneading type, vapor deposition It is also possible to carry out antistatic treatment of a mold or the like.
  • the peelability from the resin layer can be further enhanced by appropriately performing the peeling treatment such as silicone treatment, long-chain alkyl treatment, fluorine treatment and the like on the surface of the release liner.
  • the resin layer (a substrate-less pressure-sensitive adhesive sheet, a single-sided pressure-sensitive adhesive sheet with a substrate, or a resin layer constituting a double-sided pressure-sensitive adhesive sheet with a substrate) disclosed herein may be a polypropylene (PP) plate
  • the room temperature 180 ° peel adhesion (hereinafter also referred to as PP room temperature adhesion) measured as an adherend is preferably 10 N / 20 mm or more, more preferably 11 N / 20 mm or more.
  • the room temperature adhesion of the resin layer to PP may be, for example, 12 N / 20 mm or more, or 13 N / 20 mm or more.
  • the upper limit of the adhesion to PP room temperature is not particularly limited, and may be, for example, about 30 N / 20 mm or less.
  • the resin layer disclosed herein preferably has a room temperature of 180 ° peel adhesion (hereinafter also referred to as "plywood room temperature adhesion") of 8 N / 20 mm or more, which is measured using softwood plywood as an adherend.
  • the above-mentioned plywood room temperature adhesion is more preferably 10 N / 20 mm or more, further preferably 15 N / 20 mm or more, and may be 18 N / 20 mm or more or 20 N / 20 mm or more.
  • the upper limit of the room temperature adhesion to the plywood is not particularly limited, and may be, for example, about 50 N / 20 mm or less, or about 40 N / 20 mm or less.
  • the resin layer disclosed herein preferably has a room temperature of 180 ° peel adhesion (hereinafter also referred to as an adhesion to a silica glass plate at room temperature) measured with a calcium silicate plate as an adherend of 10 N / 20 mm or more.
  • the above-mentioned carbonal plate room temperature adhesive strength is more preferably 15 N / 20 mm or more, and may be 20 N / 20 mm or more.
  • low-temperature 180 ° peel adhesion (hereinafter also referred to as low-temperature adhesion to plywood) measured with softwood plywood as an adherend is, for example, 1 N / 20 mm or more or 3 N / 20 mm or more And may preferably be 5 N / 20 mm or more.
  • the above-mentioned low-temperature adhesion to plywood may be, for example, 7 N / 20 mm or more, and 9 N / 20 mm or more.
  • the (meth) acrylic polymer is a polymer of a monomer component containing the monomer A1 and the monomer A2 in a specific ratio, and therefore, is excellent in flexibility even in a low temperature range.
  • the upper limit of the low-temperature adhesion to plywood is not particularly limited, and may be, for example, about 50 N / 20 mm or less, or about 40 N / 20 mm or less.
  • the room temperature 180 ° peel adhesion and the low temperature 180 ° peel adhesion of the resin layer are measured by the methods described in the examples below.
  • a backing material for example, one side of the above-mentioned resin layer
  • a PET film having a thickness of about 25 ⁇ m can be attached and reinforced. The same applies to a retention test to be described later. Further, the same reinforcement can be performed as needed also in the resin layer constituting the single-sided pressure-sensitive adhesive sheet with a substrate or the double-sided pressure-sensitive adhesive sheet with a substrate.
  • the resin layer disclosed herein preferably has a displacement distance of less than 1.0 mm, more preferably 0.8 mm or less, in a holding power test measured by the method described in the examples described later.
  • the resin layer has a moderately high cohesive force. According to such a resin layer, the adherend can be firmly bonded or fixed.
  • the resin layer disclosed herein can be preferably used for applications to be applied to adherends or plastics having rough surfaces.
  • adherends having a rough surface include concrete, mortar, gypsum board, softwood plywood, wood-based cement board, calcium silicate board, tile, and fiber-reinforced cement board, but are not limited thereto.
  • the arithmetic mean roughness Ra of the rough surface may be, for example, about 1 ⁇ m to 800 ⁇ m.
  • the above-mentioned laminated sheet can be preferably used particularly for an adherend having a rough surface having an arithmetic mean roughness Ra of 1 ⁇ m to 500 ⁇ m.
  • the arithmetic mean roughness Ra of the rough surface may be, for example, about 3 ⁇ m to 300 ⁇ m, or about 5 ⁇ m to 150 ⁇ m.
