WO2018012161A1 - Resin composition, resin layer, and laminated sheet - Google Patents

Resin composition, resin layer, and laminated sheet Download PDF

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Publication number
WO2018012161A1
WO2018012161A1 PCT/JP2017/021435 JP2017021435W WO2018012161A1 WO 2018012161 A1 WO2018012161 A1 WO 2018012161A1 JP 2017021435 W JP2017021435 W JP 2017021435W WO 2018012161 A1 WO2018012161 A1 WO 2018012161A1
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Prior art keywords
meth
acrylate
weight
monomer
resin composition
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Application number
PCT/JP2017/021435
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French (fr)
Japanese (ja)
Inventor
昌嗣 東
裕 戸崎
Original Assignee
日東電工株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Priority claimed from JP2017108906A external-priority patent/JP6893124B2/en
Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Priority to US16/316,769 priority Critical patent/US20190292414A1/en
Priority to KR1020187031100A priority patent/KR102288096B1/en
Priority to CN201780034772.9A priority patent/CN109312139A/en
Priority to EP17827293.6A priority patent/EP3486284A4/en
Publication of WO2018012161A1 publication Critical patent/WO2018012161A1/en

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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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1515—Three-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
    • 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
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen

Definitions

  • the present invention relates to a resin composition, a resin layer, and a laminated sheet.
  • pressure-sensitive adhesive sheets include concrete, mortar, gypsum board, softwood plywood, wood-based cement board, calcium silicate board, tile, and Adhesive strength to adherends having rough surfaces (surfaces with irregularities) such as fiber reinforced cement boards is not sufficient, and adhesives are often used for adherends having rough surfaces. It was. However, in recent years, with the increase in the need to attach and fix these adherends to each other and other adherends more easily, even for adherends having these rough surfaces, lamination of adhesive sheets and the like It is strongly desired to join using a sheet.
  • Patent Document 1 discloses a pressure-sensitive adhesive sheet provided with a rubber-based pressure-sensitive adhesive layer that exhibits good adhesion to an adherend having a rough surface such as concrete.
  • the formation of the rubber-based pressure-sensitive adhesive layer requires curing after the application of the rubber-based pressure-sensitive adhesive, and there is a concern from the viewpoint of production efficiency.
  • tackifier since a large amount of tackifier is added, there is a concern about a decrease in adhesive strength at low temperatures.
  • Patent Document 2 discloses adhesives for optical members using various (meth) acrylates. However, it does not disclose the adhesive force to the adherend having the rough surface as described above.
  • the laminated sheet such as the pressure-sensitive adhesive sheet used for the adherend having a rough surface as described above, in addition to the adhesive force, from the viewpoint of holding a heavy object fixed to the adherend for a long period of time. Holding power is also required.
  • An object of the present invention is to provide a resin composition capable of achieving both high adhesive force and high holding force for an adherend having a rough surface.
  • the present invention also aims to provide a resin layer formed from the resin composition, and further to provide a laminated sheet having the resin layer.
  • the present invention provides 50 to 97% by weight of alkyl (meth) acrylate (a1) having a Tg of a homopolymer of ⁇ 50 ° C. or less and having a branched alkyl group having 8 to 18 carbon atoms at the terminal of the ester group.
  • the Tg obtained by polymerizing a monomer component containing 3 to 50% by weight of (meth) acrylate (a2) having a Tg of the homopolymer of ⁇ 40 ° C. or less and having an ether bond in the molecular skeleton.
  • the present invention relates to a resin composition comprising a (meth) acrylic polymer having a temperature of ⁇ 40 ° C. or lower.
  • the total ratio of the alkyl (meth) acrylate (a1) and the (meth) acrylate (a2) having an ether bond is based on the total monomer components forming the (meth) acrylic polymer. It is preferably 75% by weight or more.
  • the (meth) acrylate (a2) having an ether bond has the general formula (1): CH 2 ⁇ CR 1 —COO— (AO) n —R 2 [the above general formula (1) Wherein R 1 is a hydrogen atom or a methyl group, AO is an alkyleneoxy group having 2 to 3 carbon atoms, n is 1 to 8 indicating the average number of moles added of the alkyleneoxy group, and R 2 is an aromatic ring or a straight chain A branched chain or alicyclic alkyl group. It is preferable that it is a monomer represented by this.
  • the monomer component further includes a monomer having at least one functional group selected from a monomer having a hydroxyl group, a monomer having a carboxyl group, and a monomer having an epoxy group. preferable.
  • the monomer component may further contain a polyfunctional monomer in an amount of 5% by weight or less based on the total monomer components forming the (meth) acrylic polymer.
  • the (meth) acrylic polymer preferably has a weight average molecular weight of 350,000 or more.
  • the resin composition of the present invention preferably further contains 0.01 to 5 parts by weight of a crosslinking agent with respect to 100 parts by weight of the (meth) acrylic polymer.
  • the crosslinking agent is preferably an isocyanate crosslinking agent and / or an epoxy crosslinking agent.
  • the present invention relates to a resin layer obtained from a resin composition.
  • the resin layer of the present invention preferably has a gel fraction of 20 to 95% by weight.
  • the present invention relates to a laminated sheet characterized in that the resin layer is provided on at least one side of a support.
  • the 180 ° peel adhesive strength of the resin layer to the adherend is preferably 10 N / 20 mm or more under the condition of a peeling rate of 300 mm / min.
  • the support is any one of a plastic film, paper, nonwoven fabric, and a bubble-containing sheet.
  • AO in the general formula (1) is an oxyethylene group.
  • n in the general formula (1) is preferably 2-8.
  • R 2 in the general formula (1) is an unsubstituted aromatic ring having 1 to 6 carbon atoms, or a linear, branched, or alicyclic alkyl group. Is preferred.
  • the monomer having a hydroxyl group is preferably 0.01% by weight or more and 3% by weight or less based on all monomer components forming the (meth) acrylic polymer.
  • the monomer having a carboxyl group is preferably 0.1% by weight or more and 5% by weight or less based on all monomer components forming the (meth) acrylic polymer.
  • the adherend of the laminated sheet of the present invention is preferably one of concrete, mortar, gypsum board, softwood plywood, wood cement board, calcium silicate board, tile, and fiber reinforced cement board. It can be strongly bonded to other smooth adherends.
  • the resin composition, resin layer and laminated sheet of the present invention can be used as, for example, an adhesive composition, an adhesive layer and an adhesive sheet.
  • the (meth) acrylic polymer as the main component in the resin composition of the present invention is a monomer component containing a specific amount of an alkyl (meth) acrylate having a long-chain branched alkyl group and a (meth) acrylate having an ether bond. It was obtained by polymerizing. In addition, each homopolymer of the alkyl (meth) acrylate having a branched alkyl group having a long chain and the (meth) acrylate having an ether bond has a low glass transition temperature (Tg) and was obtained (meth) Acrylic polymers also have low Tg.
  • Tg glass transition temperature
  • an adherend having a rough surface is obtained by the action of the alkyl (meth) acrylate having a long-chain branched alkyl group and the (meth) acrylate having an ether bond.
  • a high adhesive force and a high holding force can be expressed.
  • An alkyl (meth) acrylate having a branched alkyl group having 8 to 18 carbon atoms has a low Tg and appropriate cohesion and adhesiveness
  • the (meth) acrylate having an ether bond has a low Tg and appropriate polarity.
  • the resin composition of the present invention has an appropriate softness, cohesion, and interaction with the interface, and has a rough surface.
  • the monomer component further includes a monomer having at least one functional group selected from a monomer having a hydroxyl group, a monomer having a carboxyl group, and a monomer having an epoxy group.
  • the gel fraction of the resin layer formed from the resin composition of the present invention is, for example, about 20 to 95% by weight, the softness of the resin layer can be maintained, and aggregation can be achieved by forming an appropriate crosslinked network. Since a force can be applied, it is presumed that a higher adhesive force and a higher holding force can be expressed on an adherend having a rough surface.
  • the resin composition of the present invention comprises an alkyl (meth) acrylate (a1) having a Tg of a homopolymer of ⁇ 50 ° C. or lower and a branched alkyl group having 8 to 18 carbon atoms at the end of the ester group. It was obtained by polymerizing a monomer component containing 3 to 50% by weight of (meth) acrylate (a2) having a weight% and Tg of the homopolymer of ⁇ 40 ° C. or less and having an ether bond in the molecular skeleton.
  • a (meth) acrylic polymer having a Tg of ⁇ 40 ° C. or lower is included.
  • (meth) acrylate means an acrylate and / or a methacrylate.
  • Alkyl (meth) acrylate (a1) having a branched alkyl group having 8 to 18 carbon atoms at the terminal of the ester group >
  • the Tg of the homopolymer of alkyl (meth) acrylate (a1) having a branched alkyl group having 8 to 18 carbon atoms at the end of the ester group of the present invention is ⁇ 50 ° C. or lower.
  • the Tg of the alkyl (meth) acrylate (a1) is preferably ⁇ 55 ° C. or less, more preferably ⁇ 60 ° C. or less, from the viewpoint of increasing the adhesive force to the adherend having a rough surface.
  • the Tg of the alkyl (meth) acrylate (a1) is preferably ⁇ 80 ° C. or higher, and more preferably ⁇ 75 ° C. or higher, from the viewpoint of increasing the holding power for the adherend having a rough surface.
  • the number of carbon atoms of the alkyl group of the alkyl (meth) acrylate (a1) is preferably 8 to 16 from the viewpoint of imparting appropriate softness to the resin layer and increasing the cohesive strength of the resin layer. More preferably, it is -14.
  • the Tg of the homopolymer of each monomer is a numerical value described in “Polymer Handbook” (3rd edition, John Wiley & Sons, Inc. 1989) (when there are a plurality of numerical values, a conventional value is adopted, If not stated, use the catalog value of the monomer manufacturer).
  • the Tg of a homopolymer of a monomer not described in the above literature is a value obtained by the following measurement method. That is, in a reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser, 100 parts by weight of the monomer to be measured, 0.1 part by weight of azobisisobutyronitrile, and 200 parts by weight of ethyl acetate as a polymerization solvent. Stir for 1 hour while charging nitrogen gas. After removing oxygen in the polymerization system in this way, the temperature is raised to 60 ° C. and reacted for 12 hours.
  • this homopolymer solution is cast-coated on a release liner, and it dries and produces the test sample (sheet-like homopolymer) about 50 micrometers thick. 2 to 3 mg of the obtained sample is collected, placed in an aluminum container, crimped, and subjected to DSC measurement (TA-Instruments Q-2000). The temperature program was measured under an atmosphere gas of ⁇ 80 ° C. to 150 ° C. (measurement speed 10 ° C./min) and nitrogen (50 ml / min). A value of Tmg (midpoint glass transition temperature) was read from the obtained chart, and this value was defined as Tg of the homopolymer.
  • the alkyl (meth) acrylate (a1) can be used alone or in combination.
  • the alkyl (meth) acrylate (a1) is preferably an alkyl acrylate from the viewpoint of increasing the adhesive strength of the resin layer and from the viewpoint of polymerization reactivity.
  • the Tg of the homopolymer of (meth) acrylate (a2) having an ether bond of the present invention is ⁇ 40 ° C. or lower.
  • the Tg of the (meth) acrylate (a2) having an ether bond is preferably ⁇ 45 ° C. or less, more preferably ⁇ 50 ° C. or less, from the viewpoint of increasing the adhesion to an adherend having a rough surface. preferable.
  • the Tg of the (meth) acrylate (a2) having an ether bond is preferably ⁇ 90 ° C. or higher, and preferably ⁇ 80 ° C.
  • the ether bond means a chain ether bond and is different from a cyclic ether bond such as an epoxy group or an oxetane group.
  • the (meth) acrylate (a2) having an ether bond those having an unsaturated double bond of a (meth) acryloyl group and having a chain ether bond can be used without particular limitation.
  • Examples of the (meth) acrylate (a2) having an ether bond include, for example, the general formula (1): CH 2 ⁇ CR 1 —COO— (AO) n —R 2 [in the general formula (1), R 1 represents A hydrogen atom or a methyl group, AO is an alkyleneoxy group having 2 to 3 carbon atoms, n is 1 to 8 indicating the average number of moles added of the alkyleneoxy group, and R 2 is an aromatic ring, a straight chain, a branched chain, or An alicyclic alkyl group. ] (Wherein R 2 in the general formula (1) does not include an ether bond), and the like.
  • the (meth) acrylate (a2) having an ether bond can be used alone or in combination.
  • Examples of the monomer represented by the general formula (1) include methoxypolyethylene glycol (meth) acrylate, ethoxypolyethyleneglycol (meth) acrylate, and propoxypolyethyleneglycol (meth) having an oxyethylene group having an average addition mole number of 1 to 8.
  • An acrylate etc. are mentioned.
  • methoxypolypropylene glycol (meth) acrylate, ethoxypolypropylene glycol (meth) acrylate, propoxypolypropylene glycol (meth) acrylate and the like having an oxypropylene group having an average addition mole number of 1 to 8 can be mentioned.
  • AO in the general formula (1) is preferably an oxyethylene group which is an alkyleneoxy group having 2 carbon atoms from the viewpoint of having an appropriate polarity balance.
  • n in the general formula (1) is preferably 2 to 8, more preferably 2 to 5, from the viewpoint of the polar level and the polymerization reactivity.
  • R 2 in the general formula (1) is preferably an unsubstituted aromatic ring, or a linear, branched, or alicyclic alkyl group.
  • the aromatic ring of R 2 include a phenyl group, a linear alkyl group of R 2 , a branched chain alkyl such as an isopropyl group, an ethyl group, and a methyl group, and an alicyclic alkyl group of R 2 includes a cyclohexyl group and the like.
  • a linear alkyl group is preferable.
  • R 2 preferably has 1 to 6 carbon atoms, and more preferably 1 to 5 carbon atoms from the viewpoint of appropriate polarity.
  • the alkyl (meth) acrylate (a1) is 50 to 97% by weight based on all monomer components forming the (meth) acrylic polymer.
  • the alkyl (meth) acrylate (a1) is 55% by weight or more from the viewpoint of increasing the adhesive force and holding power to the adherend having a rough surface with respect to all monomer components forming the (meth) acrylic polymer.
  • it is 58 wt% or more, more preferably 59 wt% or more.
  • the alkyl (meth) acrylate (a1) is 95% by weight or less from the viewpoint of increasing the adhesion and holding power to the adherend having a rough surface with respect to all monomer components forming the (meth) acrylic polymer.
  • it is 93% by weight or less, more preferably 91% by weight or less.
  • the (meth) acrylate (a2) having an ether bond is 3 to 50% by weight based on all monomer components forming the (meth) acrylic polymer.
  • the (meth) acrylate (a2) having an ether bond is from the viewpoint of enhancing the adhesion and holding power to the adherend having a rough surface with respect to all monomer components forming the (meth) acrylic polymer. It is preferably 5% by weight or more, more preferably 4% by weight or more, and further preferably 4.5% by weight or more.
  • the (meth) acrylate (a2) having an ether bond is 48% by weight from the viewpoint of increasing the adhesion and holding power to the adherend having a rough surface with respect to all monomer components forming the (meth) acrylic polymer. % Or less, more preferably 45% by weight or less, and even more preferably 40% by weight or less.
  • the total ratio of the alkyl (meth) acrylate (a1) and the (meth) acrylate (a2) having an ether bond is preferably 75% by weight or more.
  • the total proportion of the alkyl (meth) acrylate (a1) and the ether-bonded (meth) acrylate (a2) is a deposition having a rough surface with respect to all monomer components forming the (meth) acrylic polymer. From the viewpoint of enhancing the adhesion and holding power to the body, it is more preferably 80% by weight or more, further preferably 85% by weight or more, and still more preferably 90% by weight or more.
  • the monomer component forming the (meth) acrylic polymer of the present invention further includes a monomer having at least one functional group selected from a monomer having a hydroxyl group, a monomer having a carboxyl group, and a monomer having an epoxy group Can be included.
  • a monomer 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
  • examples of the monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 6-hydroxy.
  • Hydroxyalkyl (meth) acrylates such as hexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate; (4-hydroxymethylcyclohexyl) And hydroxyalkylcycloalkane (meth) acrylates such as methyl (meth) acrylate.
  • Other examples include hydroxyethyl (meth) acrylamide, allyl alcohol, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, and the like.
  • the monomer having a hydroxyl group can be used alone or in combination. Of these, hydroxyalkyl (meth) acrylate is preferable, and 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate are particularly preferable.
  • a monomer 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
  • examples of the monomer having a carboxyl group include (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid.
  • the monomers having a carboxyl group can be used alone or in combination. Among these, acrylic acid and methacrylic acid are preferable, and acrylic acid is particularly preferable.
  • a monomer having an epoxy group a monomer 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 can be used without particular limitation.
  • the monomer having an epoxy group include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and the like.
  • the monomers having the epoxy group can be used alone or in combination.
  • the monomer having a hydroxyl group is preferably 0.01% by weight or more from the viewpoint of increasing cohesion with respect to all monomer components forming the (meth) acrylic polymer. More preferably, it is at least wt%.
  • the monomer having a hydroxyl group is preferably 3% by weight or less from the viewpoint of suppressing excessive viscosity increase and gelation of the polymer with respect to all monomer components forming the (meth) acrylic polymer. More preferably, it is less than or equal to weight percent.
  • the monomer having a carboxyl group has a viewpoint of increasing cohesive force and a molecular interaction with the adherend surface with respect to all monomer components forming the (meth) acrylic polymer. Therefore, it is preferably 0.1% by weight or more, and more preferably 0.2% by weight or more.
  • the monomer having a carboxyl group is 5% by weight or less from the viewpoint of increasing the followability to a rough surface and maintaining high adhesive strength at low temperatures with respect to all monomer components forming the (meth) acrylic polymer. Preferably, it is 3% by weight or less, more preferably 2% by weight or less.
  • the monomer having an epoxy group is preferably 0.1% by weight or more from the viewpoint of increasing cohesion with respect to all monomer components forming the (meth) acrylic polymer, More preferably, it is at least wt%.
  • the monomer having an epoxy group is preferably 1% by weight or less from the viewpoint of suppressing gelation and viscosity increase with respect to all monomer components forming the (meth) acrylic polymer, and 0.5% by weight. % Or less is more preferable. This is not the case when the (meth) acrylic polymer is a graft polymer.
  • the monomer component forming the (meth) acrylic polymer of the present invention may contain a copolymerization monomer other than the monomer having the functional group.
  • the copolymer monomer include, for example, the general formula (2): CH 2 ⁇ CR 3 —COO—R 4 (wherein R 3 is a hydrogen atom or a methyl group, and R 4 is an unsubstituted alkyl group having 1 to 24 carbon atoms). Or a substituted alkyl group, except for branched alkyl groups having 8 to 18 carbon atoms).
  • Copolymerization monomers can be used alone or in combination.
  • An 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, except for branched alkyl groups having 8 to 18 carbon atoms.
  • R 4 include a linear alkyl group having 1 to 18 carbon atoms, a branched alkyl group having 3 to 7 carbon atoms, and a cyclic alkyl group.
  • the substituent is preferably an aryl group having 3 to 7 carbon atoms or an aryloxy group having 3 to 7 carbon atoms.
  • the aryl group is not limited, but is preferably a phenyl group.
  • Examples of the monomer represented by the 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 (meth) acrylate, terpene ( Data) acrylate, dicyclopentanyl (meth) acrylate.
  • copolymerization monomer examples include vinyl monomers such as vinyl acetate, vinyl propionate, styrene, ⁇ -methylstyrene, N-vinylcaprolactam, N-vinylpyrrolidone; tetrahydrofurfuryl (meth) acrylate, fluorine Acrylic acid ester monomers such as (meth) acrylate, silicone (meth) acrylate and 2-methoxyethyl acrylate; amide group-containing monomers, amino group-containing monomers, imide group-containing monomers, N-acryloylmorpholine, vinyl ether monomers, etc. are also used. be able to.
  • examples of the copolymerization monomer include a silane monomer containing a silicon atom.
  • examples of the silane monomer include 3-acryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 4-vinylbutyltrimethoxysilane, 4-vinylbutyltriethoxysilane, and 8-vinyloctyltrimethoxysilane.
  • the copolymerization monomer is preferably 20% by weight or less, and more preferably 15% by weight or less, based on all monomer components forming the (meth) acrylic polymer.
  • the content of the comonomer exceeds 20% by weight, for example, adhesion to a rough surface may be lowered.
  • the monomer component that forms the (meth) acrylic polymer of the present invention may contain a polyfunctional monomer as necessary in order to adjust the cohesive strength of the resin composition.
  • Polyfunctional monomers can be used alone or in combination.
  • the polyfunctional monomer is a monomer having at least two polymerizable functional groups having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group, such as (poly) ethylene glycol di (meth) acrylate.
  • the polyfunctional monomer can be used at 5% by weight or less based on the total monomer components forming the (meth) acrylic polymer.
  • the said polyfunctional monomer changes with the molecular weight, the number of functional groups, etc., 3 weight% or less is preferable with respect to all the monomer components which form a (meth) acrylic-type polymer, Furthermore, 2 weight% or less is preferable.
  • the content of the polyfunctional monomer exceeds 5% by weight, for example, the elastic modulus of the resin composition becomes too high, and the adhesive force may be reduced.
  • the Tg of the (meth) acrylic polymer of the present invention is ⁇ 40 ° C. or lower.
  • the Tg of the (meth) acrylic polymer is preferably ⁇ 45 ° C. or less, and more preferably ⁇ 50 ° C. or less, from the viewpoint of increasing the adhesive force to the adherend having a rough surface.
  • the Tg of the (meth) acrylic polymer is preferably ⁇ 85 ° C. or higher, and more preferably ⁇ 80 ° C. or higher, from the viewpoint of increasing the adhesion and holding power to the adherend having a rough surface.
  • the Tg of the (meth) acrylic polymer is a theoretical value calculated from the following FOX formula from the monomer units constituting the (meth) acrylic polymer and the ratio thereof.
  • Tg glass transition temperature (unit: K) of the (meth) acrylic polymer
  • the (meth) acrylic polymer For the production of the (meth) acrylic polymer, known production methods such as solution polymerization, radiation polymerization such as electron beam and UV, bulk polymerization, emulsion polymerization and the like can be appropriately selected. Further, the (meth) acrylic polymer obtained may be any of a random copolymer, a block copolymer, a graft copolymer, and the like.
  • the polymerization initiator, chain transfer agent, emulsifier and the like used for the radical polymerization are not particularly limited and can be appropriately selected and used.
  • the weight average molecular weight of a (meth) acrylic-type polymer can be controlled by the usage-amount of a polymerization initiator and a chain transfer agent, and reaction conditions, The usage-amount is suitably adjusted according to these kinds.
  • solution polymerization for example, ethyl acetate, toluene or the like is used as a polymerization solvent.
  • the reaction is carried out in an inert gas stream such as nitrogen and a polymerization initiator is added, and the reaction is usually performed at about 50 to 70 ° C. under reaction conditions for about 5 to 30 hours.
  • polymerization initiator examples include 2,2′-azobisisobutyronitrile, 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), 2, Azo-based initiators such as 2′-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate (manufactured by Wako Pure Chemical Industries, Ltd., VA-057), and persulfates such as potassium persulfate and ammonium persulfate Salt, di (2-ethylhexyl) peroxydicarbonate, di (4-tert-butylcyclohexyl) peroxydicarbonate, di-sec-butyl Peroxydi
  • the polymerization initiators can be used alone or in combination, but the total amount used is preferably about 0.005 to 1 part by weight with respect to 100 parts by weight of the monomer component, and 0.01 to 0.5 More preferably, it is about parts by weight.
  • polymerization initiator for example, 2,2′-azobisisobutyronitrile is preferably used.
