WO2023188627A1 - Active energy ray-curable adhesive composition - Google Patents

Active energy ray-curable adhesive composition Download PDF

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Publication number
WO2023188627A1
WO2023188627A1 PCT/JP2022/047349 JP2022047349W WO2023188627A1 WO 2023188627 A1 WO2023188627 A1 WO 2023188627A1 JP 2022047349 W JP2022047349 W JP 2022047349W WO 2023188627 A1 WO2023188627 A1 WO 2023188627A1
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Prior art keywords
meth
acrylate
active energy
energy ray
curable adhesive
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PCT/JP2022/047349
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French (fr)
Japanese (ja)
Inventor
直毅 臣
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サカタインクス株式会社
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Publication of WO2023188627A1 publication Critical patent/WO2023188627A1/en

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Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C09J201/02—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16

Definitions

  • the present invention relates to an active energy ray-curable adhesive composition.
  • Various laminated films widely used as flexible packaging materials are manufactured by methods such as dry lamination, extrusion lamination, and hot melt lamination. These lamination methods all laminate various base materials such as film, aluminum foil, paper, and cloth through an adhesive layer, and adhesives include urethane resin, epoxy resin, phenol resin, and acrylic acid. Various resins are used, such as ester resins and vinyl acetate resins. Among these adhesives, reactive adhesives are usually used in laminating plastic films, which particularly require high adhesive strength and high heat resistance.
  • the mainstream of reactive adhesives is urethane-based adhesives, in which the adhesive components polyol and polyisocyanate form a urethane bond, resulting in high molecular weight and crosslinking, which then hardens to form a bond. It is.
  • two-component curing urethane adhesives are excellent in meeting the multifaceted performance requirements after adhesion, but the adhesive strength is low immediately after lamination, and in order to obtain the desired performance, it is necessary to Requires heating aging for 3 days. For this reason, it is not possible to process the film immediately after lamination, resulting in poor productivity, and the need for a larger aging room, resulting in increased costs for equipment, utilities, etc., which is a major problem.
  • volatile solvents VOCs
  • VOCs volatile solvents
  • Patent Documents 1 to 4 To address the above-mentioned problems, a number of active energy ray-curable adhesives have been proposed, as shown in Patent Documents 1 to 4. These use prepolymers that have radically polymerizable unsaturated bonds in their molecules, and when irradiated with active energy rays, radical polymerization proceeds and instantly cures, but linear polyurethane resins that do not participate in radical polymerization are also used. Since it is contained in a large amount, it does not have the multifaceted performance of two-component urethane adhesives.
  • an adhesive has been proposed that uses a combination of a hydroxyl group-containing radically polymerizable prepolymer, a linear polymer having hydroxyl groups at both ends, an isocyanate group-containing radically polymerizable prepolymer, and polyisocyanate. .
  • This system develops a certain degree of adhesive strength by irradiating it with active energy rays, and it is possible to perform slitting immediately after lamination, but it still takes several days to adjust the temperature to the specified temperature in order to achieve the desired performance. aging is required, which cannot be said to be sufficient in terms of productivity.
  • the active energy ray-curable adhesive is not water-soluble, it may not be possible to treat it by simple means, such as the need to use an organic solvent when cleaning the adhesive after use. .
  • the problem to be solved by the present invention is to provide an active energy ray-curable adhesive composition that has excellent adhesion without aging after adhesion, is easily available, has carbon neutrality, and has high productivity in the adhesion process. Even if it adheres to articles or equipment such as containers or jigs during the manufacturing process or usage process, it can be washed away with water that does not contain volatile organic solvents, making it an inexpensive (and highly economical) product. )