  • the resin layer and the laminate sheet disclosed herein can also be firmly adhered to a smooth adherend, and can be preferably applied to such adherends.
  • the resin layer disclosed herein takes advantage of the characteristic of being able to adhere well to any of rough surfaces and plastics, and uses which can be applied to both rough surfaces and plastics (for example, adherends having rough surfaces and the like) It can be preferably used in the application of joining with a plastic member.
  • the plastic may be a low polarity plastic such as, for example, a polyolefin resin such as PP or PE.
  • (meth) acrylic polymers having a glass transition temperature of ⁇ 40 ° C. or less, 5 parts by weight or more and 40 parts by weight or less of a tackifier resin with respect to 100 parts by weight of the (meth) acrylic polymer
  • a resin composition containing The above (meth) acrylic polymer is 50 to 97% by weight of an alkyl (meth) acrylate (A1) having a branched alkyl group having a carbon number of 8 to 18 and having a glass transition temperature of -50 ° C.
  • a resin composition which is a polymer of a monomer component containing [2] The ratio of the total of the above alkyl (meth) acrylate (A1) and the above (meth) acrylate (A2) having an ether bond is 75 weight with respect to all the monomer components forming the above (meth) acrylic polymer The resin composition as described in said [1] which is% or more.
  • the above-mentioned tackifying resin contains at least one selected from the group consisting of rosin-based tackifying resin, terpene-based tackifying resin, petroleum-based tackifying resin, and styrene-based tackifying resin, The resin composition in any one of 6].
  • the above-mentioned monomer component contains at least one functional group-containing monomer selected from the group consisting of monomers having a hydroxyl group, monomers having a carboxyl group, and monomers having an epoxy group.
  • the adherend is made of concrete, mortar, gypsum board, softwood plywood, wood based cement board, calcium silicate board, tile and fiber reinforced cement board
  • the adherend comprising the adherend having a rough surface, and the laminated sheet according to any one of the above [20] to [23], wherein the resin layer adheres to the rough surface, and the adherend and the above adhere Laminated structure integrated with a laminated sheet.
  • the adherend having the above rough surface is selected from concrete, mortar, gypsum board, softwood plywood, wood based cement board, calcium silicate board, tile and fiber reinforced cement board, the above [26] or [26] 27] laminated structure.
  • Example 1 (Preparation of (meth) acrylic polymer)
  • 2EHA 2-ethylhexyl acrylate
  • CBA ethyl carbitol acrylate
  • 4HBA 4-hydroxybutyl acrylate 0.25 parts and 1 part of acrylic acid (AA)
  • AIBN 2,2'-azobisisobutyronitrile
  • the liquid temperature in the flask was kept at around 60 to 65 ° C., and polymerization reaction was carried out for 10 hours to prepare a (meth) acrylic polymer solution.
  • the (meth) acrylic polymer had a Mw of 850,000 as determined by GPC.
  • a polymerizing rosin ester (trade name: Pencel D125, manufactured by Arakawa Chemical Industries, Ltd., a softening point of 120 to 130 as a tackifying resin in 100 parts of solid content of the polymer in the (meth) acrylic polymer solution obtained above.
  • the resin composition solution was applied to the release surface of the release liner such that the thickness of the resin layer after drying was 85 ⁇ m, and drying was performed at 130 ° C. for 3 minutes to form a resin layer.
  • a laminated sheet having a resin layer on one side of the release liner i.e., a releasable support
  • As the release liner a 38 ⁇ m-thick PET film (Diafoil MRF, manufactured by Mitsubishi Resins Co., Ltd.), one surface of which is a release surface by silicone treatment, was used.
  • the said resin layer may be grasped also as a substrate-less pressure-sensitive adhesive layer.
  • Example 1 the type and composition ratio of the monomer used for preparation of the (meth) acrylic polymer, the type and amount of tackifier resin and the type and amount of the crosslinking agent are as shown in Table 1 respectively.
  • a resin layer having a thickness of 85 ⁇ m was produced on the release surface of the release liner by the same procedure as in Example 1 except that a laminated sheet was obtained.
  • Mw and Tg of the (meth) acrylic polymer according to each example are shown in Table 1.