  • chain transfer agent examples include lauryl mercaptan, glycidyl mercaptan, mercaptoacetic acid, 2-mercaptoethanol, thioglycolic acid, 2-ethylhexyl thioglycolate, and 2,3-dimercapto-1-propanol.
  • the chain transfer agent may be used alone or in combination of two or more, but the total amount used is 0.1 parts by weight with respect to 100 parts by weight of the total amount of monomer components. Less than or equal to
  • emulsifier used in the emulsion polymerization examples include anionic emulsifiers such as sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, ammonium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkylphenyl ether sulfate, and polyoxyethylene.
  • anionic emulsifiers such as alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene fatty acid esters, polyoxyethylene-polyoxypropylene block polymers and the like can be mentioned.
  • the emulsifiers can be used alone or in combination.
  • the reactive emulsifier as an emulsifier into which a radical polymerizable functional group such as propenyl group or allyl ether group is introduced, specifically, for example, Aqualon HS-10, HS-20, KH-10, BC-05, BC-10, BC-20 (all of which are manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Adekaria soap SE10N (manufactured by ADEKA), and the like.
  • Reactive emulsifiers are preferable because they are incorporated into the polymer chain after polymerization and thus have improved water resistance.
  • the amount of the emulsifier used is preferably 0.3 to 5 parts by weight with respect to 100 parts by weight of the total amount of monomer components, and more preferably 0.5 to 1 part by weight from the viewpoint of polymerization stability and mechanical stability.
  • the (meth) acrylic polymer When the (meth) acrylic polymer is produced by radiation polymerization, it can be produced by polymerizing the monomer component by irradiating with radiation such as electron beam or UV.
  • radiation polymerization When the radiation polymerization is performed with an electron beam, it is not particularly necessary to include a photopolymerization initiator in the monomer component.
  • the radiation polymerization is performed with UV polymerization, the polymerization time is particularly short.
  • a photopolymerization initiator can be contained in the monomer component because of the advantages that can be achieved.
  • a photoinitiator can be used individually or in combination.
  • the photopolymerization disclosure agent is not particularly limited as long as it initiates photopolymerization, and a commonly used photopolymerization initiator can be used.
  • a commonly used photopolymerization initiator can be used.
  • benzoin ether, acetophenone, ⁇ -ketol, photoactive oxime, benzoin, benzyl, benzophenone, ketal, thioxanthone, and the like can be used.
  • the amount of the photopolymerization initiator used is 0.05 to 1.5 parts by weight, preferably 0.1 to 1 part by weight, based on 100 parts by weight of the monomer component.
  • the weight average molecular weight of the (meth) acrylic polymer of the present invention is preferably 350,000 or more.
  • the weight average molecular weight of the (meth) acrylic polymer is more preferably 400,000 or more, and even more preferably 500,000 or more, from the viewpoint of enhancing the durability and cohesion of the resin layer.
  • the weight average molecular weight of the (meth) acrylic polymer is preferably 3 million or less, and preferably 2.5 million or less from the viewpoints of enhancing the bonding property and the adhesive strength, and suppressing the viscosity of the resin composition. Is more preferably 2 million or less, even more preferably 1.5 million or less, and even more preferably 1.2 million or less.
  • the weight average molecular weight of the (meth) acrylic polymer can be measured by GPC (gel permeation chromatography) and calculated in terms of polystyrene.
  • the sample used was a filtrate obtained by dissolving the sample in tetrahydrofuran to make a 0.1 wt% solution, which was allowed to stand overnight, and then filtered through a 0.45 ⁇ m membrane filter.
  • the resin composition of the present invention can 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, alkyletherified melamine crosslinking agents, metal chelate crosslinking agents, Crosslinkers such as oxides are included.
  • an isocyanate type crosslinking agent and an epoxy-type crosslinking agent are suitable.
  • the crosslinking agent can be used alone or in combination, but the total content of the crosslinking agent is 0.01 to 5 parts by weight with respect to 100 parts by weight of the (meth) acrylic polymer. Is preferred.
  • the content of the crosslinking agent is more preferably 0.01 to 4 parts by weight, and further preferably 0.02 to 3 parts by weight.
  • the polyfunctional monomer may be used as a crosslinking agent. In this case, the polyfunctional monomer is used in an amount of 0.001 to 2 parts by weight with respect to 100 parts by weight of the (meth) acrylic polymer. It is preferably contained, and more preferably in the range of 0.003 to 1 part by weight.
  • the isocyanate-based crosslinking agent refers to a compound having two or more isocyanate groups (including isocyanate-regenerating functional groups in which the isocyanate group is temporarily protected by a blocking agent or quantification) in one molecule.
  • isocyanate-based crosslinking agent examples include aromatic isocyanates such as tolylene diisocyanate and xylene diisocyanate, alicyclic isocyanates such as isophorone diisocyanate, and aliphatic isocyanates such as hexamethylene diisocyanate.
  • isocyanate-based crosslinking agent for example, lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate, alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate, and isophorone diisocyanate, Aromatic diisocyanates such as 2,4-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, polymethylene polyphenyl isocyanate, trimethylolpropane / tolylene diisocyanate trimer adduct (manufactured by Nippon Polyurethane Industry Co., Ltd.) , Trade name Coronate L), trimethylolpropane / hexamethylene diisocyanate trimer adduct (made by Nippon Polyurethane Industry Co., Ltd., trade name
  • the isocyanate crosslinking agent can be used alone or in combination, but the total content is 0.01 to 5 parts by weight of the isocyanate crosslinking agent with respect to 100 parts by weight of the (meth) acrylic polymer. Preferably, it is contained in an amount of 0.03 to 4 parts by weight, more preferably 0.05 to 3 parts by weight, and still more preferably 0.08 to 2 parts by weight. It can be appropriately contained in consideration of cohesive force, prevention of peeling in a durability test, and the like.
  • the epoxy-based crosslinking agent refers to a polyfunctional epoxy compound having two or more epoxy groups in one molecule.
  • the epoxy crosslinking agent include N, N, N ′, N′-tetraglycidyl-m-xylenediamine, diglycidylaniline, 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 agent can be used alone or in combination, but the total content is 0.005 to 1 part by weight of the epoxy crosslinking agent with respect to 100 parts by weight of the (meth) acrylic polymer.
  • the content is preferably 0.01 to 0.5 parts by weight, more preferably 0.015 to 0.3 parts by weight. It can be appropriately contained in consideration of cohesive force, prevention of peeling in a durability test, and the like.
  • any radical active species can be used as long as it generates radical active species by heating to advance the crosslinking of the base polymer of the resin composition.
  • 1 minute It is preferable to use a peroxide having a half-life temperature of 80 ° C. to 160 ° C., and more preferable to use a peroxide having a 90 ° C. to 140 ° C.
  • peroxide examples include di (2-ethylhexyl) peroxydicarbonate (1 minute half-life temperature: 90.6 ° C.), di (4-t-butylcyclohexyl) peroxydicarbonate (1 minute half-life).
  • di (4-t-butylcyclohexyl) peroxydicarbonate (1 minute half-life temperature: 92.1 ° C.)
  • dilauroyl peroxide (1 minute half-life temperature: 116. 4 ° C.
  • dibenzoyl peroxide (1 minute half-life temperature: 130.0 ° C.) and the like are preferably used.
  • the half-life of the peroxide is an index representing the decomposition rate of the peroxide, and means the time until the remaining amount of peroxide is reduced to half.
  • the decomposition temperature for obtaining a half-life at an arbitrary time and the half-life time at an arbitrary temperature are described in the manufacturer catalog and the like, for example, “Organic peroxide catalog 9th edition of Nippon Oil & Fats Co., Ltd.” (May 2003) ".
  • the peroxides can be used alone or in combination, but the total content is 0.02 to 2 parts by weight of the peroxide with respect to 100 parts by weight of the (meth) acrylic polymer. It is preferably contained in an amount of 05 to 1 part by weight. In order to adjust processability, reworkability, cross-linking stability, releasability, etc., it is appropriately selected within this range.
  • the peroxide decomposition amount remaining after the reaction treatment for example, it can be measured by HPLC (high performance liquid chromatography). Specifically, for example, about 0.2 g of the resin layer after the reaction treatment is taken out, immersed in 10 ml of ethyl acetate, extracted with shaking at 25 ° C. and 120 rpm for 3 hours, and then at room temperature for 3 days. Leave still. Next, 10 ml of acetonitrile was added, shaken at 120 rpm at 25 ° C. for 30 minutes, and about 10 ⁇ l of the extract obtained by filtration through a membrane filter (0.45 ⁇ m) was injected into the HPLC for analysis. The amount of peroxide can be set.
  • HPLC high performance liquid chromatography
  • examples of the metal chelate-based crosslinking agent include polyfunctional metal chelates in which a polyvalent metal is covalently or coordinately bonded to an organic compound.
  • examples of polyvalent metal atoms include Al, Cr, Zr, Co, Cu, Fe, Ni, V, Zn, In, Ca, Mg, Mn, Y, Ce, Sr, Ba, Mo, La, Sn, Ti, and the like.
  • examples of the atom in the organic compound that is covalently bonded or coordinated include an oxygen atom
  • examples of the organic compound include an alkyl ester, an alcohol compound, a carboxylic acid compound, an ether compound, and a ketone compound.
  • the resin composition of the present invention can contain a (meth) acrylic oligomer in order to improve the adhesive strength.
  • the (meth) acrylic oligomer is preferably a polymer having a Tg higher than that of the (meth) acrylic polymer of the present invention and a small weight average molecular weight.
  • the (meth) acrylic oligomer functions as a tackifier resin and can improve the adhesive force.
  • the (meth) acrylic oligomer desirably has a Tg of about 0 ° C. or higher and 300 ° C. or lower, preferably about 20 ° C. or higher and 300 ° C. or lower, more preferably about 40 ° C. or higher and 300 ° C. or lower. If the Tg is less than about 0 ° C., the cohesive strength of the resin layer at room temperature or higher may be reduced, and the holding characteristics and adhesiveness at high temperatures may be reduced.
  • the Tg of the (meth) acrylic oligomer is a theoretical value calculated on the basis of the Fox equation, similar to the Tg of the (meth) acrylic polymer.
  • the weight average molecular weight of the (meth) acrylic oligomer is 1000 or more and less than 30000, preferably 1500 or more and less than 20000, and more preferably 2000 or more and less than 10,000. If the weight average molecular weight is 30000 or more, the effect of improving the adhesive strength may not be sufficiently obtained. On the other hand, if the molecular weight is less than 1000, the molecular weight may be low, which may cause a decrease in adhesive strength and retention characteristics.
  • the measurement of the weight average molecular weight of a (meth) acrylic-type oligomer can be calculated
  • Examples of the monomer constituting the (meth) acrylic oligomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, and isobutyl (meth).
  • Examples of the (meth) acrylic oligomer include alkyl (meth) acrylates having an alkyl group having a branched structure, such as isobutyl (meth) acrylate and t-butyl (meth) acrylate; cyclohexyl (meth) acrylate, isobornyl (meta) ) Esters of (meth) acrylic acid and alicyclic alcohols such as acrylate dicyclopentanyl (meth) acrylate; cyclic structures such as aryl (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate It is preferable that an acrylic monomer having a relatively bulky structure typified by (meth) acrylate having a monomer content is included as a monomer unit.
  • the adhesiveness of the resin layer can be further improved.
  • those having a ring structure in terms of bulkiness are highly effective, and those having a plurality of rings are more effective.
  • ultraviolet rays ultraviolet rays
  • those having a saturated bond are preferable because they are less likely to cause polymerization inhibition.
  • An alkyl (meth) acrylate having a branched structure in the group or an ester with an alicyclic alcohol can be suitably used as a monomer constituting the (meth) acrylic oligomer.
  • suitable (meth) acrylic oligomers include, for example, a copolymer of cyclohexyl methacrylate (CHMA) and isobutyl methacrylate (IBMA), and a copolymer of cyclohexyl methacrylate (CHMA) and isobornyl methacrylate (IBXMA).
  • CHMA cyclohexyl methacrylate
  • IBMA isobutyl methacrylate
  • IBXMA isobornyl methacrylate
  • the (meth) acrylic oligomer when used, its content is not particularly limited, but it is preferably 70 parts by weight or less with respect to 100 parts by weight of the (meth) acrylic polymer, The amount is more preferably 1 to 70 parts by weight, further preferably 2 to 50 parts by weight, and further preferably 3 to 40 parts by weight.
  • the addition amount of the (meth) acrylic oligomer exceeds 70 parts by weight, there is a possibility that the elastic modulus becomes too high and the adhesiveness at a low temperature is deteriorated.
  • the resin composition of the present invention can contain a tackifier (tackifier) for improving the interaction with the adherend interface and for imparting the cohesive force of the resin composition bulk.
  • a tackifier for improving the interaction with the adherend interface and for imparting the cohesive force of the resin composition bulk.
  • a tackifier for improving the interaction with the adherend interface and for imparting the cohesive force of the resin composition bulk.
  • rosin ester pencel series Arakawa Chemical Industries
  • terpene tackifier Yamashi Chemical
  • Haritac series Harmonic series
  • the tackifier (tackifier) is preferably added in an amount of 5 to 40 parts by weight with respect to 100 parts by weight of the (meth) acrylic polymer.
  • the resin composition of the present invention can contain a silane coupling agent in order to increase the adhesion reliability at the interface with the adherend.
  • the amount of the silane coupling agent is preferably 1 part by weight or less, more preferably 0.01 to 1 part by weight, and still more preferably 0.02 to 0 part per 100 parts by weight of the (meth) acrylic polymer. .6 parts by weight. If the amount of the silane coupling agent is too large, crosslinking may be inhibited or the adhesive properties may be impaired. If the amount is too small, the effect cannot be obtained, which is not preferable.
  • silane coupling agent examples include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 2- (3,4 epoxycyclohexyl) ethyltri Epoxy group-containing silane coupling agents such as methoxysilane, 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-triethoxysilyl-N- (1,3- (Meth) such as dimethylbutylidene) propylamine, amino group-containing silane coupling agents such as N-phenyl- ⁇ -aminopropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, etc.
  • the resin composition of the present invention may contain other known additives, such as powders such as colorants, pigments, dyes, surfactants, plasticizers, tackifiers, surfaces.
  • powders such as colorants, pigments, dyes, surfactants, plasticizers, tackifiers, surfaces.
  • the resin layer of the present invention is formed from the resin composition.
  • the thickness of the resin layer is not particularly limited and is, for example, about 1 to 1000 ⁇ m.
  • the thickness of the resin layer is preferably 3 to 500 ⁇ m, more preferably 5 to 200 ⁇ m.
  • the gel fraction of the resin layer is preferably 20 to 95% by weight.
  • the gel fraction of the resin layer is more preferably 25% by weight or more, further preferably 30% by weight or more, and more preferably 35% by weight or more from the viewpoint of increasing the cohesive force and holding power of the resin layer. Is even more preferable.
  • the gel fraction of the resin layer is more preferably 80% by weight or less, more preferably 70% by weight or less, and still more preferably 65% by weight or less, from the viewpoint of increasing the adhesive strength of the resin layer. preferable.
  • the gel fraction should be controlled by adjusting the total amount of the cross-linking agent and taking into consideration the effects of the cross-linking temperature and the cross-linking time. Can do.
  • the resin layer can be formed as a laminated sheet by, for example, applying the resin composition to one or both sides of a support and removing the polymerization solvent by heating and drying.
  • one or more solvents other than the polymerization solvent may be added as appropriate.
  • Various methods are used as a method for applying the resin composition. Specifically, for example, by 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. Examples thereof include an extrusion coating method.
  • the temperature of the heat drying is preferably 40 to 200 ° C., more preferably 50 to 180 ° C., and particularly preferably 70 to 170 ° C. By setting the heating temperature within the above range, a resin layer having excellent adhesive properties can be obtained.
  • the heat drying time is preferably 5 seconds to 20 minutes, more preferably 5 seconds to 15 minutes, and particularly preferably 10 seconds to 10 minutes.
  • the resin layer is formed by producing the (meth) acrylic polymer of the present invention by polymerizing the monomer component by irradiating the monomer component with ultraviolet rays. At the same time, a resin layer can be formed.
  • the monomer component can contain materials that can be appropriately blended in the resin composition, such as a crosslinking agent.
  • a part of the monomer component previously polymerized into a syrup can be used for ultraviolet irradiation.
  • a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, or the like can be used for ultraviolet irradiation.
  • the support examples include plastic films such as polyethylene, polypropylene, polyethylene terephthalate, and polyester films, polyacrylic films, porous materials such as paper, cloth, and nonwoven fabric, nets, bubble-containing sheets such as polyethylene foam and acrylic foam, and metal foils. And various support films such as laminates thereof.
  • the bubbles include those due to the inclusion of hollow particles and the like.
  • the thickness of the support film is usually about 5 to 3000 ⁇ m, preferably about 10 to 2500 ⁇ m, and more preferably about 20 to 2000 ⁇ m.
  • mold release and antifouling treatment with a silicone type, fluorine type, long chain alkyl type or fatty acid amide type release agent, silica powder, etc., coating type, kneading type, vapor deposition
  • An antistatic treatment such as a mold can also be performed.
  • the resin layer when the resin layer is exposed, the resin layer may be protected with a separator until it is practically used. In practical use, the separator is peeled off.
  • plastic films such as polyethylene, polypropylene, polyethylene terephthalate, polyester film, porous materials such as paper, cloth, nonwoven fabric, nets, bubble-containing sheets, metal foils, and laminates thereof Appropriate thin leaves and the like can be mentioned.
  • a plastic film is preferably used from the viewpoint of excellent surface smoothness.
  • the plastic film is not particularly limited as long as it can protect the resin layer.
  • a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, a polymethylpentene film, a polyvinyl chloride film, and a vinyl chloride copolymer are used.
  • examples thereof include a coalesced film, a polyethylene terephthalate film, a polybutylene terephthalate film, a polyurethane film, and an ethylene-vinyl acetate copolymer film.
  • the thickness of the separator is usually about 5 to 300 ⁇ m, preferably about 5 to 200 ⁇ m.
  • silicone type, fluorine type, long chain alkyl type or fatty acid amide type release agent, mold release and antifouling treatment with silica powder, coating type, kneading type, vapor deposition type, if necessary It is also possible to perform antistatic treatment such as.
  • a release treatment such as silicone treatment, long-chain alkyl treatment, or fluorine treatment, the peelability from the resin layer can be further enhanced.
  • the resin composition, resin layer and laminated sheet of the present invention are coated with a rough surface such as concrete, mortar, gypsum board, softwood plywood, wood cement board, calcium silicate board, tile and fiber reinforced cement board. It is preferable to use it for the purpose of sticking to a kimono.
  • the surface irregularity (surface roughness) of the adherend having the rough surface is about 1 ⁇ m to several 100 ⁇ m.
  • the laminated sheet is particularly preferably used for an adherend having a rough surface with surface irregularities (surface roughness) of 1 ⁇ m to 500 ⁇ m.
  • Example 1 Preparation of (meth) acrylic polymer>
  • 2EHA 2-ethylhexyl acrylate
  • CBA ethyl carbitol acrylate
  • 4HBA 4-hydroxybutyl acrylate
  • acrylic acid (AA) 1 part by weight
  • 2,2′-azobisisobutyronitrile 0.07 part by weight as a polymerization initiator together with 105 parts by weight of ethyl acetate, and gently stirred.
  • the liquid temperature in the flask was kept at 60 to 65 ° C. and the polymerization reaction was carried out for 10 hours to prepare a (meth) acrylic polymer solution having a weight average molecular weight of 770,000. did.
  • the obtained (meth) acrylic polymer had a Tg of ⁇ 68.7 ° C.
  • the obtained resin composition solution was applied to one side of a 38 ⁇ m polyethylene terephthalate (PET) film separator (Mitsubishi Resin Co., Ltd., Diafoil MRF) subjected to silicone treatment, and the thickness of the resin layer after drying was 95 ⁇ m. Then, it was dried at 130 ° C. for 5 minutes to form a resin layer, and a laminated sheet was produced.
  • PET polyethylene terephthalate
  • Example 1 is the same as Example 1 except that the types and composition ratios of the monomers used for the preparation of the (meth) acrylic polymer and the types and amounts of the crosslinking agents are changed as shown in Table 1. Thus, a laminated sheet was produced. Table 1 shows the weight average molecular weight and Tg of the obtained (meth) acrylic polymer.
  • Example 30 Preparation of (meth) acrylic polymer syrup>
  • a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas inlet tube, and a condenser 90 parts by weight of 2-ethylhexyl acrylate (2EHA), 10 parts by weight of ethyl carbitol acrylate (CBA), 4-hydroxybutyl acrylate ( 4HBA) 0.25 parts by weight, acrylic acid (AA) 1 part by weight, photopolymerization initiator (trade name: Irgacure 184, manufactured by BASF) 0.15 parts by weight and photopolymerization initiator (trade name: Irgacure 651, BASF) 0.15 parts by weight) was added to a four-necked flask to prepare a monomer mixture.
  • the monomer mixture was partially photopolymerized by exposing it to ultraviolet rays under a nitrogen atmosphere to obtain a partially polymerized product ((meth) acrylic polymer syrup) having
  • TMPTA trimethylolpropane triacrylate
  • the final thickness is 95 ⁇ m on the release surface of the 38 ⁇ m thick polyester film (trade name: Diafoil MRF, manufactured by Mitsubishi Plastics Co., Ltd.) having the monomer component prepared above peel-treated on one side with silicone.
  • the coating layer was formed by coating as described above.
  • a 38 ⁇ m thick polyester film (trade name: Diafoil MRE, manufactured by Mitsubishi Plastics Co., Ltd.) having one surface peeled with silicone on the surface of the applied monomer component, the peel-treated surface of the film is on the coating layer side. It was coated as follows. Thereby, the coating layer of the monomer component was shielded from oxygen.
  • the sheet having the coating layer thus obtained was irradiated with ultraviolet rays having an illuminance of 5 mW / cm 2 (measured with Topcon UVR-T1 having a maximum sensitivity of about 350 nm) for 360 seconds using a chemical light lamp (manufactured by Toshiba Corporation). After irradiation, the coating layer was cured to obtain a resin layer, and then the single-sided polyester film (Diafoil MRE) was peeled off to produce a laminated sheet.
  • ultraviolet rays having an illuminance of 5 mW / cm 2 (measured with Topcon UVR-T1 having a maximum sensitivity of about 350 nm) for 360 seconds using a chemical light lamp (manufactured by Toshiba Corporation).
  • the coating layer was cured to obtain a resin layer, and then the single-sided polyester film (Diafoil MRE) was peeled off to produce a laminated sheet.
  • Example 31 a laminated sheet was produced in the same manner as in Example 30, except that the composition ratio of the monomers used for the preparation of the (meth) acrylic polymer syrup was changed as shown in Table 2.
  • Table 2 shows Tg of the obtained (meth) acrylic polymer.
  • a sample for evaluation was prepared by attaching a PET film having a thickness of 25 ⁇ m (Lumirror S10, manufactured by Toray Industries, Inc.) to the adhesive surfaces of the samples obtained in Examples and Comparative Examples.
  • the sample for evaluation was cut into a width of 20 mm and a length of about 100 mm, and then the separator (manufactured by Mitsubishi Plastics, Diafoil MRF) was peeled off to form a gypsum board (manufactured by Yoshino Gypsum Co., Ltd., product)
  • a 2 kg roll was pasted in one reciprocation on a name Tiger board (9.5 mm thickness), softwood plywood (Shimadachu Homes acquisition 12 mm thickness), or a calcium silicate board (Keical board, Shimatada Homes acquisition 5 mm thickness).
  • the peel adhesive force (N / 20mm) was measured by the peeling angle of 180 degrees and the peeling speed of 300 mm / min.