  • the present invention is as follows. 1. Contains 45.0 to 95.0% by mass of hydroxyl group-containing (meth)acrylate in all polymerizable components, An active energy ray-curable adhesive composition further comprising a resin having one or more of carboxylic acid groups, hydroxyl groups, and urethane groups and/or ethylenically unsaturated groups and having a weight average molecular weight of 500 to 100,000. thing. 2. 2.
  • the hydroxyl group-containing (meth)acrylate contains a hydroxyl group-containing poly(meth)acrylate, and the hydroxyl group-containing poly(meth)acrylate contains pentaerythritol, dipentaerythritol, glycerin, diglycerin, trimethylolpropane, and ditrimethylolpropane.
  • 8. 8 The active energy ray curable adhesive composition according to any one of 1 to 7, wherein the active energy ray curable adhesive composition has a water content of 0.01 to 5.00% by mass. 9.
  • the active energy ray-curable adhesive composition according to any one of 1 to 11 is applied to the surface of one adherend, and the other adherend is laminated on the active energy ray-curable adhesive composition layer. and then irradiating the active energy ray curable adhesive composition layer with active energy rays. 13.
  • the active energy ray-curable adhesive composition of the present invention has excellent adhesion without aging after bonding, is easily available, has carbon neutrality, has high productivity in the bonding process, and has active energy Even if it adheres to objects or equipment such as containers or jigs during the manufacturing or use process of line-curable adhesive compositions, the adhered substances can be washed away with water that does not contain volatile organic solvents. It is possible to obtain an inexpensive (excellent economic efficiency) active energy ray curable adhesive composition, a method for producing a laminate using the active energy ray curable adhesive composition, and a laminate.
  • the active energy ray-curable adhesive composition of the present invention can also be used as a laminating adhesive. At this time, an active energy ray-curable adhesive composition is applied to the surface of one adherend, the other adherend is laminated on the active energy ray-curable adhesive composition layer, and then the active energy ray-curable adhesive composition is applied to the surface of one adherend.
  • a method for producing a laminate in which the line-curable adhesive composition layer is irradiated with active energy rays can be adopted.
  • the active energy ray-curable adhesive composition of the present invention, the method for producing a laminate, and the obtained laminate will be explained in order below. Note that the active energy ray-curable adhesive composition of the present invention is sometimes simply referred to as a "composition.”
  • the active energy rays in the present invention refer to energy rays such as electron beams and ultraviolet rays that can harden acrylic monomers.
  • the active energy ray-curable adhesive composition of the present invention preferably has a surface tension value HLB (Davis method) of 8.0 or more, more preferably 8.6 or more, and still more preferably 9.0 or more. Further, it is preferably 20.0 or less, more preferably 16.0 or less, and even more preferably 14.0 or less.
  • HLB surface tension value
  • the hydroxyl value can be determined by the method specified in JIS K 0070:1992. When 1 g of sample is acetylated, the number of mg of potassium hydroxide required to neutralize the acetic acid bonded to the hydroxyl group is determined and obtained.
  • the hydroxyl value of the entire hydroxyl group-containing (meth)acrylate contained in the active energy ray-curable adhesive composition of the present invention is preferably 30 to 400 mgKOH/g, more preferably 50 mgKOH/g or more, and 100 mgKOH/g. The above is more preferable. Moreover, 350 mgKOH/g or less is more preferable, and 300 mgKOH/g or less is even more preferable.
  • the hydroxyl value of the entire polymerizable component by active energy rays is 30 mgKOH/g or more.