  • ⁇ Measurement of polymer gel fraction> A sample of a predetermined amount (first weight W1) is taken from the resin layer, immersed in an ethyl acetate solution and left at room temperature for 1 week, then the insoluble matter is taken out and the dried weight (W2) is measured.
  • the polymer gel fraction was calculated from the obtained resin layer gel fraction by the following equation.
  • the number of tackifying resin parts in the following formula means the number of tackifying resin parts contained in the resin layer relative to 100 parts of the polymer contained in the resin layer.
  • Polymer gel fraction (%) resin layer gel fraction (%) ⁇ (100 + number of tackifying resin parts) / 100
  • ⁇ Measurement of storage elastic modulus G '> The resin layers were superposed to prepare a laminate having a thickness of about 2 mm. A sample in which the above laminate was punched into a disk shape having a diameter of 7.9 mm was sandwiched between parallel plates, and temperature dispersion measurement was performed under the following conditions using a viscoelasticity tester. From the results, storage modulus G '(unit; Pa) at 23 ° C and -10 ° C was read.
  • the adhesive surface of the above test piece (that is, the other side of the resin layer) is softwood plywood (obtained from Shimada Holmes, thickness 12 mm) as an adherend, Calcium silicate board (Keikaru board, stained # 400 made by A & A Materials Co., Ltd., thickness 6 mm), or polypropylene board (Kobe Kobel sheet manufactured by Shin-Kobe Electric Co., Ltd., thickness 2 mm) I put it back and forth. After this was allowed to stand for 30 minutes in the above standard environment, the peel adhesion (N / 20 mm) was measured under the conditions of a peeling angle of 180 ° and a peeling speed of 300 mm / min in the same environment.
  • the adhesive surface (that is, the other surface of the resin layer) of the above test piece is a glass plate (made by Matsunami Glass Industry Co., Ltd., thickness 1) as an adherend 1)
  • a 2 kg roller was attached to 1 .2 mm). After this was allowed to stand for 30 minutes in the above standard environment, the peel adhesion (N / 20 mm) was measured under the conditions of a peeling angle of 180 ° and a peeling speed of 300 mm / min in the same environment.
  • ⁇ Holding force measurement> The evaluation sample prepared in the same manner as the above room temperature adhesion measurement was cut into a width of 10 mm and a length of about 100 mm to prepare a test piece. Subsequently, the adhesive surface of the above test piece was crimped to a Bakelite plate (made by Sumitomo Bakelite Co., Ltd., thickness 2 mm) as an adherend with 1 kg of a 2 kg roller reciprocating with a bonding area of 10 mm in width and 20 mm in length. . After leaving the adherend on which the test piece is attached in this manner for 30 minutes at room temperature (23 ° C.), the test piece is suspended so that the length direction of the test piece is in the vertical direction. After a load of 500 g was applied to the free end and the sample was left in a 40 ° C. environment for 1 hour, the displacement distance (mm) from the first application position of the test piece was measured.
  • a Bakelite plate made by Sumitomo Bakelite Co., Ltd., thickness 2
  • the resin layer according to each example is attached to one surface of alkali-free glass with a total light transmittance of 93.3% and a haze value of 0.1% as a test piece, and the haze value of the test piece is a haze meter (MR-100 And Murakami Color Research Laboratory).
  • the above test piece was placed so that the resin layer was on the light source side. Since the haze value of the non-alkali glass is 0.1%, the value obtained by subtracting 0.1% from the measured value is taken as the haze value of the resin layer.
  • C trimethylolpropane / 2,4-tolylene diisocyanate trimer adduct (manufactured by Tosoh Corporation, trade name: Coronate L).
  • DN trimethylolpropane adduct of xylylene diisocyanate (Mitsui Chemical Co., Ltd., trade name: Takenate D110N)
  • D Polymerized rosin ester having a softening point of 120 to 130 ° C. (manufactured by Arakawa Chemical Industries, Ltd., trade name: Pencel D125).
  • A Rosin ester having a softening point of 95 to 105 ° C. (manufactured by Arakawa Chemical Industries, trade name: Pencel AZ).
  • T Terpene phenol resin having a softening point of 125 to 135 ° C. (Yashara Chemical Co., Ltd., trade name: YS Polystar T130)
  • ND Not rated.
  • the resin layers formed from the resin compositions of Examples 1 to 16 exhibit high room temperature adhesion to both rough surfaces and plastics, and have rough surfaces at low temperatures. It showed good adhesion. These resin layers were also excellent in holding power.