  • the peel adhesive strength is preferably 10 N / 20 mm or more, more preferably 12 N / 20 mm or more, and further preferably 15 N / 20 mm or more.
  • a sample for evaluation was prepared by attaching a PET film having a thickness of 25 ⁇ m (Lumirror S10, manufactured by Toray Industries, Inc.) to the adhesive surfaces of the samples obtained in Examples and Comparative Examples. After the sample for evaluation was cut into a width of 10 mm and a length of 100 mm, the separator (manufactured by Mitsubishi Plastics, Diafoil MRF) was peeled off, and as an adherend, softwood plywood (Shimadachi Holmes obtained 12 mm thickness), A 2 kg roll was pasted in one reciprocation so that the pasting area would be 10 mm wide x 20 mm long.
  • the separator manufactured by Mitsubishi Plastics, Diafoil MRF
  • the softwood plywood was drooped and the load of 500g was provided to the free end of the sample piece.
  • the sample was left in an environment of 40 ° C. for 1 hour in the state where the load was applied, and the displacement distance (mm) of the sample tape from the first attachment position was measured, and the holding force (mm / h) was calculated.
  • the holding force is preferably 2.0 mm / h or less, more preferably 1.5 mm / h or less, and more preferably 1.0 mm / h or less.
  • C / L represents trimethylolpropane / 2,4-tolylene diisocyanate trimer adduct (trade name Coronate L manufactured by Tosoh Corporation);
  • D110N is a trimethylolpropane adduct of xylylene diisocyanate (manufactured by Mitsui Chemicals, trade name: Takenate D110N);
  • D120N is a trimethylolpropane adduct of xylylene diisocyanate (trade name: Takenate D120N, manufactured by Mitsui Chemicals);
  • D140N is a trimethylolpropane adduct of isophorone diisocyanate (trade name: Takenate D140N, manufactured by Mitsui Chemicals);
  • T / C is 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane (trade name Tetrad C, manufactured by Mitsubishi Gas Chemical Company);
  • TMPTA indicates trimethyl

Abstract

A resin composition characterized by including a (meth)acrylic polymer having a Tg of -40°C or lower obtained by polymerizing a monomer component including an alkyl (meth)acrylate (a1), the Tg of a homopolymer of which is -50°C or lower, that has a C8-18 branched alkyl group at the end of the ester group and a (meth)acrylate (a2), the Tg of a homopolymer of which is -40°C or lower, that has an ether bond within the molecular skeleton. The resin composition can achieve both high adhesive strength and high holding power to an adherend having a rough surface.

Description

樹脂組成物、樹脂層、および積層シートResin composition, resin layer, and laminated sheet
　本発明は、樹脂組成物、樹脂層、および積層シートに関する。 The present invention relates to a resin composition, a resin layer, and a laminated sheet.
　粘着剤に求められる基本性能の一つは、様々な被着体に対して強く接着し得ることである。一般的に、従来の粘着シート又は粘着テープ（以下、粘着シートと称する）等の積層シートでは、コンクリ－ト、モルタル、石膏ボード、針葉樹合板、木質系セメント板、ケイ酸カルシウム板、タイル、及び繊維強化セメント板等の粗面（凸凹形状を有する表面）を有する被着体への接着力が十分ではないため、これら粗面を有する被着体に対しては接着剤が用いられる事が多かった。しかし、近年、より簡便にそれらの被着体同士およびその他の被着体に貼りつけ固定したいというニーズの増加に伴い、これらの粗面を有する被着体に対しても、粘着シート等の積層シートを用いて接合することが強く望まれている。 One of the basic performances required for pressure-sensitive adhesives is that they can adhere strongly to various adherends. In general, laminated sheets such as conventional pressure-sensitive adhesive sheets or pressure-sensitive adhesive tapes (hereinafter referred to as pressure-sensitive adhesive sheets) include concrete, mortar, gypsum board, softwood plywood, wood-based cement board, calcium silicate board, tile, and Adhesive strength to adherends having rough surfaces (surfaces with irregularities) such as fiber reinforced cement boards is not sufficient, and adhesives are often used for adherends having rough surfaces. It was. However, in recent years, with the increase in the need to attach and fix these adherends to each other and other adherends more easily, even for adherends having these rough surfaces, lamination of adhesive sheets and the like It is strongly desired to join using a sheet.
　特許文献１では、コンクリート等の粗面を有する被着体に対して良好な接着力を示す、ゴム系粘着剤層が設けられた粘着シートが開示されている。しかし、ゴム系粘着剤層の形成には、ゴム系粘着剤の塗布後に養生が必要であり、生産効率の観点からの問題が懸念された。また、粘着付与剤が多く添加されているため、低温での接着力低下も懸念された。 Patent Document 1 discloses a pressure-sensitive adhesive sheet provided with a rubber-based pressure-sensitive adhesive layer that exhibits good adhesion to an adherend having a rough surface such as concrete. However, the formation of the rubber-based pressure-sensitive adhesive layer requires curing after the application of the rubber-based pressure-sensitive adhesive, and there is a concern from the viewpoint of production efficiency. In addition, since a large amount of tackifier is added, there is a concern about a decrease in adhesive strength at low temperatures.
　また、養生が不要な粘着剤としては、（メタ）アクリル系ポリマーを含む粘着剤が広く知られている。特許文献２では、種々の（メタ）アクリレートを用いた光学部材用の粘着剤が開示されている。しかし、上記のような粗面を有する被着体への接着力については開示されていない。 Also, as an adhesive that does not require curing, an adhesive containing a (meth) acrylic polymer is widely known. Patent Document 2 discloses adhesives for optical members using various (meth) acrylates. However, it does not disclose the adhesive force to the adherend having the rough surface as described above.
特開平０８－１０４８４７号公報Japanese Patent Laid-Open No. 08-104847 国際公開第２０１３／０９９６８３号International Publication No. 2013/099683
　上記のような粗面を有する被着体に対して用いられる粘着シート等の積層シートには、接着力のほかに、被着体に固定した重量物を固定した状態で長期に保持する観点から、保持力も必要とされる。 The laminated sheet such as the pressure-sensitive adhesive sheet used for the adherend having a rough surface as described above, in addition to the adhesive force, from the viewpoint of holding a heavy object fixed to the adherend for a long period of time. Holding power is also required.
　本発明は、粗面を有する被着体に対して、高い接着力及び高い保持力を両立することができる樹脂組成物を提供することを目的とする。 An object of the present invention is to provide a resin composition capable of achieving both high adhesive force and high holding force for an adherend having a rough surface.
　また、本発明は、前記樹脂組成物により形成された樹脂層を提供すること、さらには、当該樹脂層を有する積層シートを提供することを目的とする。 The present invention also aims to provide a resin layer formed from the resin composition, and further to provide a laminated sheet having the resin layer.
　本発明者らは前記課題を解決すべく鋭意検討を重ねた結果、下記樹脂組成物を見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have found the following resin composition and have completed the present invention.
　すなわち、本発明は、ホモポリマーのＴｇが－５０℃以下であり、かつ炭素数８～１８の分岐したアルキル基をエステル基の末端に有するアルキル（メタ）アクリレート（ａ１）を５０～９７重量％、及びホモポリマーのＴｇが－４０℃以下であり、かつ分子骨格内にエーテル結合を有する（メタ）アクリレート（ａ２）を３～５０重量％を含むモノマー成分を重合することにより得られたＴｇが－４０℃以下である（メタ）アクリル系ポリマーを含むことを特徴とする樹脂組成物、に関する。 That is, the present invention provides 50 to 97% by weight of alkyl (meth) acrylate (a1) having a Tg of a homopolymer of −50 ° C. or less and having a branched alkyl group having 8 to 18 carbon atoms at the terminal of the ester group. And the Tg obtained by polymerizing a monomer component containing 3 to 50% by weight of (meth) acrylate (a2) having a Tg of the homopolymer of −40 ° C. or less and having an ether bond in the molecular skeleton. The present invention relates to a resin composition comprising a (meth) acrylic polymer having a temperature of −40 ° C. or lower.
　本発明の樹脂組成物は、前記アルキル（メタ）アクリレート（ａ１）及び前記エーテル結合を有する（メタ）アクリレート（ａ２）の合計の割合が、（メタ）アクリル系ポリマーを形成する全モノマー成分に対して、７５重量％以上であることが好ましい。 In the resin composition of the present invention, the total ratio of the alkyl (meth) acrylate (a1) and the (meth) acrylate (a2) having an ether bond is based on the total monomer components forming the (meth) acrylic polymer. It is preferably 75% by weight or more.
　本発明の樹脂組成物は、前記エーテル結合を有する（メタ）アクリレート（ａ２）が、一般式（１）：ＣＨ２＝ＣＲ１－ＣＯＯ－（ＡＯ）ｎ－Ｒ２［前記一般式（１）中、Ｒ１は水素原子又はメチル基、ＡＯは炭素数２～３のアルキレンオキシ基、ｎはアルキレンオキシ基の平均付加モル数を示す１～８であり、Ｒ２は芳香環、又は直鎖、分岐鎖、もしくは脂環式アルキル基である。］で表されるモノマーであることが好ましい。 In the resin composition of the present invention, the (meth) acrylate (a2) having an ether bond has the general formula (1): CH 2 ═CR 1 —COO— (AO) n —R 2 [the above general formula (1) Wherein R 1 is a hydrogen atom or a methyl group, AO is an alkyleneoxy group having 2 to 3 carbon atoms, n is 1 to 8 indicating the average number of moles added of the alkyleneoxy group, and R 2 is an aromatic ring or a straight chain A branched chain or alicyclic alkyl group. It is preferable that it is a monomer represented by this.
　本発明の樹脂組成物は、前記モノマー成分が、さらに、ヒドロキシル基を有するモノマー、カルボキシル基を有するモノマー、及びエポキシ基を有するモノマーから選ばれるいずれか少なくとも１つの官能基を有するモノマーを含むことが好ましい。 In the resin composition of the present invention, the monomer component further includes a monomer having at least one functional group selected from a monomer having a hydroxyl group, a monomer having a carboxyl group, and a monomer having an epoxy group. preferable.
　本発明の樹脂組成物は、前記モノマー成分が、さらに、多官能性モノマーを、（メタ）アクリル系ポリマーを形成する全モノマー成分に対して、５重量％以下含むことができる。 In the resin composition of the present invention, the monomer component may further contain a polyfunctional monomer in an amount of 5% by weight or less based on the total monomer components forming the (meth) acrylic polymer.
　本発明の樹脂組成物は、前記（メタ）アクリル系ポリマーの重量平均分子量が、３５万以上であることが好ましい。 In the resin composition of the present invention, the (meth) acrylic polymer preferably has a weight average molecular weight of 350,000 or more.
　本発明の樹脂組成物は、さらに、前記（メタ）アクリル系ポリマー１００重量部に対して、架橋剤を、０．０１～５重量部含むことが好ましい。 The resin composition of the present invention preferably further contains 0.01 to 5 parts by weight of a crosslinking agent with respect to 100 parts by weight of the (meth) acrylic polymer.
　本発明の樹脂組成物は、前記架橋剤が、イソシアネート系架橋剤、及び／又はエポキシ系架橋剤であることが好ましい。 In the resin composition of the present invention, the crosslinking agent is preferably an isocyanate crosslinking agent and / or an epoxy crosslinking agent.
　本発明は、樹脂組成物から得られることを特徴とする樹脂層に関する。 The present invention relates to a resin layer obtained from a resin composition.
　本発明の樹脂層は、ゲル分率が２０～９５重量％であることが好ましい。 The resin layer of the present invention preferably has a gel fraction of 20 to 95% by weight.
　本発明は、支持体の少なくとも片側に、前記樹脂層が設けられていることを特徴とする積層シート、に関する。 The present invention relates to a laminated sheet characterized in that the resin layer is provided on at least one side of a support.
　本発明の積層シートは、前記樹脂層の被着体に対する１８０°ピール接着力が、剥離速度３００ｍｍ／分の条件下で、１０Ｎ／２０ｍｍ以上であることが好ましい。 In the laminated sheet of the present invention, the 180 ° peel adhesive strength of the resin layer to the adherend is preferably 10 N / 20 mm or more under the condition of a peeling rate of 300 mm / min.
　本発明の積層シートは、前記支持体が、プラスチックフィルム、紙、不織布、気泡含有シートのいずれかであることが好ましい。 In the laminated sheet of the present invention, it is preferable that the support is any one of a plastic film, paper, nonwoven fabric, and a bubble-containing sheet.
　本発明の樹脂組成物は、前記一般式（１）中のＡＯがオキシエチレン基であることが好ましい。 In the resin composition of the present invention, it is preferable that AO in the general formula (1) is an oxyethylene group.
　本発明の樹脂組成物は、前記一般式（１）中のｎが２～８であることが好ましい。 In the resin composition of the present invention, n in the general formula (1) is preferably 2-8.
　本発明の樹脂組成物は、前記一般式（１）中のＲ２が、炭素数が１～６である無置換の芳香環、又は直鎖、分岐鎖、もしくは脂環式アルキル基であることが好ましい。 In the resin composition of the present invention, R 2 in the general formula (1) is an unsubstituted aromatic ring having 1 to 6 carbon atoms, or a linear, branched, or alicyclic alkyl group. Is preferred.
　本発明の樹脂組成物は、前記ヒドロキシル基を有するモノマーが、（メタ）アクリル系ポリマーを形成する全モノマー成分に対して、０．０１重量％以上、３重量％以下であることが好ましい。 In the resin composition of the present invention, the monomer having a hydroxyl group is preferably 0.01% by weight or more and 3% by weight or less based on all monomer components forming the (meth) acrylic polymer.
　本発明の樹脂組成物は、前記カルボキシル基を有するモノマーが、（メタ）アクリル系ポリマーを形成する全モノマー成分に対して、０．１重量％以上、５重量％以下であることが好ましい。 In the resin composition of the present invention, the monomer having a carboxyl group is preferably 0.1% by weight or more and 5% by weight or less based on all monomer components forming the (meth) acrylic polymer.
　本発明の積層シートの被着体が、コンクリ－ト、モルタル、石膏ボード、針葉樹合板、木質系セメント板、ケイ酸カルシウム板、タイル、及び繊維強化セメント板のいずれかであることが好ましいが、その他の平滑な被着体にも強力に接着可能である。 The adherend of the laminated sheet of the present invention is preferably one of concrete, mortar, gypsum board, softwood plywood, wood cement board, calcium silicate board, tile, and fiber reinforced cement board. It can be strongly bonded to other smooth adherends.
　本発明の樹脂組成物、樹脂層および積層シートは、例えば粘着剤組成物、粘着層および粘着シートとして利用可能である。 The resin composition, resin layer and laminated sheet of the present invention can be used as, for example, an adhesive composition, an adhesive layer and an adhesive sheet.
　本発明の樹脂組成物における主成分となる（メタ）アクリル系ポリマーは、特定量の長鎖の分岐したアルキル基を有するアルキル（メタ）アクリレートとエーテル結合を有する（メタ）アクリレートを含有するモノマー成分を重合することにより得られたものである。また、前記長鎖の分岐したアルキル基を有するアルキル（メタ）アクリレートとエーテル結合を有する（メタ）アクリレートのそれぞれのホモポリマーは低ガラス転移温度（Ｔｇ）を有し、かつ得られた（メタ）アクリル系ポリマーも低Ｔｇを有するものである。かかる本発明の樹脂組成物によれば、前記長鎖の分岐したアルキル基を有するアルキル（メタ）アクリレートと、前記エーテル結合を有する（メタ）アクリレートの作用により、粗面を有する被着体に対して、高い接着力及び高い保持力を発現することができる。 The (meth) acrylic polymer as the main component in the resin composition of the present invention is a monomer component containing a specific amount of an alkyl (meth) acrylate having a long-chain branched alkyl group and a (meth) acrylate having an ether bond. It was obtained by polymerizing. In addition, each homopolymer of the alkyl (meth) acrylate having a branched alkyl group having a long chain and the (meth) acrylate having an ether bond has a low glass transition temperature (Tg) and was obtained (meth) Acrylic polymers also have low Tg. According to such a resin composition of the present invention, an adherend having a rough surface is obtained by the action of the alkyl (meth) acrylate having a long-chain branched alkyl group and the (meth) acrylate having an ether bond. Thus, a high adhesive force and a high holding force can be expressed.
　炭素数８～１８の分岐したアルキル基を有するアルキル（メタ）アクリレートは、低Ｔｇかつ適度な凝集力と粘着性を有し、前記エーテル結合を有する（メタ）アクリレートは、低Ｔｇかつ適度な極性を有し、被着体表面との相互作用を有するため、結果として本発明の樹脂組成物は、適度な柔らかさと凝集力、界面との相互作用を有し、粗面を有する被着体に対して、高い接着力と高い保持力を発揮することができるものと推定される。 An alkyl (meth) acrylate having a branched alkyl group having 8 to 18 carbon atoms has a low Tg and appropriate cohesion and adhesiveness, and the (meth) acrylate having an ether bond has a low Tg and appropriate polarity. As a result, the resin composition of the present invention has an appropriate softness, cohesion, and interaction with the interface, and has a rough surface. On the other hand, it is estimated that a high adhesive force and a high holding force can be exhibited.
　また、本発明の樹脂組成物には、前記モノマー成分に、さらに、ヒドロキシル基を有するモノマー、カルボキシル基を有するモノマー、及びエポキシ基を有するモノマーから選ばれるいずれか少なくとも１つの官能基を有するモノマーを含有することにより、樹脂層の柔らかさを維持しつつ架橋ネットワーク形成と分子間相互作用のコントロールが可能となり、樹脂層の凝集力を高めることができ、粗面を有する被着体に対して、より高い保持力を発現することができるものと推定される。 In the resin composition of the present invention, the monomer component further includes a monomer having at least one functional group selected from a monomer having a hydroxyl group, a monomer having a carboxyl group, and a monomer having an epoxy group. By containing, it becomes possible to control the formation of a crosslinked network and intermolecular interaction while maintaining the softness of the resin layer, the cohesive force of the resin layer can be increased, and the adherend having a rough surface, It is presumed that higher holding power can be expressed.
　さらに、本発明の樹脂組成物から形成される樹脂層のゲル分率は、例えば、２０～９５重量％程度であれば、樹脂層の柔らかさを維持でき、かつ適度な架橋ネットワークの形成によって凝集力を付与することができるため、粗面を有する被着体に対して、より高い接着力及び高い保持力を発現することができるものと推定される。 Furthermore, if the gel fraction of the resin layer formed from the resin composition of the present invention is, for example, about 20 to 95% by weight, the softness of the resin layer can be maintained, and aggregation can be achieved by forming an appropriate crosslinked network. Since a force can be applied, it is presumed that a higher adhesive force and a higher holding force can be expressed on an adherend having a rough surface.
　以下、本発明の実施の形態について詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail.
　本発明の樹脂組成物は、ホモポリマーのＴｇが－５０℃以下であり、かつ炭素数８～１８の分岐したアルキル基をエステル基の末端に有するアルキル（メタ）アクリレート（ａ１）を５０～９７重量％、及びホモポリマーのＴｇが－４０℃以下であり、かつ分子骨格内にエーテル結合を有する（メタ）アクリレート（ａ２）を３～５０重量％を含むモノマー成分を重合することにより得られたＴｇが－４０℃以下である（メタ）アクリル系ポリマーを含む。尚、（メタ）アクリレートは、アクリレート及び／又はメタクリレートを意味する。 The resin composition of the present invention comprises an alkyl (meth) acrylate (a1) having a Tg of a homopolymer of −50 ° C. or lower and a branched alkyl group having 8 to 18 carbon atoms at the end of the ester group. It was obtained by polymerizing a monomer component containing 3 to 50% by weight of (meth) acrylate (a2) having a weight% and Tg of the homopolymer of −40 ° C. or less and having an ether bond in the molecular skeleton. A (meth) acrylic polymer having a Tg of −40 ° C. or lower is included. In addition, (meth) acrylate means an acrylate and / or a methacrylate.
＜炭素数８～１８の分岐したアルキル基をエステル基の末端に有するアルキル（メタ）アクリレート（ａ１）＞
　本発明の炭素数８～１８の分岐したアルキル基をエステル基の末端に有するアルキル（メタ）アクリレート（ａ１）のホモポリマーのＴｇは、－５０℃以下である。前記アルキル（メタ）アクリレート（ａ１）のＴｇは、粗面を有する被着体に対する接着力を高める観点から、－５５℃以下であることが好ましく、－６０℃以下であることがより好ましい。前記アルキル（メタ）アクリレート（ａ１）のＴｇは、粗面を有する被着体に対する保持力を高める観点から、－８０℃以上であることが好ましく、－７５℃以上であることがより好ましい。前記アルキル（メタ）アクリレート（ａ１）のアルキル基の炭素数は、樹脂層に適度な柔らかさを付与する観点、及び樹脂層の凝集力を高める観点から、８～１６であることが好ましく、８～１４であることがより好ましい。 <Alkyl (meth) acrylate (a1) having a branched alkyl group having 8 to 18 carbon atoms at the terminal of the ester group>
The Tg of the homopolymer of alkyl (meth) acrylate (a1) having a branched alkyl group having 8 to 18 carbon atoms at the end of the ester group of the present invention is −50 ° C. or lower. The Tg of the alkyl (meth) acrylate (a1) is preferably −55 ° C. or less, more preferably −60 ° C. or less, from the viewpoint of increasing the adhesive force to the adherend having a rough surface. The Tg of the alkyl (meth) acrylate (a1) is preferably −80 ° C. or higher, and more preferably −75 ° C. or higher, from the viewpoint of increasing the holding power for the adherend having a rough surface. The number of carbon atoms of the alkyl group of the alkyl (meth) acrylate (a1) is preferably 8 to 16 from the viewpoint of imparting appropriate softness to the resin layer and increasing the cohesive strength of the resin layer. More preferably, it is -14.
　本発明において、各モノマーのホモポリマーのＴｇは、「Ｐｏｌｙｍｅｒ　Ｈａｎｄｂｏｏｋ」（第３版、ＪｏｈｎＷｉｌｅｙ＆Ｓｏｎｓ，Ｉｎｃ．１９８９年）に記載の数値である（数値が複数ある場合は、conventionalの値を採用する、記載がない場合はモノマー製造企業のカタログ値を採用する）。 In the present invention, the Tg of the homopolymer of each monomer is a numerical value described in “Polymer Handbook” (3rd edition, John Wiley & Sons, Inc. 1989) (when there are a plurality of numerical values, a conventional value is adopted, If not stated, use the catalog value of the monomer manufacturer).
　上記文献に記載されていないモノマーのホモポリマーのＴｇは、以下の測定方法により得られる値である。即ち、温度計、攪拌機、窒素導入管及び還流冷却管を備えた反応器に、測定対象のモノマー１００重量部、アゾビスイソブチロニトリル０．１重量部及び重合溶媒として酢酸エチル２００重量部を投入し、窒素ガスを投入しながら１時間攪拌する。このようにして重合系内の酸素を除去した後、６０℃に昇温し１２時間反応させる。次いで、室温まで冷却し、このホモポリマー溶液を剥離ライナー上に流延塗布し、乾燥して厚さ約５０μｍの試験サンプル（シート状のホモポリマー）を作製する。得られた試料を２～３ｍｇ採取し、アルミ製容器に入れ、クリンプしＤＳＣ測定（TA Instruments製 Q-2000）を行う。温度プログラムは－８０℃～１５０℃（測定速度１０℃／ｍｉｎ）、窒素（５０ｍｌ／ｍｉｎ）雰囲気ガス下で測定した。得られたチャートよりＴｍｇ（中点ガラス転移温度）の数値を読み取りこの値をホモポリマーのＴｇとした。 The Tg of a homopolymer of a monomer not described in the above literature is a value obtained by the following measurement method. That is, in a reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser, 100 parts by weight of the monomer to be measured, 0.1 part by weight of azobisisobutyronitrile, and 200 parts by weight of ethyl acetate as a polymerization solvent. Stir for 1 hour while charging nitrogen gas. After removing oxygen in the polymerization system in this way, the temperature is raised to 60 ° C. and reacted for 12 hours. Subsequently, it cools to room temperature, this homopolymer solution is cast-coated on a release liner, and it dries and produces the test sample (sheet-like homopolymer) about 50 micrometers thick. 2 to 3 mg of the obtained sample is collected, placed in an aluminum container, crimped, and subjected to DSC measurement (TA-Instruments Q-2000). The temperature program was measured under an atmosphere gas of −80 ° C. to 150 ° C. (measurement speed 10 ° C./min) and nitrogen (50 ml / min). A value of Tmg (midpoint glass transition temperature) was read from the obtained chart, and this value was defined as Tg of the homopolymer.
　前記アルキル（メタ）アクリレート（ａ１）としては、例えば、２－エチルヘキシルアクリレート（炭素数８，ホモポリマーのＴｇ＝－７０℃）、イソオクチルアクリレート（炭素数８，ホモポリマーのＴｇ＝－５８℃）、イソノニルアクリレート（炭素数９，ホモポリマーのＴｇ＝－５８℃）、イソデシルアクリレート（炭素数１０，ホモポリマーのＴｇ＝－６０℃）、イソミスチリルアクリレート（炭素数１４，Ｔｇ＝－５６℃）イソウンデシルアクリレート、イソドデシルアクリレート、イソペンタデシルアクリレート、イソヘキサデシルアクリレート、イソヘプタデシルアクリレート、イソオクタデシルアクリレート及び前記例示のメタクリレートを例示できる。前記アルキル（メタ）アクリレート（ａ１）は、単独でまたは組み合わせて使用できる。尚、前記アルキル（メタ）アクリレート（ａ１）は、樹脂層の粘着力を高める観点、重合反応性の観点から、アルキルアクリレートが好適である。 Examples of the alkyl (meth) acrylate (a1) include 2-ethylhexyl acrylate (carbon number 8, homopolymer Tg = −70 ° C.), isooctyl acrylate (carbon number 8, homopolymer Tg = −58 ° C.). , Isononyl acrylate (carbon number 9, homopolymer Tg = −58 ° C.), isodecyl acrylate (carbon number 10, homopolymer Tg = −60 ° C.), isomisticyl acrylate (carbon number 14, Tg = −56 ° C.) ) Isoundecyl acrylate, isododecyl acrylate, isopentadecyl acrylate, isohexadecyl acrylate, isoheptadecyl acrylate, isooctadecyl acrylate, and the above exemplified methacrylates. The alkyl (meth) acrylate (a1) can be used alone or in combination. The alkyl (meth) acrylate (a1) is preferably an alkyl acrylate from the viewpoint of increasing the adhesive strength of the resin layer and from the viewpoint of polymerization reactivity.
＜分子骨格内にエーテル結合を有する（メタ）アクリレート（ａ２）＞
　本発明のエーテル結合を有する（メタ）アクリレート（ａ２）のホモポリマーのＴｇは、－４０℃以下である。前記エーテル結合を有する（メタ）アクリレート（ａ２）のＴｇは、粗面を有する被着体に対する接着力を高める観点から、－４５℃以下であることが好ましく、－５０℃以下であることがより好ましい。前記エーテル結合を有する（メタ）アクリレート（ａ２）のＴｇは、粗面を有する被着体に対する接着力及び保持力を高める観点から、－９０℃以上であることが好ましく、－８０℃以上であることがより好ましい。尚、前記エーテル結合は、鎖状エーテル結合を意味し、エポキシ基、オキセタン基等の環状エーテル結合とは異なる。 <(Meth) acrylate (a2) having ether bond in molecular skeleton>
The Tg of the homopolymer of (meth) acrylate (a2) having an ether bond of the present invention is −40 ° C. or lower. The Tg of the (meth) acrylate (a2) having an ether bond is preferably −45 ° C. or less, more preferably −50 ° C. or less, from the viewpoint of increasing the adhesion to an adherend having a rough surface. preferable. The Tg of the (meth) acrylate (a2) having an ether bond is preferably −90 ° C. or higher, and preferably −80 ° C. or higher, from the viewpoint of increasing the adhesion and holding power to the adherend having a rough surface. It is more preferable. The ether bond means a chain ether bond and is different from a cyclic ether bond such as an epoxy group or an oxetane group.
　前記エーテル結合を有する（メタ）アクリレート（ａ２）としては、（メタ）アクリロイル基の不飽和二重結合を有し、かつ鎖状エーテル結合を有するものを特に制限なく用いることができる。前記エーテル結合を有する（メタ）アクリレート（ａ２）としては、例えば、一般式（１）：ＣＨ２＝ＣＲ１－ＣＯＯ－（ＡＯ）ｎ－Ｒ２［前記一般式（１）中、Ｒ１は水素原子又はメチル基、ＡＯは炭素数２～３のアルキレンオキシ基、ｎはアルキレンオキシ基の平均付加モル数を示す１～８であり、Ｒ２は芳香環、又は直鎖、分岐鎖、もしくは脂環式アルキル基である。］で表されるモノマー（但し、前記一般式（１）中のＲ２はエーテル結合を含まない）等が挙げられる。前記エーテル結合を有する（メタ）アクリレート（ａ２）は、単独でまたは組み合わせて使用できる。 As the (meth) acrylate (a2) having an ether bond, those having an unsaturated double bond of a (meth) acryloyl group and having a chain ether bond can be used without particular limitation. Examples of the (meth) acrylate (a2) having an ether bond include, for example, the general formula (1): CH 2 ═CR 1 —COO— (AO) n —R 2 [in the general formula (1), R 1 represents A hydrogen atom or a methyl group, AO is an alkyleneoxy group having 2 to 3 carbon atoms, n is 1 to 8 indicating the average number of moles added of the alkyleneoxy group, and R 2 is an aromatic ring, a straight chain, a branched chain, or An alicyclic alkyl group. ] (Wherein R 2 in the general formula (1) does not include an ether bond), and the like. The (meth) acrylate (a2) having an ether bond can be used alone or in combination.
　前記一般式（１）で表されるモノマーとしては、平均付加モル数１～８のオキシエチレン基を有する、メトキシポリエチレングリコール（メタ）アクリレート、エトキシポリエチレングリコール（メタ）アクリレート、プロポキシポリエチレングリコール（メタ）アクリレート等が挙げられる。また、平均付加モル数１～８のオキシプロピレン基を有する、メトキシポリプロピレングリコール（メタ）アクリレート、エトキシポリプロピレングリコール（メタ）アクリレート、プロポキシポリプロピレングリコール（メタ）アクリレート等が挙げられる。 Examples of the monomer represented by the general formula (1) include methoxypolyethylene glycol (meth) acrylate, ethoxypolyethyleneglycol (meth) acrylate, and propoxypolyethyleneglycol (meth) having an oxyethylene group having an average addition mole number of 1 to 8. An acrylate etc. are mentioned. Further, methoxypolypropylene glycol (meth) acrylate, ethoxypolypropylene glycol (meth) acrylate, propoxypolypropylene glycol (meth) acrylate and the like having an oxypropylene group having an average addition mole number of 1 to 8 can be mentioned.
　前記一般式（１）中のＡＯは、適度な極性バランスを有する観点から、炭素数２のアルキレンオキシ基である、オキシエチレン基が好ましい。また、前記一般式（１）中のｎは、極性レベルと重合反応性の観点から、２～８であることが好ましく、２～５であることがより好ましい。具体的な化合物としては、エチルカルビトールアクリレート（エトキシエトキシエチルアクリレート）（ホモポリマーのＴｇ＝－６７℃）、メトキシトリエチレングリコールアクリレート（ホモポリマーのＴｇ＝－５７℃）等が挙げられる。 AO in the general formula (1) is preferably an oxyethylene group which is an alkyleneoxy group having 2 carbon atoms from the viewpoint of having an appropriate polarity balance. Further, n in the general formula (1) is preferably 2 to 8, more preferably 2 to 5, from the viewpoint of the polar level and the polymerization reactivity. Specific examples of the compound include ethyl carbitol acrylate (ethoxyethoxyethyl acrylate) (homopolymer Tg = −67 ° C.), methoxytriethylene glycol acrylate (homopolymer Tg = −57 ° C.), and the like.
　前記一般式（１）中のＲ２は、無置換の芳香環、又は直鎖、分岐鎖、もしくは脂環式アルキル基であることが好ましい。Ｒ２の芳香環としては、フェニル基等、Ｒ２の直鎖アルキル基、分岐鎖アルキルとしては、イソプロピル基、エチル基、メチル基等、Ｒ２の脂環式アルキル基としてはシクロヘキシル基等が挙げられ、中でも直鎖アルキル基が好ましい。Ｒ２は適度な極性を有する観点から、炭素数が１～６であることが好ましく、１～５であることがより好ましい。 R 2 in the general formula (1) is preferably an unsubstituted aromatic ring, or a linear, branched, or alicyclic alkyl group. Examples of the aromatic ring of R 2 include a phenyl group, a linear alkyl group of R 2 , a branched chain alkyl such as an isopropyl group, an ethyl group, and a methyl group, and an alicyclic alkyl group of R 2 includes a cyclohexyl group and the like. Among them, a linear alkyl group is preferable. R 2 preferably has 1 to 6 carbon atoms, and more preferably 1 to 5 carbon atoms from the viewpoint of appropriate polarity.
　本発明において、前記アルキル（メタ）アクリレート（ａ１）は、（メタ）アクリル系ポリマーを形成する全モノマー成分に対して、５０～９７重量％である。前記アルキル（メタ）アクリレート（ａ１）は、（メタ）アクリル系ポリマーを形成する全モノマー成分に対して、粗面を有する被着体に対する接着力及び保持力を高める観点から、５５重量％以上であることが好ましく、５８重量％以上であることがより好ましく、５９重量％以上であることがさらに好ましい。前記アルキル（メタ）アクリレート（ａ１）は、（メタ）アクリル系ポリマーを形成する全モノマー成分に対して、粗面を有する被着体に対する接着力及び保持力を高める観点から、９５重量％以下であることが好ましく、９３重量％以下であることがより好ましく、９１重量％以下であることがさらに好ましい。 In the present invention, the alkyl (meth) acrylate (a1) is 50 to 97% by weight based on all monomer components forming the (meth) acrylic polymer. The alkyl (meth) acrylate (a1) is 55% by weight or more from the viewpoint of increasing the adhesive force and holding power to the adherend having a rough surface with respect to all monomer components forming the (meth) acrylic polymer. Preferably, it is 58 wt% or more, more preferably 59 wt% or more. The alkyl (meth) acrylate (a1) is 95% by weight or less from the viewpoint of increasing the adhesion and holding power to the adherend having a rough surface with respect to all monomer components forming the (meth) acrylic polymer. Preferably, it is 93% by weight or less, more preferably 91% by weight or less.
　本発明において、前記エーテル結合を有する（メタ）アクリレート（ａ２）は、（メタ）アクリル系ポリマーを形成する全モノマー成分に対して、３～５０重量％である。前記エーテル結合を有する（メタ）アクリレート（ａ２）は、（メタ）アクリル系ポリマーを形成する全モノマー成分に対して、粗面を有する被着体に対する接着力及び保持力を高める観点から、３．５重量％以上であることが好ましく、４重量％以上であることがより好ましく、４．５重量％以上であることがさらに好ましい。前記エーテル結合を有する（メタ）アクリレート（ａ２）は、（メタ）アクリル系ポリマーを形成する全モノマー成分に対して、粗面を有する被着体に対する接着力及び保持力を高める観点から、４８重量％以下であることが好ましく、４５重量％以下であることがより好ましく、４０重量％以下であることがさらに好ましい。 In the present invention, the (meth) acrylate (a2) having an ether bond is 3 to 50% by weight based on all monomer components forming the (meth) acrylic polymer. The (meth) acrylate (a2) having an ether bond is from the viewpoint of enhancing the adhesion and holding power to the adherend having a rough surface with respect to all monomer components forming the (meth) acrylic polymer. It is preferably 5% by weight or more, more preferably 4% by weight or more, and further preferably 4.5% by weight or more. The (meth) acrylate (a2) having an ether bond is 48% by weight from the viewpoint of increasing the adhesion and holding power to the adherend having a rough surface with respect to all monomer components forming the (meth) acrylic polymer. % Or less, more preferably 45% by weight or less, and even more preferably 40% by weight or less.
　本発明において、前記アルキル（メタ）アクリレート（ａ１）及び前記エーテル結合を有する（メタ）アクリレート（ａ２）の合計の割合は、７５重量％以上であることが好ましい。前記アルキル（メタ）アクリレート（ａ１）及び前記エーテル結合を有する（メタ）アクリレート（ａ２）の合計の割合は、（メタ）アクリル系ポリマーを形成する全モノマー成分に対して、粗面を有する被着体に対する接着力及び保持力を高める観点から、８０重量％以上であることがより好ましく、８５重量％以上であることがさらに好ましく、９０重量％以上であることがよりさらに好ましい。 In the present invention, the total ratio of the alkyl (meth) acrylate (a1) and the (meth) acrylate (a2) having an ether bond is preferably 75% by weight or more. The total proportion of the alkyl (meth) acrylate (a1) and the ether-bonded (meth) acrylate (a2) is a deposition having a rough surface with respect to all monomer components forming the (meth) acrylic polymer. From the viewpoint of enhancing the adhesion and holding power to the body, it is more preferably 80% by weight or more, further preferably 85% by weight or more, and still more preferably 90% by weight or more.
＜官能基を有するモノマー＞
　本発明の（メタ）アクリル系ポリマーを形成するモノマー成分には、さらに、ヒドロキシル基を有するモノマー、カルボキシル基を有するモノマー、及びエポキシ基を有するモノマーから選ばれるいずれか少なくとも１つの官能基を有するモノマーを含むことができる。 <Monomer having a functional group>
The monomer component forming the (meth) acrylic polymer of the present invention further includes a monomer having at least one functional group selected from a monomer having a hydroxyl group, a monomer having a carboxyl group, and a monomer having an epoxy group Can be included.
　前記ヒドロキシル基を有するモノマーとしては、（メタ）アクリロイル基またはビニル基等の不飽和二重結合を有する重合性の官能基を有し、かつヒドロキシル基を有するものを特に制限なく用いることができる。前記ヒドロキシル基を有するモノマーとしては、例えば、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、３－ヒドロキシプロピル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、６－ヒドロキシヘキシル（メタ）アクリレート、８－ヒドロキシオクチル（メタ）アクリレート、１０－ヒドロキシデシル（メタ）アクリレート、１２－ヒドロキシラウリル（メタ）アクリレート等のヒドロキシアルキル（メタ）アクリレート；（４－ヒドロキシメチルシクロへキシル）メチル（メタ）アクリレート等のヒドロキシアルキルシクロアルカン（メタ）アクリレートが挙げられる。その他、ヒドロキシエチル（メタ）アクリルアミド、アリルアルコール、２－ヒドロキシエチルビニルエーテル、４－ヒドロキシブチルビニルエーテル、ジエチレングリコールモノビニルエーテル等が挙げられる。前記ヒドロキシル基を有するモノマーは単独でまたは組み合わせて使用できる。これらのなかでもヒドロキシアルキル（メタ）アクリレートが好適であり、特に２－ヒドロキシエチル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレートが好ましい。 As the monomer having a hydroxyl group, a monomer 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 can be used without particular limitation. Examples of the monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 6-hydroxy. Hydroxyalkyl (meth) acrylates such as hexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate; (4-hydroxymethylcyclohexyl) And hydroxyalkylcycloalkane (meth) acrylates such as methyl (meth) acrylate. Other examples include hydroxyethyl (meth) acrylamide, allyl alcohol, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, and the like. The monomer having a hydroxyl group can be used alone or in combination. Of these, hydroxyalkyl (meth) acrylate is preferable, and 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate are particularly preferable.
　前記カルボキシル基を有するモノマーとしては、（メタ）アクリロイル基またはビニル基等の不飽和二重結合を有する重合性の官能基を有し、かつカルボキシル基を有するものを特に制限なく用いることができる。前記カルボキシル基を有するモノマーとしては、例えば、（メタ）アクリル酸、カルボキシエチル（メタ）アクリレート、カルボキシペンチル（メタ）アクリレート、イタコン酸、マレイン酸、フマール酸、クロトン酸、イソクロトン酸等が挙げられる。前記カルボキシル基を有するモノマーは単独でまたは組み合わせて使用できる。これらのなかでもアクリル酸、メタクリル酸が好適であり、特にアクリル酸が好適である。 As the monomer having a carboxyl group, a monomer 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 can be used without particular limitation. Examples of the monomer having a carboxyl group include (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid. The monomers having a carboxyl group can be used alone or in combination. Among these, acrylic acid and methacrylic acid are preferable, and acrylic acid is particularly preferable.
　前記エポキシ基を有するモノマーとしては、（メタ）アクリロイル基またはビニル基等の不飽和二重結合を有する重合性の官能基を有し、かつエポキシ基を有するものを特に制限なく用いることができる。前記エポキシ基を有するモノマーとしては、例えば、グリシジル（メタ）アクリレート、３，４－エポキシシクロヘキシルメチル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレートグリシジルエーテル等が挙げられる。前記エポキシ基を有するモノマーは単独でまたは組み合わせて使用できる。 As the monomer having an epoxy group, a monomer 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 can be used without particular limitation. Examples of the monomer having an epoxy group include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and the like. The monomers having the epoxy group can be used alone or in combination.
　本発明において、前記ヒドロキシル基を有するモノマーは、（メタ）アクリル系ポリマーを形成する全モノマー成分に対して、凝集力を高める観点から、０．０１重量％以上であることが好ましく、０．０３重量％以上であることがより好ましい。前記ヒドロキシル基を有するモノマーは、（メタ）アクリル系ポリマーを形成する全モノマー成分に対して、ポリマーの過度な粘度上昇やゲル化を抑制する観点から、３重量％以下であることが好ましく、２重量％以下であることがより好ましい。 In the present invention, the monomer having a hydroxyl group is preferably 0.01% by weight or more from the viewpoint of increasing cohesion with respect to all monomer components forming the (meth) acrylic polymer. More preferably, it is at least wt%. The monomer having a hydroxyl group is preferably 3% by weight or less from the viewpoint of suppressing excessive viscosity increase and gelation of the polymer with respect to all monomer components forming the (meth) acrylic polymer. More preferably, it is less than or equal to weight percent.
　本発明において、前記カルボキシル基を有するモノマーは、（メタ）アクリル系ポリマーを形成する全モノマー成分に対して、凝集力を高める観点、及び被着体表面との分子的な相互作用を付与する観点から、０．１重量％以上であることが好ましく、０．２重量％以上であることがより好ましい。前記カルボキシル基を有するモノマーは、（メタ）アクリル系ポリマーを形成する全モノマー成分に対して、粗面への追従性を高める観点や低温での粘着力を高く維持する観点から、５重量％以下であることが好ましく、３重量％以下であることがより好ましく、さらに２重量％以下であることがより好ましい。 In the present invention, the monomer having a carboxyl group has a viewpoint of increasing cohesive force and a molecular interaction with the adherend surface with respect to all monomer components forming the (meth) acrylic polymer. Therefore, it is preferably 0.1% by weight or more, and more preferably 0.2% by weight or more. The monomer having a carboxyl group is 5% by weight or less from the viewpoint of increasing the followability to a rough surface and maintaining high adhesive strength at low temperatures with respect to all monomer components forming the (meth) acrylic polymer. Preferably, it is 3% by weight or less, more preferably 2% by weight or less.
　本発明において、前記エポキシ基を有するモノマーは、（メタ）アクリル系ポリマーを形成する全モノマー成分に対して、凝集力を高める観点から、０．１重量％以上であることが好ましく、０．２重量％以上であることがより好ましい。前記エポキシ基を有するモノマーは、（メタ）アクリル系ポリマーを形成する全モノマー成分に対して、ゲル化や高粘度化を抑制する観点から、１重量％以下であることが好ましく、０．５重量％以下であることがより好ましい。（メタ）アクリル系ポリマーがグラフト重合体の場合、この限りではない。 In the present invention, the monomer having an epoxy group is preferably 0.1% by weight or more from the viewpoint of increasing cohesion with respect to all monomer components forming the (meth) acrylic polymer, More preferably, it is at least wt%. The monomer having an epoxy group is preferably 1% by weight or less from the viewpoint of suppressing gelation and viscosity increase with respect to all monomer components forming the (meth) acrylic polymer, and 0.5% by weight. % Or less is more preferable. This is not the case when the (meth) acrylic polymer is a graft polymer.
＜共重合モノマー＞
　本発明の（メタ）アクリル系ポリマーを形成するモノマー成分には、前記官能基を有するモノマー以外の共重合モノマーを含むことができる。前記共重合モノマーとしては、例えば、一般式（２）：ＣＨ２＝ＣＲ３－ＣＯＯ－Ｒ４（前記Ｒ３は水素原子又はメチル基、Ｒ４は炭素数１～２４の無置換のアルキル基又は置換されたアルキル基を表す。但し、炭素数８～１８の分岐したアルキル基の場合を除く。）で表されるモノマーが挙げられる。共重合モノマーは単独でまたは組み合わせて使用できる。 <Copolymerized monomer>
The monomer component forming the (meth) acrylic polymer of the present invention may contain a copolymerization monomer other than the monomer having the functional group. Examples of the copolymer monomer include, for example, the general formula (2): CH 2 ═CR 3 —COO—R 4 (wherein R 3 is a hydrogen atom or a methyl group, and R 4 is an unsubstituted alkyl group having 1 to 24 carbon atoms). Or a substituted alkyl group, except for branched alkyl groups having 8 to 18 carbon atoms). Copolymerization monomers can be used alone or in combination.
　前記一般式（２）中のＲ４としての、炭素数１～２４（より好ましくは炭素数１～１８）の無置換のアルキル基または置換されたアルキル基は、直鎖、分岐鎖のアルキル基、あるいは環状のシクロアルキル基を示し、炭素数８～１８の分岐したアルキル基の場合を除く。Ｒ４は具体的には、炭素数１～１８の直鎖状アルキル基、炭素数３～７の分岐したアルキル基、環状のアルキル基が挙げられる。置換されたアルキル基の場合は、置換基としては、炭素数３－７個のアリール基または炭素数３－７個のアリールオキシ基であることが好ましい。アリール基としては、限定はされないが、フェニル基が好ましい。 An 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, except for branched alkyl groups having 8 to 18 carbon atoms. Specific examples of R 4 include a linear alkyl group having 1 to 18 carbon atoms, a branched alkyl group having 3 to 7 carbon atoms, and a cyclic alkyl group. In the case of a substituted alkyl group, the substituent is preferably an aryl group having 3 to 7 carbon atoms or an aryloxy group having 3 to 7 carbon atoms. The aryl group is not limited, but is preferably a phenyl group.
　前記一般式（２）で表されるモノマーの例としては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、ｓ－ブチル（メタ）アクリレート、ｔ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｎ－ペンチル（メタ）アクリレート、イソペンチル（メタ）アクリレート、へキシル（メタ）アクリレート、ヘプチル（メタ）アクリレート、イソアミル（メタ）アクリレート、ｎ－オクチル（メタ）アクリレート、ｎ－ノニル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、ベンジル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、３，３，５－トリメチルシクロヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート、テルペン（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート等が挙げられる。 Examples of the monomer represented by the 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 (meth) acrylate, terpene ( Data) acrylate, dicyclopentanyl (meth) acrylate.