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  • Adhesive Tapes (AREA)

Abstract

L'invention concerne une couche de résine apte à adhérer fortement à une surface rugueuse et à une matière plastique, la couche de résine ayant une puissance de maintien élevée et présentant une bonne adhérence même à basse température, une composition de résine appropriée pour former la couche de résine, et une feuille stratifiée comprenant la couche de résine. La composition de résine selon la présente invention contient un polymère (méth)acrylique ayant une Tg de -40 °C ou moins, et 5 à 40 parties en poids d'une résine collante par rapport à 100 parties en poids du polymère (méth)acrylique. Le polymère (méth)acrylique est un polymère de constituants monomères comprenant : 50 à 97 % en poids d'un (méth)acrylate d'alkyle (A1) ayant un groupe alkyle ramifié en C8-18 à une extrémité terminale d'un groupe ester, un homopolymère du (méth)acrylate d'alkyle (A1) ayant une Tg de -50 °C ou moins ; et 3 à 50 % en poids d'un (méth)acrylate (A2) ayant une liaison éther dans son squelette moléculaire, un homopolymère du (méth)acrylate (A2) ayant une Tg de -40 °C ou moins.
PCT/JP2018/040971 2017-12-28 2018-11-05 Composition de résine, couche de résine, et feuille stratifiée WO2019130822A1 (fr)

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JP2018194150A JP7185479B2 (ja) 2017-12-28 2018-10-15 樹脂組成物、樹脂層、および積層シート

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021111568A1 (fr) * 2019-12-04 2021-06-10 昭和電工マテリアルズ株式会社 Film absorbant les chocs, composition de résine photodurcissable, matériau en feuille et dispositif d'affichage d'image
WO2022054789A1 (fr) * 2020-09-14 2022-03-17 日東電工株式会社 Feuille adhésive

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JP2008069261A (ja) * 2006-09-14 2008-03-27 Soken Chem & Eng Co Ltd 粘着剤組成物および粘着シート
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JP2018016785A (ja) * 2016-07-14 2018-02-01 日東電工株式会社 樹脂組成物、樹脂層、および積層シート
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JP2003277709A (ja) * 2002-03-26 2003-10-02 Nippon Shokubai Co Ltd 粘着剤組成物および粘着製品
JP2008069261A (ja) * 2006-09-14 2008-03-27 Soken Chem & Eng Co Ltd 粘着剤組成物および粘着シート
JP2008280375A (ja) * 2007-05-08 2008-11-20 Soken Chem & Eng Co Ltd 表面保護フィルム用粘着剤組成物
JP2013159662A (ja) * 2012-02-02 2013-08-19 Nitto Denko Corp 表面保護フィルム
JP2015187261A (ja) * 2014-03-13 2015-10-29 Dic株式会社 粘着シート
JP2017095598A (ja) * 2015-11-25 2017-06-01 東洋インキＳｃホールディングス株式会社 粘着剤および粘着テープ
JP2018016785A (ja) * 2016-07-14 2018-02-01 日東電工株式会社 樹脂組成物、樹脂層、および積層シート
JP2018130934A (ja) * 2017-02-17 2018-08-23 日東電工株式会社 積層シート

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021111568A1 (fr) * 2019-12-04 2021-06-10 昭和電工マテリアルズ株式会社 Film absorbant les chocs, composition de résine photodurcissable, matériau en feuille et dispositif d'affichage d'image
WO2022054789A1 (fr) * 2020-09-14 2022-03-17 日東電工株式会社 Feuille adhésive

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