　また、前記共重合モノマーとしては、例えば、酢酸ビニル、プロピオン酸ビニル、スチレン、α－メチルスチレン、Ｎ－ビニルカプロラクタム、Ｎ－ビニルピロリドン等のビニル系モノマー；（メタ）アクリル酸テトラヒドロフルフリル、フッ素（メタ）アクリレート、シリコーン（メタ）アクリレートや２－メトキシエチルアクリレート等のアクリル酸エステル系モノマー；アミド基含有モノマー、アミノ基含有モノマー、イミド基含有モノマー、Ｎ－アクリロイルモルホリン、ビニルエーテルモノマー等も使用することができる。 Examples of the copolymerization monomer include vinyl monomers such as vinyl acetate, vinyl propionate, styrene, α-methylstyrene, N-vinylcaprolactam, N-vinylpyrrolidone; tetrahydrofurfuryl (meth) acrylate, fluorine Acrylic acid ester monomers such as (meth) acrylate, silicone (meth) acrylate and 2-methoxyethyl acrylate; amide group-containing monomers, amino group-containing monomers, imide group-containing monomers, N-acryloylmorpholine, vinyl ether monomers, etc. are also used. be able to.
　さらに、前記共重合モノマーとしては、ケイ素原子を含有するシラン系モノマー等が挙げられる。シラン系モノマーとしては、例えば、３－アクリロキシプロピルトリエトキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、４－ビニルブチルトリメトキシシラン、４－ビニルブチルトリエトキシシラン、８－ビニルオクチルトリメトキシシラン、８－ビニルオクチルトリエトキシシラン、１０－メタクリロイルオキシデシルトリメトキシシラン、１０－アクリロイルオキシデシルトリメトキシシラン、１０－メタクリロイルオキシデシルトリエトキシシラン、１０－アクリロイルオキシデシルトリエトキシシラン等が挙げられる。 Furthermore, examples of the copolymerization monomer include a silane monomer containing a silicon atom. Examples of the silane monomer include 3-acryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 4-vinylbutyltrimethoxysilane, 4-vinylbutyltriethoxysilane, and 8-vinyloctyltrimethoxysilane. , 8-vinyloctyltriethoxysilane, 10-methacryloyloxydecyltrimethoxysilane, 10-acryloyloxydecyltrimethoxysilane, 10-methacryloyloxydecyltriethoxysilane, 10-acryloyloxydecyltriethoxysilane, and the like.
　本発明において、前記共重合モノマーは、（メタ）アクリル系ポリマーを形成する全モノマー成分に対して、２０重量％以下であることが好ましく、１５重量％以下であることがより好ましい。共重合モノマーの含有量が、２０重量％を超えると、例えば、粗面への接着性が低下する場合がある。 In the present invention, the copolymerization monomer is preferably 20% by weight or less, and more preferably 15% by weight or less, based on all monomer components forming the (meth) acrylic polymer. When the content of the comonomer exceeds 20% by weight, for example, adhesion to a rough surface may be lowered.
＜多官能性モノマー＞
　本発明の（メタ）アクリル系ポリマーを形成するモノマー成分には、樹脂組成物の凝集力を調整するために、必要に応じて多官能性モノマーを含有することができる。多官能性モノマーは単独でまたは組み合わせて使用できる。 <Multifunctional monomer>
The monomer component that forms the (meth) acrylic polymer of the present invention may contain a polyfunctional monomer as necessary in order to adjust the cohesive strength of the resin composition. Polyfunctional monomers can be used alone or in combination.
　前記多官能性モノマーは、（メタ）アクリロイル基またはビニル基等の不飽和二重結合を有する重合性の官能基を少なくとも２つ有するモノマーであり、例えば、（ポリ）エチレングリコールジ（メタ）アクリレート、（ポリ）プロピレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、ペンタエリスリトールジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、１，２－エチレングリコールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、１，１２－ドデカンジオールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、テトラメチロールメタントリ（メタ）アクリレート等の多価アルコールと（メタ）アクリル酸とのエステル化合物；アリル（メタ）アクリレート、ビニル（メタ）アクリレート、ジビニルベンゼン、エポキシアクリレート、ポリエステルアクリレート、ウレタンアクリレート、ブチルジ（メタ）アクリレート、ヘキシルジ（メタ）アクリレート等が挙げられる。これらのなかでも、トリメチロールプロパントリ（メタ）アクリレート、ヘキサンジオールジ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレートが好適である。 The polyfunctional monomer is a monomer having at least two polymerizable functional groups having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group, such as (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, tetramethylolmethanetri (meth) Ester compound of polyhydric alcohol such as acrylate and (meth) acrylic acid; allyl (meth) acrylate, vinyl (meth) acrylate, divinylbenzene, epoxy acrylate, polyester acrylate, urethane acrylate, butyl di (meth) acrylate, hexyl di (meth) ) Acrylate and the like. Among these, trimethylolpropane tri (meth) acrylate, hexanediol di (meth) acrylate, and dipentaerythritol hexa (meth) acrylate are preferable.
　前記多官能性モノマーは、（メタ）アクリル系ポリマーを形成する全モノマー成分に対して、５重量％以下で用いることができる。前記多官能性モノマーは、その分子量や官能基数等により異なるが、（メタ）アクリル系ポリマーを形成する全モノマー成分に対して、３重量％以下が好ましく、さらには２重量％以下が好ましい。多官能性モノマーの含有量が、５重量％を超えると、例えば、樹脂組成物の弾性率が高くなりすぎ、接着力が低下する場合がある。 The polyfunctional monomer can be used at 5% by weight or less based on the total monomer components forming the (meth) acrylic polymer. Although the said polyfunctional monomer changes with the molecular weight, the number of functional groups, etc., 3 weight% or less is preferable with respect to all the monomer components which form a (meth) acrylic-type polymer, Furthermore, 2 weight% or less is preferable. When the content of the polyfunctional monomer exceeds 5% by weight, for example, the elastic modulus of the resin composition becomes too high, and the adhesive force may be reduced.
＜（メタ）アクリル系ポリマー、及びその製造方法＞
　本発明の（メタ）アクリル系ポリマーのＴｇは、－４０℃以下である。前記（メタ）アクリル系ポリマーのＴｇは、粗面を有する被着体に対する接着力を高める観点から、－４５℃以下であることが好ましく、－５０℃以下であることがより好ましい。前記（メタ）アクリル系ポリマーのＴｇは、粗面を有する被着体に対する接着力及び保持力を高める観点から、－８５℃以上であることが好ましく、－８０℃以上であることがより好ましい。尚、（メタ）アクリル系ポリマーのＴｇは、（メタ）アクリル系ポリマーを構成するモノマー単位とその割合から、以下のＦＯＸの式より算出される理論値である。 <(Meth) acrylic polymer and production method thereof>
The Tg of the (meth) acrylic polymer of the present invention is −40 ° C. or lower. The Tg of the (meth) acrylic polymer is preferably −45 ° C. or less, and more preferably −50 ° C. or less, from the viewpoint of increasing the adhesive force to the adherend having a rough surface. The Tg of the (meth) acrylic polymer is preferably −85 ° C. or higher, and more preferably −80 ° C. or higher, from the viewpoint of increasing the adhesion and holding power to the adherend having a rough surface. The Tg of the (meth) acrylic polymer is a theoretical value calculated from the following FOX formula from the monomer units constituting the (meth) acrylic polymer and the ratio thereof.
　ＦＯＸの式：１／Ｔｇ＝Ｗ１／Ｔｇ１＋Ｗ２／Ｔｇ２＋・・・＋Ｗｎ／Ｔｇｎ
［式中、Ｔｇは（メタ）アクリル系ポリマーのガラス転移温度（単位：Ｋ）、Ｔｇｉ（ｉ＝１、２、・・・ｎ）は、モノマーｉがホモポリマーを形成した際のガラス転移温度（単位：Ｋ）、Ｗｉ（ｉ＝１、２、・・・ｎ）は、モノマーｉの全モノマー成分中の質量分率を表す。］ Formula of FOX: 1 / Tg = W 1 / Tg 1 + W 2 / Tg 2 +... + W n / Tg n
[Wherein, Tg is the glass transition temperature (unit: K) of the (meth) acrylic polymer, and Tg i (i = 1, 2,... N) is the glass transition when the monomer i forms a homopolymer. Temperature (unit: K), W i (i = 1, 2,... N) represents a mass fraction of all monomer components of monomer i. ]
　前記（メタ）アクリル系ポリマーの製造は、溶液重合、電子線やＵＶ等の放射線重合、塊状重合、乳化重合等の各種ラジカル重合等の公知の製造方法を適宜選択できる。また、得られる（メタ）アクリル系ポリマーは、ランダム共重合体、ブロック共重合体、グラフト共重合体等のいずれでもよい。 For the production of the (meth) acrylic polymer, known production methods such as solution polymerization, radiation polymerization such as electron beam and UV, bulk polymerization, emulsion polymerization and the like can be appropriately selected. Further, the (meth) acrylic polymer obtained may be any of a random copolymer, a block copolymer, a graft copolymer, and the like.
　前記ラジカル重合に用いられる重合開始剤、連鎖移動剤、乳化剤等は特に限定されず適宜選択して使用することができる。尚、（メタ）アクリル系ポリマーの重量平均分子量は、重合開始剤、連鎖移動剤の使用量、反応条件により制御可能であり、これらの種類に応じて適宜のその使用量が調整される。 The polymerization initiator, chain transfer agent, emulsifier and the like used for the radical polymerization are not particularly limited and can be appropriately selected and used. In addition, the weight average molecular weight of a (meth) acrylic-type polymer can be controlled by the usage-amount of a polymerization initiator and a chain transfer agent, and reaction conditions, The usage-amount is suitably adjusted according to these kinds.
　前記溶液重合においては、重合溶媒として、例えば、酢酸エチル、トルエン等が用いられる。具体的な溶液重合例としては、反応は窒素等の不活性ガス気流下で、重合開始剤を加え、通常、５０～７０℃程度で、５～３０時間程度の反応条件で行われる。 In the solution polymerization, for example, ethyl acetate, toluene or the like is used as a polymerization solvent. As a specific example of solution polymerization, the reaction is carried out in an inert gas stream such as nitrogen and a polymerization initiator is added, and the reaction is usually performed at about 50 to 70 ° C. under reaction conditions for about 5 to 30 hours.
　前記重合開始剤としては、例えば、２，２’－アゾビスイソブチロニトリル、２，２’－アゾビス（２－アミジノプロパン）ジヒドロクロライド、２，２’－アゾビス［２－（５－メチル－２－イミダゾリン－２－イル）プロパン］ジヒドロクロライド、２，２’－アゾビス（２－メチルプロピオンアミジン）二硫酸塩、２，２’－アゾビス（Ｎ，Ｎ’－ジメチレンイソブチルアミジン）、２，２’－アゾビス［Ｎ－（２－カルボキシエチル）－２－メチルプロピオンアミジン］ハイドレート（和光純薬社製、ＶＡ－０５７）等のアゾ系開始剤、過硫酸カリウム、過硫酸アンモニウム等の過硫酸塩、ジ（２－エチルヘキシル）パーオキシジカーボネート、ジ（４－ｔ－ブチルシクロヘキシル）パーオキシジカーボネート、ジ－ｓｅｃ－ブチルパーオキシジカーボネート、ｔ－ブチルパーオキシネオデカノエート、ｔ－ヘキシルパーオキシピバレート、ｔ－ブチルパーオキシピバレート、ジラウロイルパーオキシド、ジ－ｎ－オクタノイルパーオキシド、１，１，３，３－テトラメチルブチルパーオキシ－２－エチルヘキサノエート、ジ（４－メチルベンゾイル）パーオキシド、ジベンゾイルパーオキシド、ｔ－ブチルパーオキシイソブチレート、１，１－ジ（ｔ－ヘキシルパーオキシ）シクロヘキサン、ｔ－ブチルハイドロパーオキシド、過酸化水素等の過酸化物系開始剤、過硫酸塩と亜硫酸水素ナトリウムの組み合わせ、過酸化物とアスコルビン酸ナトリウムの組み合わせ等の過酸化物と還元剤とを組み合わせたレドックス系開始剤等を挙げることができるが、これらに限定されるものではない。 Examples of the polymerization initiator include 2,2′-azobisisobutyronitrile, 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), 2, Azo-based initiators such as 2′-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate (manufactured by Wako Pure Chemical Industries, Ltd., VA-057), and persulfates such as potassium persulfate and ammonium persulfate Salt, di (2-ethylhexyl) peroxydicarbonate, di (4-tert-butylcyclohexyl) peroxydicarbonate, di-sec-butyl Peroxydicarbonate, t-butylperoxyneodecanoate, t-hexylperoxypivalate, t-butylperoxypivalate, dilauroyl peroxide, di-n-octanoyl peroxide, 1,1,3 , 3-tetramethylbutylperoxy-2-ethylhexanoate, di (4-methylbenzoyl) peroxide, dibenzoyl peroxide, t-butylperoxyisobutyrate, 1,1-di (t-hexylperoxy) ) Peroxides such as cyclohexane, t-butyl hydroperoxide, hydrogen peroxide, peroxides and sodium bisulfite, peroxides and sodium ascorbate, etc. Redox initiators combined with Not shall.
　前記重合開始剤は単独でまたは組み合わせて使用できるが、全体としての使用量はモノマー成分１００重量部に対して、０．００５～１重量部程度であることが好ましく、０．０１～０．５重量部程度であることがより好ましい。 The polymerization initiators can be used alone or in combination, but the total amount used is preferably about 0.005 to 1 part by weight with respect to 100 parts by weight of the monomer component, and 0.01 to 0.5 More preferably, it is about parts by weight.
　前記重合開始剤として、例えば、２，２’－アゾビスイソブチロニトリルを用いることが好ましい。 As the polymerization initiator, for example, 2,2′-azobisisobutyronitrile is preferably used.
　前記連鎖移動剤としては、例えば、ラウリルメルカプタン、グリシジルメルカプタン、メルカプト酢酸、２－メルカプトエタノール、チオグリコール酸、チオグルコール酸２－エチルヘキシル、２，３－ジメルカプト－１－プロパノール等が挙げられる。連鎖移動剤は、単独で使用してもよく、また２種以上を混合して使用してもよいが、全体としての使用量はモノマー成分の全量１００重量部に対して、０．１重量部程度以下である。 Examples of the chain transfer agent include lauryl mercaptan, glycidyl mercaptan, mercaptoacetic acid, 2-mercaptoethanol, thioglycolic acid, 2-ethylhexyl thioglycolate, and 2,3-dimercapto-1-propanol. The chain transfer agent may be used alone or in combination of two or more, but the total amount used is 0.1 parts by weight with respect to 100 parts by weight of the total amount of monomer components. Less than or equal to
　前記乳化重合する場合に用いる乳化剤としては、例えば、ラウリル硫酸ナトリウム、ラウリル硫酸アンモニウム、ドデシルベンゼンスルホン酸ナトリウム、ポリオキシエチレンアルキルエーテル硫酸アンモニウム、ポリオキシエチレンアルキルフェニルエーテル硫酸ナトリウム等のアニオン系乳化剤、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル、ポリオキシエチレン脂肪酸エステル、ポリオキシエチレン－ポリオキシプロピレンブロックポリマー等のノニオン系乳化剤等が挙げられる。前記乳化剤は単独でまたは組み合わせて使用できる。 Examples of the emulsifier used in the emulsion polymerization include anionic emulsifiers such as sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, ammonium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkylphenyl ether sulfate, and polyoxyethylene. Nonionic emulsifiers such as alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene fatty acid esters, polyoxyethylene-polyoxypropylene block polymers and the like can be mentioned. The emulsifiers can be used alone or in combination.
　前記反応性乳化剤として、プロペニル基、アリルエーテル基等のラジカル重合性官能基が導入された乳化剤として、具体的には、例えば、アクアロンＨＳ－１０、ＨＳ－２０、ＫＨ－１０、ＢＣ－０５、ＢＣ－１０、ＢＣ－２０（以上、いずれも第一工業製薬社製）、アデカリアソープＳＥ１０Ｎ（ＡＤＥＫＡ社製）等がある。反応性乳化剤は、重合後にポリマー鎖に取り込まれるため、耐水性がよくなり好ましい。乳化剤の使用量は、モノマー成分の全量１００重量部に対して、０．３～５重量部、重合安定性や機械的安定性から０．５～１重量部がより好ましい。 As the reactive emulsifier, as an emulsifier into which a radical polymerizable functional group such as propenyl group or allyl ether group is introduced, specifically, for example, Aqualon HS-10, HS-20, KH-10, BC-05, BC-10, BC-20 (all of which are manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Adekaria soap SE10N (manufactured by ADEKA), and the like. Reactive emulsifiers are preferable because they are incorporated into the polymer chain after polymerization and thus have improved water resistance. The amount of the emulsifier used is preferably 0.3 to 5 parts by weight with respect to 100 parts by weight of the total amount of monomer components, and more preferably 0.5 to 1 part by weight from the viewpoint of polymerization stability and mechanical stability.
　前記（メタ）アクリル系ポリマーは、放射線重合により製造する場合には、前記モノマー成分を、電子線、ＵＶ等の放射線を照射することにより重合して製造することができる。前記放射線重合を電子線で行う場合には、前記モノマー成分には光重合開始剤を含有させることは特に必要ではないが、前記放射線重合をＵＶ重合で行う場合には、特に、重合時間を短くすることができる利点等から、モノマー成分に光重合開始剤を含有させることができる。光重合開始剤は単独でまたは組み合わせて使用できる。 When the (meth) acrylic polymer is produced by radiation polymerization, it can be produced by polymerizing the monomer component by irradiating with radiation such as electron beam or UV. When the radiation polymerization is performed with an electron beam, it is not particularly necessary to include a photopolymerization initiator in the monomer component. However, when the radiation polymerization is performed with UV polymerization, the polymerization time is particularly short. For example, a photopolymerization initiator can be contained in the monomer component because of the advantages that can be achieved. A photoinitiator can be used individually or in combination.
　前記光重合開示剤としては、光重合を開始するものであれば特に制限されず、通常用いられる光重合開始剤を用いることができる。例えば、ベンゾインエーテル系、アセトフェノン系、α‐ケトール系、光活性オキシム系、ベンゾイン系、ベンジル系、ベンゾフェノン系、ケタール系、チオキサントン系等を用いることができる。光重合開始剤の使用量は、モノマー成分１００重量部に対して、０．０５～１．５重量部であり、好ましくは０．１～１重量部である。 The photopolymerization disclosure agent is not particularly limited as long as it initiates photopolymerization, and a commonly used photopolymerization initiator can be used. For example, benzoin ether, acetophenone, α-ketol, photoactive oxime, benzoin, benzyl, benzophenone, ketal, thioxanthone, and the like can be used. The amount of the photopolymerization initiator used is 0.05 to 1.5 parts by weight, preferably 0.1 to 1 part by weight, based on 100 parts by weight of the monomer component.
　本発明の（メタ）アクリル系ポリマーの重量平均分子量は、３５万以上であることが好ましい。前記（メタ）アクリル系ポリマーの重量平均分子量は、樹脂層の耐久性及び凝集力を高める観点から、４０万以上であることがより好ましく、５０万以上であることがさらに好ましい。前記（メタ）アクリル系ポリマーの重量平均分子量は、貼り合わせ性、及び粘着力を高める観点、樹脂組成物の粘度を抑制する観点から、３００万以下であることが好ましく、２５０万以下であることがより好ましく、２００万以下であることがさらに好ましく、１５０万以下であることがよりさらに好ましく、１２０万以下であることがよりさらに好ましい。 The weight average molecular weight of the (meth) acrylic polymer of the present invention is preferably 350,000 or more. The weight average molecular weight of the (meth) acrylic polymer is more preferably 400,000 or more, and even more preferably 500,000 or more, from the viewpoint of enhancing the durability and cohesion of the resin layer. The weight average molecular weight of the (meth) acrylic polymer is preferably 3 million or less, and preferably 2.5 million or less from the viewpoints of enhancing the bonding property and the adhesive strength, and suppressing the viscosity of the resin composition. Is more preferably 2 million or less, even more preferably 1.5 million or less, and even more preferably 1.2 million or less.
　前記（メタ）アクリル系ポリマーの重量平均分子量は、ＧＰＣ（ゲルパーミネーション・クロマトグラフィー）により測定し、ポリスチレン換算により算出できる。サンプルは、試料をテトラヒドロフランに溶解して０．１重量％の溶液とし、これを一晩静置した後、０．４５μｍのメンブレンフィルターで濾過した濾液を用いた。
・分析装置：東ソー社製、ＨＬＣ－８１２０ＧＰＣ
・カラム：東ソー社製、（メタ）アクリル系ポリマー：ＧＭ７０００ＨＸＬ＋ＧＭＨＸＬ＋ＧＭＨＸＬ
　芳香族系ポリマー：Ｇ３０００ＨＸＬ＋２０００ＨＸＬ＋Ｇ１０００ＨＸＬ
・カラムサイズ；各７．８ｍｍφ×３０ｃｍ　計９０ｃｍ・溶離液：テトラヒドロフラン（濃度０．１重量％）
・流量：０．８ｍｌ／ｍｉｎ
・入口圧：１．６ＭＰａ
・検出器：示差屈折計（ＲＩ）
・カラム温度：４０℃
・注入量：１００μｌ
・溶離液：テトラヒドロフラン
・検出器：示差屈折計
・標準試料：ポリスチレン The weight average molecular weight of the (meth) acrylic polymer can be measured by GPC (gel permeation chromatography) and calculated in terms of polystyrene. The sample used was a filtrate obtained by dissolving the sample in tetrahydrofuran to make a 0.1 wt% solution, which was allowed to stand overnight, and then filtered through a 0.45 μm membrane filter.
・ Analyzer: manufactured by Tosoh Corporation, HLC-8120GPC
Column: manufactured by Tosoh Corporation, (meth) acrylic polymer: GM7000HXL + GMHXL + GMHXL
Aromatic polymer: G3000HXL + 2000HXL + G1000HXL
Column size: 7.8 mmφ × 30 cm each 90 cm in total Eluent: Tetrahydrofuran (concentration 0.1% by weight)
・ Flow rate: 0.8ml / min
・ Inlet pressure: 1.6 MPa
・ Detector: Differential refractometer (RI)
-Column temperature: 40 ° C
・ Injection volume: 100 μl
・ Eluent: Tetrahydrofuran ・ Detector: Differential refractometer ・ Standard sample: Polystyrene
＜架橋剤＞
　本発明の樹脂組成物は、架橋剤を含有することができる。架橋剤としては、イソシアネート系架橋剤、エポキシ系架橋剤、シリコーン系架橋剤、オキサゾリン系架橋剤、アジリジン系架橋剤、シラン系架橋剤、アルキルエーテル化メラミン系架橋剤、金属キレート系架橋剤、過酸化物等の架橋剤が含まれる。前記架橋剤としては、イソシアネート系架橋剤、エポキシ系架橋剤が好適である。 <Crosslinking agent>
The resin composition of the present invention can contain a crosslinking agent. Examples of crosslinking agents include isocyanate crosslinking agents, epoxy crosslinking agents, silicone crosslinking agents, oxazoline crosslinking agents, aziridine crosslinking agents, silane crosslinking agents, alkyletherified melamine crosslinking agents, metal chelate crosslinking agents, Crosslinkers such as oxides are included. As said crosslinking agent, an isocyanate type crosslinking agent and an epoxy-type crosslinking agent are suitable.
　前記架橋剤は単独でまたは組み合わせて使用できるが、全体としての含有量は、前記（メタ）アクリル系ポリマー１００重量部に対し、前記架橋剤を０．０１～５重量部の範囲で含有することが好ましい。架橋剤の含有量は、０．０１～４重量部含有することがより好ましく、０．０２～３重量部含有することがさらに好ましい。また、架橋剤として、前記多官能性モノマーを用いてもよく、この場合、前記多官能性モノマーは、前記（メタ）アクリル系ポリマー１００重量部に対し、０．００１～２重量部の範囲で含有することが好ましく、０．００３～１重量部の範囲で含有することがさらに好ましい。 The crosslinking agent can be used alone or in combination, but the total content of the crosslinking agent is 0.01 to 5 parts by weight with respect to 100 parts by weight of the (meth) acrylic polymer. Is preferred. The content of the crosslinking agent is more preferably 0.01 to 4 parts by weight, and further preferably 0.02 to 3 parts by weight. Further, the polyfunctional monomer may be used as a crosslinking agent. In this case, the polyfunctional monomer is used in an amount of 0.001 to 2 parts by weight with respect to 100 parts by weight of the (meth) acrylic polymer. It is preferably contained, and more preferably in the range of 0.003 to 1 part by weight.
　前記イソシアネート系架橋剤は、イソシアネート基（イソシアネート基をブロック剤または数量体化等により一時的に保護したイソシアネート再生型官能基を含む）を１分子中に２つ以上有する化合物をいう。 The isocyanate-based crosslinking agent refers to a compound having two or more isocyanate groups (including isocyanate-regenerating functional groups in which the isocyanate group is temporarily protected by a blocking agent or quantification) in one molecule.
　前記イソシアネート系架橋剤としては、トリレンジイソシアネート、キシレンジイソシアネート等の芳香族イソシアネート、イソホロンジイソシアネート等の脂環族イソシアネート、ヘキサメチレンジイソシアネート等の脂肪族イソシアネート等が挙げられる。 Examples of the isocyanate-based crosslinking agent include aromatic isocyanates such as tolylene diisocyanate and xylene diisocyanate, alicyclic isocyanates such as isophorone diisocyanate, and aliphatic isocyanates such as hexamethylene diisocyanate.
　前記イソシアネート系架橋剤としては、より具体的には、例えば、ブチレンジイソシアネート、ヘキサメチレンジイソシアネート等の低級脂肪族ポリイソシアネート類、シクロペンチレンジイソシアネート、シクロヘキシレンジイソシアネート、イソホロンジイソシアネート等の脂環族イソシアネート類、２，４－トリレンジイソシアネート、４，４’－ジフェニルメタンジイソシアネート、キシリレンジイソシアネート、ポリメチレンポリフェニルイソシアネート等の芳香族ジイソシアネート類、トリメチロールプロパン／トリレンジイソシアネート３量体付加物（日本ポリウレタン工業社製，商品名コロネートＬ）、トリメチロールプロパン／ヘキサメチレンジイソシアネート３量体付加物（日本ポリウレタン工業社製，商品名コロネートＨＬ）、ヘキサメチレンジイソシアネートのイソシアヌレート体（日本ポリウレタン工業社製，商品名コロネートＨＸ）等のイソシアネート付加物、キシリレンジイソシアネートのトリメチロールプロパン付加物（三井化学社製，商品名：タケネートＤ１１０Ｎ）、キシリレンジイソシアネートのトリメチロールプロパン付加物（三井化学社製，商品名：タケネートＤ１２０Ｎ）、イソホロンジイソシアネートのトリメチロールプロパン付加物（三井化学社製，商品名：タケネートＤ１４０Ｎ）、ヘキサメチレンジイソシアネートのトリメチロールプロパン付加物（三井化学社製，商品名：タケネートＤ１６０Ｎ）；ポリエーテルポリイソシアネート、ポリエステルポリイソシアネート、ならびにこれらと各種のポリオールとの付加物、イソシアヌレート結合、ビューレット結合、アロファネート結合等で多官能化したポリイソシアネート等を挙げることができる。これらのなかでも芳香族イソシアネートや脂環式イソシアネートを用いることが、粘着力と保持力に関する特性をバランスよく発現させるために好ましい。 More specifically, as the isocyanate-based crosslinking agent, for example, lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate, alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate, and isophorone diisocyanate, Aromatic diisocyanates such as 2,4-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, polymethylene polyphenyl isocyanate, trimethylolpropane / tolylene diisocyanate trimer adduct (manufactured by Nippon Polyurethane Industry Co., Ltd.) , Trade name Coronate L), trimethylolpropane / hexamethylene diisocyanate trimer adduct (made by Nippon Polyurethane Industry Co., Ltd., trade name Coronet) HL), isocyanurate of hexamethylene diisocyanate (product name: Coronate HX, manufactured by Nippon Polyurethane Industry Co., Ltd.), trimethylolpropane adduct of xylylene diisocyanate (product name: Takenate D110N) , Trimethylolpropane adduct of xylylene diisocyanate (Mitsui Chemicals, trade name: Takenate D120N), trimethylolpropane adduct of isophorone diisocyanate (trade name: Takenate D140N), trimethylol of hexamethylene diisocyanate Propane adduct (Mitsui Chemicals, trade name: Takenate D160N); polyether polyisocyanate, polyester polyisocyanate, and adducts of these with various polyols, Isocyanurate bond, biuret bond include at allophanate bond such multi-functionalized polyisocyanate. Among these, it is preferable to use an aromatic isocyanate or an alicyclic isocyanate in order to develop the properties relating to adhesive strength and holding power in a well-balanced manner.
　前記イソシアネート系架橋剤は単独でまたは組み合わせて使用できるが、全体としての含有量は、前記（メタ）アクリル系ポリマー１００重量部に対し、前記イソシアネート系架橋剤を０．０１～５重量部含有することが好ましく、さらには０．０３～４重量部含有することが好ましく、さらには０．０５～３重量部含有することが好ましく、０．０８～２重量部含有することがよりさらに好ましい。凝集力、耐久性試験での剥離の阻止等を考慮して適宜含有させることが可能である。 The isocyanate crosslinking agent can be used alone or in combination, but the total content is 0.01 to 5 parts by weight of the isocyanate crosslinking agent with respect to 100 parts by weight of the (meth) acrylic polymer. Preferably, it is contained in an amount of 0.03 to 4 parts by weight, more preferably 0.05 to 3 parts by weight, and still more preferably 0.08 to 2 parts by weight. It can be appropriately contained in consideration of cohesive force, prevention of peeling in a durability test, and the like.
　尚、前記乳化重合にて作製した変性（メタ）アクリル系ポリマーの水分散液では、イソシアネート系架橋剤を用いなくても良いが、必要な場合には、水と反応し易いために、ブロック化したイソシアネート系架橋剤を用いることもできる。 In addition, in the aqueous dispersion of the modified (meth) acrylic polymer prepared by the emulsion polymerization, it is not necessary to use an isocyanate-based crosslinking agent. However, if necessary, it is blocked because it easily reacts with water. It is also possible to use an isocyanate-based crosslinking agent.
　前記エポキシ系架橋剤はエポキシ基を１分子中に２つ以上有する多官能エポキシ化合物をいう。エポキシ系架橋剤としては、例えば、Ｎ，Ｎ，Ｎ′，Ｎ′－テトラグリシジル－ｍ－キシレンジアミン、ジグリシジルアニリン、１，３－ビス（Ｎ，Ｎ－ジグリシジルアミノメチル）シクロヘキサン、１，６－ヘキサンジオールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、エチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル、ソルビトールポリグリシジルエーテル、グリセロールポリグリシジルエーテル、ペンタエリスリトールポリグリシジルエーテル、ポリグリセロールポリグリシジルエーテル、ソルビタンポリグリシジルエーテル、トリメチロールプロパンポリグリシジルエーテル、アジピン酸ジグリシジルエステル、ｏ－フタル酸ジグリシジルエステル、トリグリシジル－トリス（２－ヒドロキシエチル）イソシアヌレート、レゾルシンジグリシジルエーテル、ビスフェノール－Ｓ－ジグリシジルエーテルの他、分子内にエポキシ基を２つ以上有するエポキシ系樹脂等が挙げられる。上記エポキシ系架橋剤としては、例えば、三菱ガス化学社製、商品名「テトラッドＣ」、「テトラッドＸ」等の市販品も挙げられる。 The epoxy-based crosslinking agent refers to a polyfunctional epoxy compound having two or more epoxy groups in one molecule. Examples of the epoxy crosslinking agent include N, N, N ′, N′-tetraglycidyl-m-xylenediamine, diglycidylaniline, 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 polyglycidyl ether, trimethylolpropane polyglycidyl Ether, adipic acid diglycidyl ester, o-phthalic acid diglycidyl ester, triglycidyl-tris (2-hydroxyethyl) isocyanurate, resorcin diglycidyl ether, bisphenol-S-diglycidyl ether Examples thereof include an epoxy resin having two or more. Examples of the epoxy-based crosslinking agent include commercially available products such as trade names “Tetrad C” and “Tetrad X” manufactured by Mitsubishi Gas Chemical Company.
　前記エポキシ系架橋剤は単独でまたは組み合わせて使用できるが、全体としての含有量は、前記（メタ）アクリル系ポリマー１００重量部に対し、前記エポキシ系架橋剤を０．００５～１重量部含有することが好ましく、さらには０．０１～０．５重量部含有することが好ましく、さらには０．０１５～０．３重量部含有することが好ましい。凝集力、耐久性試験での剥離の阻止等を考慮して適宜含有させることが可能である。 The epoxy crosslinking agent can be used alone or in combination, but the total content is 0.005 to 1 part by weight of the epoxy crosslinking agent with respect to 100 parts by weight of the (meth) acrylic polymer. The content is preferably 0.01 to 0.5 parts by weight, more preferably 0.015 to 0.3 parts by weight. It can be appropriately contained in consideration of cohesive force, prevention of peeling in a durability test, and the like.
　前記過酸化物としては、加熱によりラジカル活性種を発生して樹脂組成物のベースポリマーの架橋を進行させるものであれば適宜使用可能であるが、作業性や安定性を勘案して、１分間半減期温度が８０℃～１６０℃である過酸化物を使用することが好ましく、９０℃～１４０℃である過酸化物を使用することがより好ましい。 As the peroxide, any radical active species can be used as long as it generates radical active species by heating to advance the crosslinking of the base polymer of the resin composition. However, in consideration of workability and stability, 1 minute It is preferable to use a peroxide having a half-life temperature of 80 ° C. to 160 ° C., and more preferable to use a peroxide having a 90 ° C. to 140 ° C.
　前記過酸化物としては、例えば、ジ（２－エチルヘキシル）パーオキシジカーボネート（１分間半減期温度：９０．６℃）、ジ（４－ｔ－ブチルシクロヘキシル）パーオキシジカーボネート（１分間半減期温度：９２．１℃）、ジ－ｓｅｃ－ブチルパーオキシジカーボネート（１分間半減期温度：９２．４℃）、ｔ－ブチルパーオキシネオデカノエート（１分間半減期温度：１０３．５℃）、ｔ－ヘキシルパーオキシピバレート（１分間半減期温度：１０９．１℃）、ｔ－ブチルパーオキシピバレート（１分間半減期温度：１１０．３℃）、ジラウロイルパーオキシド（１分間半減期温度：１１６．４℃）、ジ－ｎ－オクタノイルパーオキシド（１分間半減期温度：１１７．４℃）、１，１，３，３－テトラメチルブチルパーオキシ－２－エチルヘキサノエート（１分間半減期温度：１２４．３℃）、ジ（４－メチルベンゾイル）パーオキシド（１分間半減期温度：１２８．２℃）、ジベンゾイルパーオキシド（１分間半減期温度：１３０．０℃）、ｔ－ブチルパーオキシイソブチレート（１分間半減期温度：１３６．１℃）、１，１－ジ（ｔ－ヘキシルパーオキシ）シクロヘキサン（１分間半減期温度：１４９．２℃）等が挙げられる。なかでも特に架橋反応効率が優れることから、ジ（４－ｔ－ブチルシクロヘキシル）パーオキシジカーボネート（１分間半減期温度：９２．１℃）、ジラウロイルパーオキシド（１分間半減期温度：１１６．４℃）、ジベンゾイルパーオキシド（１分間半減期温度：１３０．０℃）等が好ましく用いられる。 Examples of the peroxide include di (2-ethylhexyl) peroxydicarbonate (1 minute half-life temperature: 90.6 ° C.), di (4-t-butylcyclohexyl) peroxydicarbonate (1 minute half-life). Temperature: 92.1 ° C.), di-sec-butyl peroxydicarbonate (1 minute half-life temperature: 92.4 ° C.), t-butyl peroxyneodecanoate (1 minute half-life temperature: 103.5 ° C.) ), T-hexyl peroxypivalate (1 minute half-life temperature: 109.1 ° C.), t-butyl peroxypivalate (1 minute half-life temperature: 110.3 ° C.), dilauroyl peroxide (half minute for 1 minute) Phase temperature: 116.4 ° C.), di-n-octanoyl peroxide (1 minute half-life temperature: 117.4 ° C.), 1,1,3,3-tetramethylbutylperoxy-2- Tylhexanoate (1 minute half-life temperature: 124.3 ° C.), di (4-methylbenzoyl) peroxide (1 minute half-life temperature: 128.2 ° C.), dibenzoyl peroxide (1 minute half-life temperature: 130 0.0 ° C.), t-butyl peroxyisobutyrate (1 minute half-life temperature: 136.1 ° C.), 1,1-di (t-hexylperoxy) cyclohexane (1 minute half-life temperature: 149.2 ° C.) ) And the like. Among them, since the crosslinking reaction efficiency is particularly excellent, di (4-t-butylcyclohexyl) peroxydicarbonate (1 minute half-life temperature: 92.1 ° C.), dilauroyl peroxide (1 minute half-life temperature: 116. 4 ° C.), dibenzoyl peroxide (1 minute half-life temperature: 130.0 ° C.) and the like are preferably used.
　尚、前記過酸化物の半減期とは、過酸化物の分解速度を表す指標であり、過酸化物の残存量が半分になるまでの時間をいう。任意の時間で半減期を得るための分解温度や、任意の温度での半減期時間に関しては、メーカーカタログ等に記載されており、例えば、日本油脂株式会社の「有機過酸化物カタログ第９版（２００３年５月）」等に記載されている。 The half-life of the peroxide is an index representing the decomposition rate of the peroxide, and means the time until the remaining amount of peroxide is reduced to half. The decomposition temperature for obtaining a half-life at an arbitrary time and the half-life time at an arbitrary temperature are described in the manufacturer catalog and the like, for example, “Organic peroxide catalog 9th edition of Nippon Oil & Fats Co., Ltd.” (May 2003) ".
　前記過酸化物は単独でまたは組み合わせて使用できるが、全体としての含有量は、前記（メタ）アクリル系ポリマー１００重量部に対し、前記過酸化物０．０２～２重量部であり、０．０５～１重量部含有することが好ましい。加工性、リワーク性、架橋安定性、剥離性等の調整の為に、この範囲内で適宜選択される。 The peroxides can be used alone or in combination, but the total content is 0.02 to 2 parts by weight of the peroxide with respect to 100 parts by weight of the (meth) acrylic polymer. It is preferably contained in an amount of 05 to 1 part by weight. In order to adjust processability, reworkability, cross-linking stability, releasability, etc., it is appropriately selected within this range.
　尚、反応処理後の残存した過酸化物分解量の測定方法としては、例えば、ＨＰＬＣ（高速液体クロマトグラフィー）により測定することができる。具体的には、例えば、反応処理後の樹脂層を約０．２ｇずつ取り出し、酢酸エチル１０ｍｌに浸漬し、振とう機で２５℃下、１２０ｒｐｍで３時間振とう抽出した後、室温で３日間静置する。次いで、アセトニトリル１０ｍｌ加えて、２５℃下、１２０ｒｐｍで３０分振とうし、メンブランフィルター（０．４５μｍ）によりろ過して得られた抽出液約１０μｌをＨＰＬＣに注入して分析し、反応処理後の過酸化物量とすることができる。 In addition, as a measuring method of the peroxide decomposition amount remaining after the reaction treatment, for example, it can be measured by HPLC (high performance liquid chromatography). Specifically, for example, about 0.2 g of the resin layer after the reaction treatment is taken out, immersed in 10 ml of ethyl acetate, extracted with shaking at 25 ° C. and 120 rpm for 3 hours, and then at room temperature for 3 days. Leave still. Next, 10 ml of acetonitrile was added, shaken at 120 rpm at 25 ° C. for 30 minutes, and about 10 μl of the extract obtained by filtration through a membrane filter (0.45 μm) was injected into the HPLC for analysis. The amount of peroxide can be set.
　また、前記金属キレート系架橋剤としては、多価金属が有機化合物と共有結合または配位結合している多官能性金属キレートが挙げられる。多価金属原子としては、Ａｌ、Ｃｒ、Ｚｒ、Ｃｏ、Ｃｕ、Ｆｅ、Ｎｉ、Ｖ、Ｚｎ、Ｉｎ、Ｃａ、Ｍｇ、Ｍｎ、Ｙ、Ｃｅ、Ｓｒ、Ｂａ、Ｍｏ、Ｌａ、Ｓｎ、Ｔｉ等が挙げられる。共有結合または配位結合する有機化合物中の原子としては酸素原子等が挙げられ、有機化合物としてはアルキルエステル、アルコール化合物、カルボン酸化合物、エーテル化合物、ケトン化合物等が挙げられる。 In addition, examples of the metal chelate-based crosslinking agent include polyfunctional metal chelates in which a polyvalent metal is covalently or coordinately bonded to an organic compound. Examples of polyvalent metal atoms include Al, Cr, Zr, Co, Cu, Fe, Ni, V, Zn, In, Ca, Mg, Mn, Y, Ce, Sr, Ba, Mo, La, Sn, Ti, and the like. Can be mentioned. Examples of the atom in the organic compound that is covalently bonded or coordinated include an oxygen atom, and examples of the organic compound include an alkyl ester, an alcohol compound, a carboxylic acid compound, an ether compound, and a ketone compound.
　本発明の樹脂組成物には、接着力を向上させるために、（メタ）アクリル系オリゴマーを含有させることができる。前記（メタ）アクリル系オリゴマーは、本発明の（メタ）アクリル系ポリマーよりもＴｇが高く、重量平均分子量が小さい重合体を用いるのが好ましい。前記（メタ）アクリル系オリゴマーは、粘着付与樹脂として機能し、かつ接着力を向上させることが可能である。 The resin composition of the present invention can contain a (meth) acrylic oligomer in order to improve the adhesive strength. The (meth) acrylic oligomer is preferably a polymer having a Tg higher than that of the (meth) acrylic polymer of the present invention and a small weight average molecular weight. The (meth) acrylic oligomer functions as a tackifier resin and can improve the adhesive force.
　前記（メタ）アクリル系オリゴマーは、Ｔｇが約０℃以上３００℃以下、好ましくは約２０℃以上３００℃以下、さらに好ましくは約４０℃以上３００℃以下であることが望ましい。Ｔｇが約０℃未満であると樹脂層の室温以上での凝集力が低下し、保持特性や高温での接着性が低下する場合がある。尚、（メタ）アクリル系オリゴマーのＴｇは、（メタ）アクリル系ポリマーのＴｇと同じく、Ｆｏｘの式に基づいて計算した理論値である。 The (meth) acrylic oligomer desirably has a Tg of about 0 ° C. or higher and 300 ° C. or lower, preferably about 20 ° C. or higher and 300 ° C. or lower, more preferably about 40 ° C. or higher and 300 ° C. or lower. If the Tg is less than about 0 ° C., the cohesive strength of the resin layer at room temperature or higher may be reduced, and the holding characteristics and adhesiveness at high temperatures may be reduced. The Tg of the (meth) acrylic oligomer is a theoretical value calculated on the basis of the Fox equation, similar to the Tg of the (meth) acrylic polymer.
　前記（メタ）アクリル系オリゴマーの重量平均分子量は、１０００以上３００００未満、好ましくは１５００以上２００００未満、さらに好ましくは２０００以上１００００未満である。重量平均分子量が３００００以上であると、接着力の向上効果が充分には得られない場合がある。また、１０００未満であると、低分子量となるため接着力や保持特性の低下を引き起こす場合がある。本発明において、（メタ）アクリル系オリゴマーの重量平均分子量の測定は、ＧＰＣ法によりポリスチレン換算して求めることができる。具体的には東ソー株式会社製のＨＰＬＣ８０２０に、カラムとしてＴＳＫｇｅｌＧＭＨ－Ｈ（２０）×２本を用いて、テトラヒドロフラン溶媒で流速約０．５ｍｌ／分の条件にて測定される。 The weight average molecular weight of the (meth) acrylic oligomer is 1000 or more and less than 30000, preferably 1500 or more and less than 20000, and more preferably 2000 or more and less than 10,000. If the weight average molecular weight is 30000 or more, the effect of improving the adhesive strength may not be sufficiently obtained. On the other hand, if the molecular weight is less than 1000, the molecular weight may be low, which may cause a decrease in adhesive strength and retention characteristics. In this invention, the measurement of the weight average molecular weight of a (meth) acrylic-type oligomer can be calculated | required in polystyrene conversion by GPC method. Specifically, it is measured on a HPLC 8020 manufactured by Tosoh Corporation using two TSKgelGMH-H (20) columns as a column and a tetrahydrofuran solvent at a flow rate of about 0.5 ml / min.
　前記（メタ）アクリル系オリゴマーを構成するモノマーとしては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｓ－ブチル（メタ）アクリレート、ｔ－ブチル（メタ）アクリレート、ペンチル（メタ）アクリレート、イソペンチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ヘプチル（メタ）アクリレート、オクチル（メタ）アクリレート、イソオクチル（メタ）アクリレート、ノニル（メタ）アクリレート、イソノニル（メタ）アクリレート、デシル（メタ）アクリレート、イソデシル（メタ）アクリレート、ウンデシル（メタ）アクリレート、ドデシル（メタ）アクリレートのようなアルキル（メタ）アクリレート；シクロヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレートのような（メタ）アクリル酸と脂環族アルコールとのエステル；フェニル（メタ）アクリレート、ベンジル（メタ）アクリレートのようなアリール（メタ）アクリレート；テルペン化合物誘導体アルコールから得られる（メタ）アクリレート；等を挙げることができる。このような（メタ）アクリレートは単独であるいは２種以上を組み合わせて使用することができる。 Examples of the monomer constituting the (meth) acrylic oligomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, and isobutyl (meth). Acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, Octyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, un Alkyl (meth) acrylates such as sil (meth) acrylate and dodecyl (meth) acrylate; (meth) acrylic acid and fat such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate and dicyclopentanyl (meth) acrylate Examples include esters with cyclic alcohols; aryl (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate; (meth) acrylates obtained from terpene compound derivative alcohols; and the like. Such (meth) acrylates can be used alone or in combination of two or more.
　前記（メタ）アクリル系オリゴマーとしては、イソブチル（メタ）アクリレートやｔ－ブチル（メタ）アクリレートのようなアルキル基が分岐構造を持ったアルキル（メタ）アクリレート；シクロヘキシル（メタ）アクリレートや、イソボルニル（メタ）アクリレートジシクロペンタニル（メタ）アクリレートのような（メタ）アクリル酸と脂環式アルコールとのエステル；フェニル（メタ）アクリレートやベンジル（メタ）アクリレートのようなアリール（メタ）アクリレート等の環状構造を持った（メタ）アクリレートに代表される、比較的嵩高い構造を有するアクリル系モノマーをモノマー単位として含んでいることが好ましい。このような嵩高い構造を（メタ）アクリル系オリゴマーに持たせることで、樹脂層の接着性をさらに向上させることができる。特に嵩高さという点で環状構造を持ったものは効果が高く、環を複数含有したものはさらに効果が高い。また、（メタ）アクリル系オリゴマーの合成の際や樹脂層の作製の際に紫外線（紫外線）を採用する場合には、重合阻害を起こしにくいという点で、飽和結合を有したものが好ましく、アルキル基が分岐構造を持ったアルキル（メタ）アクリレート、または脂環式アルコールとのエステルを、（メタ）アクリル系オリゴマーを構成するモノマーとして好適に用いることができる。 Examples of the (meth) acrylic oligomer include alkyl (meth) acrylates having an alkyl group having a branched structure, such as isobutyl (meth) acrylate and t-butyl (meth) acrylate; cyclohexyl (meth) acrylate, isobornyl (meta) ) Esters of (meth) acrylic acid and alicyclic alcohols such as acrylate dicyclopentanyl (meth) acrylate; cyclic structures such as aryl (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate It is preferable that an acrylic monomer having a relatively bulky structure typified by (meth) acrylate having a monomer content is included as a monomer unit. By giving such a bulky structure to the (meth) acrylic oligomer, the adhesiveness of the resin layer can be further improved. In particular, those having a ring structure in terms of bulkiness are highly effective, and those having a plurality of rings are more effective. In addition, when ultraviolet rays (ultraviolet rays) are used in the synthesis of (meth) acrylic oligomers or in the production of the resin layer, those having a saturated bond are preferable because they are less likely to cause polymerization inhibition. An alkyl (meth) acrylate having a branched structure in the group or an ester with an alicyclic alcohol can be suitably used as a monomer constituting the (meth) acrylic oligomer.
　このような点から、好適な（メタ）アクリル系オリゴマーとしては、例えば、シクロヘキシルメタクリレート（ＣＨＭＡ）とイソブチルメタクリレート（ＩＢＭＡ）の共重合体、シクロヘキシルメタクリレート（ＣＨＭＡ）とイソボルニルメタクリレート（ＩＢＸＭＡ）の共重合体、シクロヘキシルメタクリレート（ＣＨＭＡ）とアクリロイルモルホリン（ＡＣＭＯ）の共重合体、シクロヘキシルメタクリレート（ＣＨＭＡ）とジエチルアクリルアミド（ＤＥＡＡ）の共重合体、１－アダマンチルアクリレート（ＡＤＡ）とメチルメタクリレート（ＭＭＡ）の共重合体、ジシクロペンタニルメタクリレート（ＤＣＰＭＡ）とイソボルニルメタクリレート（ＩＢＸＭＡ）の共重合体、ジシクロペンタニルメタクリレート（ＤＣＰＭＡ）、シクロヘキシルメタクリレート（ＣＨＭＡ）、イソボルニルメタクリレート（ＩＢＸＭＡ）、イソボルニルアクリレート（ＩＢＸＡ）、シクロペンタニルメタクリレート（ＤＣＰＭＡ）とメチルメタクリレート（ＭＭＡ）の共重合体、ジシクロペンタニルアクリレート（ＤＣＰＡ）、１－アダマンチルメタクリレート（ＡＤＭＡ）、１－アダマンチルアクリレート（ＡＤＡ）の各単独重合体等を挙げることができる。特に、ＣＨＭＡを主成分として含むオリゴマーが好ましい。 From this point, suitable (meth) acrylic oligomers include, for example, a copolymer of cyclohexyl methacrylate (CHMA) and isobutyl methacrylate (IBMA), and a copolymer of cyclohexyl methacrylate (CHMA) and isobornyl methacrylate (IBXMA). Polymer, copolymer of cyclohexyl methacrylate (CHMA) and acryloylmorpholine (ACMO), copolymer of cyclohexyl methacrylate (CHMA) and diethylacrylamide (DEAA), copolymer of 1-adamantyl acrylate (ADA) and methyl methacrylate (MMA) Polymer, copolymer of dicyclopentanyl methacrylate (DCPMA) and isobornyl methacrylate (IBXMA), dicyclopentanyl methacrylate (DCPMA), Hexyl methacrylate (CHMA), isobornyl methacrylate (IBXMA), isobornyl acrylate (IBXA), a copolymer of cyclopentanyl methacrylate (DCPMA) and methyl methacrylate (MMA), dicyclopentanyl acrylate (DCPA), 1 -Adamantyl methacrylate (ADMA), 1-adamantyl acrylate (ADA) homopolymers, and the like. In particular, an oligomer containing CHMA as a main component is preferable.
　本発明の樹脂組成物において、前記（メタ）アクリル系オリゴマーを用いる場合、その含有量は特に限定されないが、（メタ）アクリル系ポリマー１００重量部に対して７０重量部以下であるのが好ましく、さらに好ましくは１～７０重量部であり、さらに好ましくは２～５０重量部であり、さらに好ましくは３～４０重量部である。（メタ）アクリル系オリゴマーの添加量が７０重量部を超えると、弾性率が高くなり過ぎ低温での接着性が悪くなるという不具合の可能性がある。尚、（メタ）アクリル系オリゴマーを１重量部以上配合する場合に、接着力の向上効果の点から有効である。 In the resin composition of the present invention, when the (meth) acrylic oligomer is used, its content is not particularly limited, but it is preferably 70 parts by weight or less with respect to 100 parts by weight of the (meth) acrylic polymer, The amount is more preferably 1 to 70 parts by weight, further preferably 2 to 50 parts by weight, and further preferably 3 to 40 parts by weight. When the addition amount of the (meth) acrylic oligomer exceeds 70 parts by weight, there is a possibility that the elastic modulus becomes too high and the adhesiveness at a low temperature is deteriorated. In addition, it is effective from the point of the improvement effect of adhesive force, when mix | blending 1 weight part or more of (meth) acrylic-type oligomers.
　また、本発明の樹脂組成物には、粘着付与剤（タッキファイヤー）を被着体界面との相互作用を向上させるため、及び樹脂組成物バルクの凝集力を付与するために含有する事ができる。例えば、ロジンエステル系のペンセルシリーズ（荒川化学工業社製）やテルペン系タッキファイヤー（ヤスハラケミカル社製）、ハリタックシリーズ（ハリマ化成社製）等が挙げられ、弾性率が高くなりタックが消失しない程度の量を添加できる。粘着付与剤（タッキファイヤー）は、（メタ）アクリル系ポリマー１００重量部に対して５～４０重量部添加することが好ましい。 Further, the resin composition of the present invention can contain a tackifier (tackifier) for improving the interaction with the adherend interface and for imparting the cohesive force of the resin composition bulk. . For example, rosin ester pencel series (Arakawa Chemical Industries), terpene tackifier (Yasuhara Chemical), Haritac series (Harima Kasei Co., Ltd.), etc., increase in elastic modulus and tack does not disappear A certain amount can be added. The tackifier (tackifier) is preferably added in an amount of 5 to 40 parts by weight with respect to 100 parts by weight of the (meth) acrylic polymer.
　さらに、本発明の樹脂組成物には、被着体との界面での接着信頼性をあげるために、シランカップリング剤を含有することができる。シランカップリング剤の配合量は、（メタ）アクリル系ポリマー１００重量部に対して１重量部以下であるのが好ましく、さらに好ましくは０．０１～１重量部、さらに好ましくは０．０２～０．６重量部である。シランカップリング剤の配合が多過ぎると架橋を阻害したり粘着特性を損なわしたりする可能性があり、少なすぎると効果が得られないため好ましくない。 Furthermore, the resin composition of the present invention can contain a silane coupling agent in order to increase the adhesion reliability at the interface with the adherend. The amount of the silane coupling agent is preferably 1 part by weight or less, more preferably 0.01 to 1 part by weight, and still more preferably 0.02 to 0 part per 100 parts by weight of the (meth) acrylic polymer. .6 parts by weight. If the amount of the silane coupling agent is too large, crosslinking may be inhibited or the adhesive properties may be impaired. If the amount is too small, the effect cannot be obtained, which is not preferable.
　前記シランカップリング剤としては、３－グリシドキシプロピルトリメトキシシラン、３－グリシドキシプロピルトリエトキシシラン、３－グリシドキシプロピルメチルジエトキシシラン、２－（３，４エポキシシクロヘキシル）エチルトリメトキシシラン等のエポキシ基含有シランカップリング剤、３－アミノプロピルトリメトキシシラン、Ｎ－２－（アミノエチル）－３－アミノプロピルメチルジメトキシシラン、３－トリエトキシシリル－Ｎ－（１，３－ジメチルブチリデン）プロピルアミン、Ｎ－フェニル－γ－アミノプロピルトリメトキシシラン等のアミノ基含有シランカップリング剤、３－アクリロキシプロピルトリメトキシシラン、３－メタクリロキシプロピルトリエトキシシラン等の（メタ）アクリル基含有シランカップリング剤、３－イソシアネートプロピルトリエトキシシラン等のイソシアネート基含有シランカップリング剤等が挙げられる。 Examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 2- (3,4 epoxycyclohexyl) ethyltri Epoxy group-containing silane coupling agents such as methoxysilane, 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-triethoxysilyl-N- (1,3- (Meth) such as dimethylbutylidene) propylamine, amino group-containing silane coupling agents such as N-phenyl-γ-aminopropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, etc. Acrylic group-containing silane cup Ing agent, isocyanate group-containing silane coupling agents such as 3-isocyanate propyl triethoxysilane and the like.
　さらに本発明の樹脂組成物には、その他の公知の添加剤を含有していてもよく、たとえば、着色剤、顔料等の粉体、染料、界面活性剤、可塑剤、粘着性付与剤、表面潤滑剤、レベリング剤、軟化剤、酸化防止剤、老化防止剤、光安定剤、紫外線吸収剤、重合禁止剤、無機または有機の充填剤、金属粉、粒子状、箔状物等を使用する用途に応じて適宜添加することができる。 Furthermore, the resin composition of the present invention may contain other known additives, such as powders such as colorants, pigments, dyes, surfactants, plasticizers, tackifiers, surfaces. Applications that use lubricants, leveling agents, softeners, antioxidants, anti-aging agents, light stabilizers, UV absorbers, polymerization inhibitors, inorganic or organic fillers, metal powders, particles, foils, etc. Depending on the case, it can be added appropriately.
＜樹脂層＞
　本発明の樹脂層は、前記樹脂組成物から形成される。樹脂層の厚さは、特に制限されず、例えば、１～１０００μｍ程度である。前記樹脂層の厚さは、好ましくは、３～５００μｍ、より好ましくは５～２００μｍである。 <Resin layer>
The resin layer of the present invention is formed from the resin composition. The thickness of the resin layer is not particularly limited and is, for example, about 1 to 1000 μm. The thickness of the resin layer is preferably 3 to 500 μm, more preferably 5 to 200 μm.
　前記樹脂層のゲル分率は、２０～９５重量％であるのが好ましい。樹脂層のゲル分率は、樹脂層の凝集力や保持力を高める観点から、２５重量％以上であることがより好ましく、３０重量％以上であることがさらに好ましく、３５重量％以上であることがよりさらに好ましい。樹脂層のゲル分率は、樹脂層の接着力を高める観点から、８０重量％以下であることがより好ましく、７０重量％以下であることがさらに好ましく、６５重量％以下であることがよりさらに好ましい。尚、前記樹脂組成物が架橋剤を含有する場合には、架橋剤全体の添加量を調整することとともに、架橋処理温度や架橋処理時間の影響を十分考慮して、ゲル分率が制御することができる。 The gel fraction of the resin layer is preferably 20 to 95% by weight. The gel fraction of the resin layer is more preferably 25% by weight or more, further preferably 30% by weight or more, and more preferably 35% by weight or more from the viewpoint of increasing the cohesive force and holding power of the resin layer. Is even more preferable. The gel fraction of the resin layer is more preferably 80% by weight or less, more preferably 70% by weight or less, and still more preferably 65% by weight or less, from the viewpoint of increasing the adhesive strength of the resin layer. preferable. When the resin composition contains a cross-linking agent, the gel fraction should be controlled by adjusting the total amount of the cross-linking agent and taking into consideration the effects of the cross-linking temperature and the cross-linking time. Can do.
　前記樹脂層は、例えば、前記樹脂組成物を支持体の片面又は両面に塗布し、重合溶剤等を加熱乾燥によって除去することにより積層シートとして形成することができる。樹脂組成物の塗布にあたっては、適宜に、重合溶剤以外の一種以上の溶剤を新たに加えてもよい。 The resin layer can be formed as a laminated sheet by, for example, applying the resin composition to one or both sides of a support and removing the polymerization solvent by heating and drying. In applying the resin composition, one or more solvents other than the polymerization solvent may be added as appropriate.
　前記樹脂組成物の塗布方法としては、各種方法が用いられる。具体的には、例えば、ロールコート、キスロールコート、グラビアコート、リバースコート、ロールブラッシュ、スプレーコート、ディップロールコート、バーコート、ナイフコート、エアーナイフコート、カーテンコート、リップコート、ダイコーター等による押出しコート法等の方法が挙げられる。 Various methods are used as a method for applying the resin composition. Specifically, for example, by 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. Examples thereof include an extrusion coating method.
　前記加熱乾燥の温度は、好ましくは４０～２００℃であり、さらに好ましくは、５０～１８０℃であり、特に好ましくは７０～１７０℃である。加熱温度を上記の範囲とすることによって、優れた粘着特性を有する樹脂層を得ることができる。前記加熱乾燥の時間は、好ましくは５秒～２０分、さらに好ましくは５秒～１５分、特に好ましくは１０秒～１０分である。 The temperature of the heat drying is preferably 40 to 200 ° C., more preferably 50 to 180 ° C., and particularly preferably 70 to 170 ° C. By setting the heating temperature within the above range, a resin layer having excellent adhesive properties can be obtained. The heat drying time is preferably 5 seconds to 20 minutes, more preferably 5 seconds to 15 minutes, and particularly preferably 10 seconds to 10 minutes.
　また、前記樹脂層の形成は、本発明の（メタ）アクリル系ポリマーを、モノマー成分を紫外線照射することにより重合して製造する場合には、前記モノマー成分から（メタ）アクリル系ポリマーを製造するとともに、樹脂層を形成することができる。モノマー成分には、適宜に架橋剤等の前記樹脂組成物に配合することができる材料を含有することができる。前記モノマー成分は、紫外線照射にあたり、事前に一部を重合してシロップにしたものを用いることができる。紫外線照射には、高圧水銀ランプ、低圧水銀ランプ、メタルハライドランプ等を用いることができる。 The resin layer is formed by producing the (meth) acrylic polymer of the present invention by polymerizing the monomer component by irradiating the monomer component with ultraviolet rays. At the same time, a resin layer can be formed. The monomer component can contain materials that can be appropriately blended in the resin composition, such as a crosslinking agent. As the monomer component, a part of the monomer component previously polymerized into a syrup can be used for ultraviolet irradiation. For ultraviolet irradiation, a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, or the like can be used.
　前記支持体としては、ポリエチレン、ポリプロピレン、ポリエチレンテレフタレート、ポリエステルフィルム等のプラスチックフィルム、ポリアクリルフィルム、紙、布、不織布等の多孔質材料、ネット、ポリエチレンフォームやアクリルフォーム等の気泡含有シート、金属箔、及びこれらのラミネート体等の各種の支持フィルムを挙げることができる。尚、前記気泡とは中空粒子等の含有によるものも含む。前記支持フィルムの厚みは、通常５～３０００μｍ、好ましくは１０～２５００μｍ、さらに好ましくは２０～２０００μｍ程度である。 Examples of the support include plastic films such as polyethylene, polypropylene, polyethylene terephthalate, and polyester films, polyacrylic films, porous materials such as paper, cloth, and nonwoven fabric, nets, bubble-containing sheets such as polyethylene foam and acrylic foam, and metal foils. And various support films such as laminates thereof. The bubbles include those due to the inclusion of hollow particles and the like. The thickness of the support film is usually about 5 to 3000 μm, preferably about 10 to 2500 μm, and more preferably about 20 to 2000 μm.
　前記支持フィルムには、必要に応じて、シリコーン系、フッ素系、長鎖アルキル系もしくは脂肪酸アミド系の離型剤、シリカ粉等による離型及び防汚処理や、塗布型、練り込み型、蒸着型等の帯電防止処理もすることもできる。 For the support film, if necessary, mold release and antifouling treatment with a silicone type, fluorine type, long chain alkyl type or fatty acid amide type release agent, silica powder, etc., coating type, kneading type, vapor deposition An antistatic treatment such as a mold can also be performed.
　本発明の積層シートは、前記樹脂層が露出する場合には、実用に供されるまでセパレーターで樹脂層を保護してもよい。実用に際しては、前記セパレーターは剥離される。 In the laminated sheet of the present invention, when the resin layer is exposed, the resin layer may be protected with a separator until it is practically used. In practical use, the separator is peeled off.
　セパレーターの構成材料としては、例えば、ポリエチレン、ポリプロピレン、ポリエチレンテレフタレート、ポリエステルフィルム等のプラスチックフィルム、紙、布、不織布等の多孔質材料、ネット、気泡含有シート、金属箔、及びこれらのラミネート体等の適宜な薄葉体等を挙げることができる。表面平滑性に優れる点からプラスチックフィルムが好適に用いられる。 As a constituent material of the separator, for example, plastic films such as polyethylene, polypropylene, polyethylene terephthalate, polyester film, porous materials such as paper, cloth, nonwoven fabric, nets, bubble-containing sheets, metal foils, and laminates thereof Appropriate thin leaves and the like can be mentioned. A plastic film is preferably used from the viewpoint of excellent surface smoothness.
　前記プラスチックフィルムとしては、前記樹脂層を保護し得るフィルムであれば特に限定されず、例えば、ポリエチレンフィルム、ポリプロピレンフィルム、ポリブテンフィルム、ポリブタジエンフィルム、ポリメチルペンテンフイルム、ポリ塩化ビニルフィルム、塩化ビニル共重合体フィルム、ポリエチレンテレフタレートフィルム、ポリブチレンテレフタレートフィルム、ポリウレタンフィルム、エチレン－酢酸ビニル共重合体フィルム等が挙げられる。 The plastic film is not particularly limited as long as it can protect the resin layer. For example, a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, a polymethylpentene film, a polyvinyl chloride film, and a vinyl chloride copolymer are used. Examples thereof include a coalesced film, a polyethylene terephthalate film, a polybutylene terephthalate film, a polyurethane film, and an ethylene-vinyl acetate copolymer film.
　前記セパレーターの厚みは、通常５～３００μｍ、好ましくは５～２００μｍ程度である。前記セパレーターには、必要に応じて、シリコーン系、フッ素系、長鎖アルキル系もしくは脂肪酸アミド系の離型剤、シリカ粉等による離型及び防汚処理や、塗布型、練り込み型、蒸着型等の帯電防止処理もすることもできる。特に、前記セパレーターの表面にシリコーン処理、長鎖アルキル処理、フッ素処理等の剥離処理を適宜おこなうことにより、前記樹脂層からの剥離性をより高めることができる。 The thickness of the separator is usually about 5 to 300 μm, preferably about 5 to 200 μm. For the separator, silicone type, fluorine type, long chain alkyl type or fatty acid amide type release agent, mold release and antifouling treatment with silica powder, coating type, kneading type, vapor deposition type, if necessary It is also possible to perform antistatic treatment such as. In particular, when the surface of the separator is appropriately subjected to a release treatment such as silicone treatment, long-chain alkyl treatment, or fluorine treatment, the peelability from the resin layer can be further enhanced.
　本発明の樹脂組成物、樹脂層及び積層シートは、コンクリ－ト、モルタル、石膏ボード、針葉樹合板、木質系セメント板、ケイ酸カルシウム板、タイル、及び繊維強化セメント板等の粗面を有する被着体に貼り付ける用途に用いることが好ましい。 The resin composition, resin layer and laminated sheet of the present invention are coated with a rough surface such as concrete, mortar, gypsum board, softwood plywood, wood cement board, calcium silicate board, tile and fiber reinforced cement board. It is preferable to use it for the purpose of sticking to a kimono.
　前記粗面を有する被着体の表面凹凸（表面の粗さ）は、１μｍ～数１００μｍ程度のものを対象としている。前記積層シートは、特に、表面凹凸（表面の粗さ）が、１μｍ～５００μｍである粗面を有する被着体に対して、好ましく用いられる。 The surface irregularity (surface roughness) of the adherend having the rough surface is about 1 μm to several 100 μm. The laminated sheet is particularly preferably used for an adherend having a rough surface with surface irregularities (surface roughness) of 1 μm to 500 μm.
　以下に、実施例によって本発明を具体的に説明するが、本発明はこれら実施例によって限定されるものではない。尚、各例中の部及び％はいずれも重量基準である。実施例等における評価項目は下記のようにして測定を行った。 Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples. In the examples, all parts and% are based on weight. Evaluation items in Examples and the like were measured as follows.
　実施例１
＜（メタ）アクリル系ポリマーの調製＞
　攪拌羽根、温度計、窒素ガス導入管、冷却器を備えた４つ口フラスコに、２－エチルヘキシルアクリレート（２ＥＨＡ）９０重量部、エチルカルビトールアクリレート（ＣＢＡ）１０重量部、４－ヒドロキシブチルアクリレート（４ＨＢＡ）０．２５重量部、アクリル酸（ＡＡ）１重量部、重合開始剤として２，２´－アゾビスイソブチロニトリル０．０７重量部を酢酸エチル１０５重量部と共に仕込み、緩やかに攪拌しながら窒素ガスを導入して１時間窒素置換した後、フラスコ内の液温を６０～６５℃付近に保って１０時間重合反応を行い、重量平均分子量７７万の（メタ）アクリル系ポリマー溶液を調製した。得られた（メタ）アクリル系ポリマーのＴｇは－６８．７℃であった。 Example 1
<Preparation of (meth) acrylic polymer>
In a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas inlet tube, and a condenser, 90 parts by weight of 2-ethylhexyl acrylate (2EHA), 10 parts by weight of ethyl carbitol acrylate (CBA), 4-hydroxybutyl acrylate ( 4HBA) 0.25 parts by weight, acrylic acid (AA) 1 part by weight, 2,2′-azobisisobutyronitrile 0.07 part by weight as a polymerization initiator together with 105 parts by weight of ethyl acetate, and gently stirred. While introducing nitrogen gas and replacing with nitrogen for 1 hour, the liquid temperature in the flask was kept at 60 to 65 ° C. and the polymerization reaction was carried out for 10 hours to prepare a (meth) acrylic polymer solution having a weight average molecular weight of 770,000. did. The obtained (meth) acrylic polymer had a Tg of −68.7 ° C.
　次いで、上記で得られた（メタ）アクリル系ポリマー溶液に、ポリマーの固形分１００重量部に対して、架橋剤として、２，４－トリレンジイソシアネートのトリメチロールプロパン付加物（東ソー社製，商品名コロネートＬ）を０．１６重量部配合して樹脂組成物溶液を調製した。 Next, in the (meth) acrylic polymer solution obtained above, 2,4-tolylene diisocyanate trimethylolpropane adduct (commercially available from Tosoh Corporation, as a crosslinking agent) with respect to 100 parts by weight of the solid content of the polymer. A resin composition solution was prepared by blending 0.16 parts by weight of the name coronate L).
　次いで、得られた樹脂組成物溶液を、シリコーン処理を施した３８μｍのポリエチレンテレフタレート（ＰＥＴ）フィルムセパレーター（三菱樹脂社製，ダイアホイルＭＲＦ）の片面に、乾燥後の樹脂層の厚さが９５μｍになるように塗布し、１３０℃で５分間乾燥を行い、樹脂層を形成し、積層シートを作製した。 Next, the obtained resin composition solution was applied to one side of a 38 μm polyethylene terephthalate (PET) film separator (Mitsubishi Resin Co., Ltd., Diafoil MRF) subjected to silicone treatment, and the thickness of the resin layer after drying was 95 μm. Then, it was dried at 130 ° C. for 5 minutes to form a resin layer, and a laminated sheet was produced.
　実施例２～２９、比較例１～５
　実施例１において、（メタ）アクリル系ポリマーの調製に用いたモノマーの種類とその組成比、架橋剤の種類とその配合量を表１に示すように変えたこと以外は、実施例１と同様の操作を行い、積層シートを作製した。得られた（メタ）アクリル系ポリマーの重量平均分子量、Ｔｇを表１に示す。 Examples 2 to 29, Comparative Examples 1 to 5
Example 1 is the same as Example 1 except that the types and composition ratios of the monomers used for the preparation of the (meth) acrylic polymer and the types and amounts of the crosslinking agents are changed as shown in Table 1. Thus, a laminated sheet was produced. Table 1 shows the weight average molecular weight and Tg of the obtained (meth) acrylic polymer.
　実施例３０
＜（メタ）アクリル系ポリマーシロップの調製＞
　攪拌羽根、温度計、窒素ガス導入管、冷却器を備えた４つ口フラスコに、２－エチルヘキシルアクリレート（２ＥＨＡ）９０重量部、エチルカルビトールアクリレート（ＣＢＡ）１０重量部、４－ヒドロキシブチルアクリレート（４ＨＢＡ）０．２５重量部、アクリル酸（ＡＡ）１重量部、光重合開始剤（商品名：イルガキュア１８４、ＢＡＳＦ社製）０．１５重量部および光重合開始剤（商品名：イルガキュア６５１、ＢＡＳＦ社製）０．１５重量部を４つ口フラスコに投入してモノマー混合物を調製した。次いで、前記モノマー混合物を窒素雰囲気下で紫外線に曝露して部分的に光重合させることによって、重合率約１０重量％の部分重合物（（メタ）アクリル系ポリマーシロップ）を得た。 Example 30
<Preparation of (meth) acrylic polymer syrup>
In a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas inlet tube, and a condenser, 90 parts by weight of 2-ethylhexyl acrylate (2EHA), 10 parts by weight of ethyl carbitol acrylate (CBA), 4-hydroxybutyl acrylate ( 4HBA) 0.25 parts by weight, acrylic acid (AA) 1 part by weight, photopolymerization initiator (trade name: Irgacure 184, manufactured by BASF) 0.15 parts by weight and photopolymerization initiator (trade name: Irgacure 651, BASF) 0.15 parts by weight) was added to a four-necked flask to prepare a monomer mixture. Next, the monomer mixture was partially photopolymerized by exposing it to ultraviolet rays under a nitrogen atmosphere to obtain a partially polymerized product ((meth) acrylic polymer syrup) having a polymerization rate of about 10% by weight.
　次いで、上述した（メタ）アクリル系ポリマーシロップの１００重量部に、架橋剤として、トリメチロールプロパントリアクリレート（ＴＭＰＴＡ）０．０１重量部を添加した後、これらを均一に混合してモノマー成分を調製した。 Next, after adding 0.01 parts by weight of trimethylolpropane triacrylate (TMPTA) as a crosslinking agent to 100 parts by weight of the above-mentioned (meth) acrylic polymer syrup, these are uniformly mixed to prepare a monomer component. did.
　次いで、上記で調整したモノマー成分を、片面をシリコーンで剥離処理した厚み３８μｍのポリエステルフィルム（商品名：ダイアホイルＭＲＦ、三菱樹脂株式会社製）の剥離処理面に、最終的な厚みが９５μｍになるように塗布して塗布層を形成した。次いで、塗布されたモノマー成分の表面に、片面をシリコーンで剥離処理した厚み３８μｍのポリエステルフィルム（商品名：ダイアホイルＭＲＥ、三菱樹脂株式会社製）を、当該フィルムの剥離処理面が塗布層側になるようにして被覆した。これにより、モノマー成分の塗布層を酸素から遮断した。このようにして得られた塗布層を有するシートにケミカルライトランプ（株式会社東芝製）を用いて照度５ｍＷ／ｃｍ２（約３５０ｎｍに最大感度をもつトプコンＵＶＲ－Ｔ１で測定）の紫外線を３６０秒間照射して、塗布層を硬化させて樹脂層を得た後、片面のポリエステルフィルム（ダイアホイルＭＲＥ）を剥離し、積層シートを作製した。 Next, the final thickness is 95 μm on the release surface of the 38 μm thick polyester film (trade name: Diafoil MRF, manufactured by Mitsubishi Plastics Co., Ltd.) having the monomer component prepared above peel-treated on one side with silicone. The coating layer was formed by coating as described above. Next, a 38 μm thick polyester film (trade name: Diafoil MRE, manufactured by Mitsubishi Plastics Co., Ltd.) having one surface peeled with silicone on the surface of the applied monomer component, the peel-treated surface of the film is on the coating layer side. It was coated as follows. Thereby, the coating layer of the monomer component was shielded from oxygen. The sheet having the coating layer thus obtained was irradiated with ultraviolet rays having an illuminance of 5 mW / cm 2 (measured with Topcon UVR-T1 having a maximum sensitivity of about 350 nm) for 360 seconds using a chemical light lamp (manufactured by Toshiba Corporation). After irradiation, the coating layer was cured to obtain a resin layer, and then the single-sided polyester film (Diafoil MRE) was peeled off to produce a laminated sheet.
　実施例３１～３３
　実施例３０において、（メタ）アクリル系ポリマーシロップの調製に用いたモノマーの組成比を表２に示すように変えたこと以外は、実施例３０と同様の操作を行い、積層シートを作製した。得られた（メタ）アクリル系ポリマーのＴｇを表２に示す。 Examples 31-33
In Example 30, a laminated sheet was produced in the same manner as in Example 30, except that the composition ratio of the monomers used for the preparation of the (meth) acrylic polymer syrup was changed as shown in Table 2. Table 2 shows Tg of the obtained (meth) acrylic polymer.
　上記の実施例及び比較例で得られた、積層シート（サンプル）について以下の評価を行った。評価結果を表１および２に示す。 The following evaluation was performed on the laminated sheets (samples) obtained in the above Examples and Comparative Examples. The evaluation results are shown in Tables 1 and 2.
＜ゲル分率の測定＞
　積層シートにおける樹脂層から所定量（最初の重量Ｗ１）を取り出し、酢酸エチル溶液に浸漬して、室温で１週間放置した後、不溶分を取り出し、乾燥させた重量（Ｗ２）を測定し、下記のように求めた。
　ゲル分率（％）＝（Ｗ２／Ｗ１）×１００ <Measurement of gel fraction>
A predetermined amount (initial weight W1) is taken out from the resin layer in the laminated sheet, immersed in an ethyl acetate solution and allowed to stand at room temperature for 1 week, then insoluble matter is taken out, and the dried weight (W2) is measured. I asked for it.
Gel fraction (%) = (W2 / W1) × 100
＜ピール接着力の測定＞
　実施例及び比較例で得られたサンプルの粘着面に厚み２５μｍのＰＥＴフィルム（東レ社製，ルミラーＳ１０）を貼り付けたものを評価用サンプルとした。当該評価用サンプルを、幅２０ｍｍ×長さ約１００ｍｍに裁断した後、前記セパレーター（三菱樹脂社製，ダイアホイルＭＲＦ）を剥離して、各種被着体として、石膏ボード（吉野石膏社製、商品名タイガーボード　９．５ｍｍ厚）、針葉樹合板（島忠ホームズ入手　１２ｍｍ厚）、又はケイ酸カルシウム板（ケイカル板、島忠ホームズ入手　５ｍｍ厚）に、２ｋｇのロールを１往復で貼付けた。次いで、室温（２３℃）で３０分静置した後、剥離角度１８０°、剥離速度３００ｍｍ／分でピール接着力（Ｎ／２０ｍｍ）を測定した。尚、前記ピール接着力は、１０Ｎ／２０ｍｍ以上であることが好ましく、１２Ｎ／２０ｍｍ以上であることがより好ましく、１５Ｎ／２０ｍｍ以上であることがさらに好ましい。 <Measurement of peel adhesion>
A sample for evaluation was prepared by attaching a PET film having a thickness of 25 μm (Lumirror S10, manufactured by Toray Industries, Inc.) to the adhesive surfaces of the samples obtained in Examples and Comparative Examples. The sample for evaluation was cut into a width of 20 mm and a length of about 100 mm, and then the separator (manufactured by Mitsubishi Plastics, Diafoil MRF) was peeled off to form a gypsum board (manufactured by Yoshino Gypsum Co., Ltd., product) A 2 kg roll was pasted in one reciprocation on a name Tiger board (9.5 mm thickness), softwood plywood (Shimadachu Homes acquisition 12 mm thickness), or a calcium silicate board (Keical board, Shimatada Homes acquisition 5 mm thickness). Subsequently, after leaving still at room temperature (23 degreeC) for 30 minutes, the peel adhesive force (N / 20mm) was measured by the peeling angle of 180 degrees and the peeling speed of 300 mm / min. The peel adhesive strength is preferably 10 N / 20 mm or more, more preferably 12 N / 20 mm or more, and further preferably 15 N / 20 mm or more.
＜保持力の測定＞
　実施例及び比較例で得られたサンプルの粘着面に厚み２５μｍのＰＥＴフィルム（東レ社製，ルミラーＳ１０）を貼り付けたものを評価用サンプルとした。当該評価用サンプルを、幅１０ｍｍ×長さ１００ｍｍに裁断した後、前記セパレーター（三菱樹脂社製，ダイアホイルＭＲＦ）を剥離して、被着体として、針葉樹合板（島忠ホームズ入手　１２ｍｍ厚）に、貼りつけ面積が幅１０ｍｍ×長さ２０ｍｍになるように２ｋｇのロールを１往復で貼付けた。次いで、室温（２３℃）で３０分静置した後、針葉樹合板を垂下し、試料片の自由端に５００ｇの荷重を付与した。当該荷重が付与された状態で４０℃の環境下に１時間放置し、最初の貼り付け位置からの試料テープのズレ距離（ｍｍ）を測定し、保持力（ｍｍ／ｈ）を算出した。尚、前記保持力は、２．０ｍｍ／ｈ以下であることが好ましく、１．５ｍｍ／ｈ以下であることがより好ましく、１．０ｍｍ／ｈ以下であることがより好ましい。 <Measurement of holding power>
A sample for evaluation was prepared by attaching a PET film having a thickness of 25 μm (Lumirror S10, manufactured by Toray Industries, Inc.) to the adhesive surfaces of the samples obtained in Examples and Comparative Examples. After the sample for evaluation was cut into a width of 10 mm and a length of 100 mm, the separator (manufactured by Mitsubishi Plastics, Diafoil MRF) was peeled off, and as an adherend, softwood plywood (Shimadachi Holmes obtained 12 mm thickness), A 2 kg roll was pasted in one reciprocation so that the pasting area would be 10 mm wide x 20 mm long. Subsequently, after leaving still at room temperature (23 degreeC) for 30 minutes, the softwood plywood was drooped and the load of 500g was provided to the free end of the sample piece. The sample was left in an environment of 40 ° C. for 1 hour in the state where the load was applied, and the displacement distance (mm) of the sample tape from the first attachment position was measured, and the holding force (mm / h) was calculated. The holding force is preferably 2.0 mm / h or less, more preferably 1.5 mm / h or less, and more preferably 1.0 mm / h or less.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表１および２中、２ＥＨＡは、２－エチルヘキシルアクリレート（大阪有機化学工業社製，ホモポリマーのＴｇ＝－７０℃）；
　ＩＮＡは、イソノニルアクリレート（大阪有機化学工業社製，ホモポリマーのＴｇ＝－５８℃）；
　ＩＭＡは、イソミスチリルアクリレート(共栄社化学株式会社，ホモポリマーのＴｇ＝－５６℃)；
　ＣＢＡは、エチルカルビトールアクリレート（大阪有機化学工業社製，ホモポリマーのＴｇ＝－６７℃）；
　♯ＭＴＧは、メトキシトリエチレングリコールアクリレート（大阪有機化学工業社製，ホモポリマーのＴｇ＝－５７℃）；
　４ＨＢＡは、４－ヒドロキシブチルアクリレート（大阪有機化学工業社製，ホモポリマーのＴｇ＝－３２℃）；
　ＨＥＡは、ヒドロキシエチルアクリレート（大阪有機化学工業社製，ホモポリマーのＴｇ＝－１５℃）；
　ＡＡはアクリル酸（東亜合成社製，ホモポリマーのＴｇ＝１０６℃）；
　ＢＡは、ブチルアクリレート（東亜合成社製，ホモポリマーのＴｇ＝－５５℃）；を示す。 In Tables 1 and 2, 2EHA is 2-ethylhexyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., homopolymer Tg = −70 ° C.);
INA is isononyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., homopolymer Tg = −58 ° C.);
IMA is isomisticyl acrylate (Kyoeisha Chemical Co., Ltd., homopolymer Tg = −56 ° C.);
CBA is ethyl carbitol acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., homopolymer Tg = −67 ° C.);
#MTG is methoxytriethylene glycol acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., homopolymer Tg = −57 ° C.);
4HBA is 4-hydroxybutyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., homopolymer Tg = −32 ° C.);
HEA is hydroxyethyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., homopolymer Tg = −15 ° C.);
AA is acrylic acid (manufactured by Toagosei Co., Ltd., homopolymer Tg = 106 ° C.);
BA represents butyl acrylate (manufactured by Toagosei Co., Ltd., homopolymer Tg = −55 ° C.).
　表１および２中、Ｃ／Ｌは、トリメチロールプロパン／２，４－トリレンジイソシアネート３量体付加物（東ソー社製，商品名コロネートＬ）；
　Ｄ１１０Ｎは、キシリレンジイソシアネートのトリメチロールプロパン付加物（三井化学社製，商品名：タケネートＤ１１０Ｎ）；
　Ｄ１２０Ｎは、キシリレンジイソシアネートのトリメチロールプロパン付加物（三井化学社製，商品名：タケネートＤ１２０Ｎ）；
　Ｄ１４０Ｎは、イソホロンジイソシアネートのトリメチロールプロパン付加物（三井化学社製，商品名：タケネートＤ１４０Ｎ）；
　Ｔ／Ｃは、１，３－ビス（Ｎ，Ｎ－ジグリシジルアミノメチル）シクロヘキサン（三菱ガス化学社製，商品名テトラッドＣ）；
　ＴＭＰＴＡは、トリメチロールプロパントリアクリレート（（大阪有機化学工業社製）；を示す。 In Tables 1 and 2, C / L represents trimethylolpropane / 2,4-tolylene diisocyanate trimer adduct (trade name Coronate L manufactured by Tosoh Corporation);
D110N is a trimethylolpropane adduct of xylylene diisocyanate (manufactured by Mitsui Chemicals, trade name: Takenate D110N);
D120N is a trimethylolpropane adduct of xylylene diisocyanate (trade name: Takenate D120N, manufactured by Mitsui Chemicals);
D140N is a trimethylolpropane adduct of isophorone diisocyanate (trade name: Takenate D140N, manufactured by Mitsui Chemicals);
T / C is 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane (trade name Tetrad C, manufactured by Mitsubishi Gas Chemical Company);
TMPTA indicates trimethylolpropane triacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.).

Claims (20)

  1. 　ホモポリマーのＴｇが－５０℃以下であり、かつ炭素数８～１８の分岐したアルキル基をエステル基の末端に有するアルキル（メタ）アクリレート（ａ１）を５０～９７重量％、及びホモポリマーのＴｇが－４０℃以下であり、かつ分子骨格内にエーテル結合を有する（メタ）アクリレート（ａ２）を３～５０重量％を含むモノマー成分を重合することにより得られたＴｇが－４０℃以下である（メタ）アクリル系ポリマーを含むことを特徴とする樹脂組成物。 50 to 97% by weight of alkyl (meth) acrylate (a1) having a Tg of the homopolymer of −50 ° C. or lower and a branched alkyl group having 8 to 18 carbon atoms at the terminal of the ester group, and the Tg of the homopolymer Tg obtained by polymerizing a monomer component containing 3 to 50% by weight of (meth) acrylate (a2) having an ether bond in the molecular skeleton is −40 ° C. or lower. A resin composition comprising a (meth) acrylic polymer.
  2. 　前記アルキル（メタ）アクリレート（ａ１）及び前記エーテル結合を有する（メタ）アクリレート（ａ２）の合計の割合が、（メタ）アクリル系ポリマーを形成する全モノマー成分に対して、７５重量％以上であることを特徴とする請求項１記載の樹脂組成物。 The total proportion of the alkyl (meth) acrylate (a1) and the (meth) acrylate (a2) having an ether bond is 75% by weight or more based on the total monomer components forming the (meth) acrylic polymer. The resin composition according to claim 1.
  3. 　前記アルキル（メタ）アクリレート（ａ１）及び前記エーテル結合を有する（メタ）アクリレート（ａ２）の合計の割合が、（メタ）アクリル系ポリマーを形成する全モノマー成分に対して、８５重量％以上であることを特徴とする請求項１記載の樹脂組成物。 The total ratio of the alkyl (meth) acrylate (a1) and the (meth) acrylate (a2) having an ether bond is 85% by weight or more based on the total monomer components forming the (meth) acrylic polymer. The resin composition according to claim 1.
  4. 　前記エーテル結合を有する（メタ）アクリレート（ａ２）が、
    　一般式（１）：ＣＨ２＝ＣＲ１－ＣＯＯ－（ＡＯ）ｎ－Ｒ２
    ［前記一般式（１）中、Ｒ１は水素原子又はメチル基、ＡＯは炭素数２～３のアルキレンオキシ基、ｎはアルキレンオキシ基の平均付加モル数を示す１～８であり、Ｒ２は芳香環、又は直鎖、分岐鎖、もしくは脂環式アルキル基である。］で表されるモノマーであることを特徴とする請求項１～３のいずれか１項に記載の樹脂組成物。     The (meth) acrylate (a2) having an ether bond is
    Formula (1): CH 2 ═CR 1 —COO— (AO) n —R 2
    [In the general formula (1), R 1 is a hydrogen atom or a methyl group, AO is an alkyleneoxy group having 2 to 3 carbon atoms, n is 1 to 8 indicating the average number of added moles of the alkyleneoxy group, and R 2 Is an aromatic ring or a linear, branched, or alicyclic alkyl group. The resin composition according to any one of claims 1 to 3, which is a monomer represented by the formula:
  5. 　前記一般式（１）中のＡＯが、オキシエチレン基であることを特徴とする請求項４記載の樹脂組成物。 The resin composition according to claim 4, wherein AO in the general formula (1) is an oxyethylene group.
  6. 　前記一般式（１）中のｎが、２～８であることを特徴とする請求項４又は５記載の樹脂組成物。 6. The resin composition according to claim 4, wherein n in the general formula (1) is 2 to 8.
  7. 　前記一般式（１）中のＲ２が、炭素数が１～６である無置換の芳香環、又は直鎖、分岐鎖、もしくは脂環式アルキル基であることを特徴とする請求項４～６のいずれか１項に記載の樹脂組成物。 The R 2 in the general formula (1) is an unsubstituted aromatic ring having 1 to 6 carbon atoms, or a linear, branched, or alicyclic alkyl group. 7. The resin composition according to any one of 6 above.
  8. 　前記モノマー成分が、さらに、ヒドロキシル基を有するモノマー、カルボキシル基を有するモノマー、及びエポキシ基を有するモノマーから選ばれるいずれか少なくとも１つの官能基を有するモノマーを含むことを特徴とする請求項１～７のいずれか１項に記載の樹脂組成物。 The monomer component further includes a monomer having at least one functional group selected from a monomer having a hydroxyl group, a monomer having a carboxyl group, and a monomer having an epoxy group. The resin composition according to any one of the above.
  9. 　前記ヒドロキシル基を有するモノマーが、（メタ）アクリル系ポリマーを形成する全モノマー成分に対して、０．０１重量％以上、３重量％以下であることを特徴とする請求項８に記載の樹脂組成物。 The resin composition according to claim 8, wherein the monomer having a hydroxyl group is 0.01 wt% or more and 3 wt% or less with respect to all monomer components forming the (meth) acrylic polymer. object.
  10. 　前記カルボキシル基を有するモノマーが、（メタ）アクリル系ポリマーを形成する全モノマー成分に対して、０．１重量％以上、５重量％以下であることを特徴とする請求項８又は９に記載の樹脂組成物。 The monomer having a carboxyl group is 0.1 wt% or more and 5 wt% or less based on all monomer components forming the (meth) acrylic polymer. Resin composition.
  11. 　前記モノマー成分が、さらに、多官能性モノマーを、（メタ）アクリル系ポリマーを形成する全モノマー成分に対して、５重量％以下含むことを特徴とする請求項１～１０のいずれか１項に記載の樹脂組成物。 11. The monomer component according to any one of claims 1 to 10, wherein the monomer component further contains a polyfunctional monomer in an amount of 5% by weight or less based on the total monomer components forming the (meth) acrylic polymer. The resin composition as described.
  12. 　前記（メタ）アクリル系ポリマーの重量平均分子量が、３５万以上であることを特徴とする請求項１～１１のいずれか１項に記載の樹脂組成物。 The resin composition according to any one of claims 1 to 11, wherein the (meth) acrylic polymer has a weight average molecular weight of 350,000 or more.
  13. 　さらに、前記（メタ）アクリル系ポリマー１００重量部に対して、架橋剤を、０．０１～５重量部含むことを特徴とする請求項１～１２のいずれか１項に記載の樹脂組成物。 The resin composition according to any one of claims 1 to 12, further comprising 0.01 to 5 parts by weight of a crosslinking agent with respect to 100 parts by weight of the (meth) acrylic polymer.
  14. 　前記架橋剤が、イソシアネート系架橋剤、及び／又はエポキシ系架橋剤であることを特徴とする請求項１３記載の樹脂組成物。 14. The resin composition according to claim 13, wherein the crosslinking agent is an isocyanate crosslinking agent and / or an epoxy crosslinking agent.
  15. 　請求項１～１４のいずれか１項に記載の樹脂組成物から得られることを特徴とする樹脂層。 A resin layer obtained from the resin composition according to any one of claims 1 to 14.
  16. 　ゲル分率が２０～９５重量％であることを特徴とする請求項１５記載の樹脂層。 The resin layer according to claim 15, wherein the gel fraction is 20 to 95% by weight.
  17. 　支持体の少なくとも片側に、請求項１５又は１６記載の樹脂層が設けられていることを特徴とする積層シート。 A laminate sheet, wherein the resin layer according to claim 15 or 16 is provided on at least one side of the support.
  18. 　前記樹脂層の被着体に対する１８０°ピール接着力が、剥離速度３００ｍｍ／分の条件下で、１０Ｎ／２０ｍｍ以上であることを特徴とする請求項１７記載の積層シート。 The laminated sheet according to claim 17, wherein 180 ° peel adhesive strength of the resin layer to the adherend is 10 N / 20 mm or more under the condition of a peeling rate of 300 mm / min.
  19. 　前記支持体が、プラスチックフィルム、紙、不織布及び気泡含有シート、のいずれかであることを特徴とする請求項１７又は１８記載の積層シート。 The laminated sheet according to claim 17 or 18, wherein the support is any one of a plastic film, paper, a nonwoven fabric and a bubble-containing sheet.
  20. 　前記被着体が、コンクリ－ト、モルタル、石膏ボード、針葉樹合板、木質系セメント板、ケイ酸カルシウム板、タイル、及び繊維強化セメント板のいずれかであることを特徴とする請求項１８又は１９記載の積層シート。 20. The adherend is any one of concrete, mortar, gypsum board, softwood plywood, wood-based cement board, calcium silicate board, tile, and fiber reinforced cement board. The laminated sheet as described.
PCT/JP2017/021435 2016-07-14 2017-06-09 Resin composition, resin layer, and laminated sheet WO2018012161A1 (en)

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CN201780034772.9A CN109312139A (en) 2016-07-14 2017-06-09 Resin combination, resin layer and laminates
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