  • the hydroxyl group-containing (meth)acrylate contained in the composition of the present invention includes hydroxyl group-containing poly(meth)acrylate, and includes: 1. (meth)acrylic acid ester of pentaerythritol, in which one or more of the hydroxyl groups of pentaerythritol remain unreacted; 2. (meth)acrylic acid ester of polypentaerythritol in which one or more of the hydroxyl groups possessed by polypentaerythritol remain unreacted; 3. (meth)acrylic acid ester of glycerin in which one or more of the hydroxyl groups of glycerin remain unreacted; 4.
  • (meth)acrylic acid ester of polyglycerin in which one or more of the hydroxyl groups of polyglycerin remain unreacted; 5.
  • (meth)acrylic acid ester of trimethylolpropane in which one or more of the hydroxyl groups of trimethylolpropane remain unreacted; 6.
  • (meth)acrylic acid ester of polytrimethylolpropane in which one or more of the hydroxyl groups possessed by polytrimethylolpropane remains unreacted;7.
  • monohydroxyalkyl mono(meth)acrylates can be employed. Above all, 1. ⁇ 6. It is preferable to contain a hydroxyl group-containing (meth)acrylate of 7. above.
  • hydroxyl group-containing (meth)acrylate it is more preferable not to contain the hydroxyl group-containing (meth)acrylate. Furthermore, above 1. ⁇ 6.
  • hydroxyl group-containing (meth)acrylates those having two or more (meth)acryloyl groups are preferred.
  • the average molecular weight of the hydroxyl group-containing (meth)acrylate is preferably 100 to 2,000, more preferably 150 or more, and even more preferably 200 or more. Moreover, 1000 or less is more preferable, and 500 or less is still more preferable.
  • the polymerizable component contained in the composition of the present invention preferably contains hydroxyl group-containing (meth)acrylate in an amount of 45.0% by mass or more, more preferably 70.0% by mass or more, and 90.0% by mass. It is more preferable that the content is 95% by mass or more, and most preferably 95% by mass or more. Furthermore, it is not excluded that (meth)acrylates other than hydroxyl group-containing (meth)acryl
  • Examples of (meth)acrylic acid esters of pentaerythritol in which one or more of the hydroxyl groups of pentaerythritol remain unreacted include (meth)acrylates of (poly)alkylene oxide-modified pentaerythritol. ) may include acrylic acid esters, and are based on compounds formed by an ester bond of pentaerythritol and (meth)acrylic acid, such as pentaerythritol mono(meth)acrylate, pentaerythritol di(meth)acrylate, and pentaerythritol triacrylate.
  • (meth)acrylate as well as ethylene oxide modified pentaerythritol mono(meth)acrylate, ethylene oxide modified pentaerythritol di(meth)acrylate, ethylene oxide modified pentaerythritol tri(meth)acrylate, propylene oxide modified pentaerythritol mono(meth)acrylate , propylene oxide-modified pentaerythritol di(meth)acrylate, propylene oxide-modified pentaerythritol tri(meth)acrylate, and the like.
  • These hydroxyl group-containing (meth)acrylic esters of pentaerythritol may or may not be included in the composition of the present invention.
  • (Meth)acrylic acid esters of polypentaerythritol in which one or more of the hydroxyl groups possessed by polypentaerythritol remain unreacted include (poly)alkylene oxide-modified polypentaerythritol (meth)acrylic acid esters may be included, and dipentaerythritol mono(meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol mono(meth)acrylate, dipentaerythritol di(meth)acrylate, etc.
  • acrylate dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, tripentaerythritol mono(meth)acrylate, tripentaerythritol di(meth)acrylate, tripentaerythritol tri(meth)acrylate, It can contain one or more of tripentaerythritol tetra(meth)acrylate, alkylene oxide modified products (adducts) of (meth)acrylic acid esters of these polypentaerythritols, and the like.
  • (meth)acrylic acid esters of hydroxyl group-containing polypentaerythritol may or may not be included in the composition of the present invention.
  • adhesive strength may decrease when using dipentaerythritol penta(meth)acrylate, tripentaerythritol penta(meth)acrylate, tripentaerythritol hexa(meth)acrylate, and tripentaerythritol hepta(meth)acrylate, depending on the content ratio of those compounds. , adhesive strength may decrease.
  • Examples of (meth)acrylic acid esters of glycerin in which one or more of the hydroxyl groups of glycerin remain unreacted include (meth)acrylic acid of glycerin modified with (poly)alkylene oxide.
  • the basic compound is a compound formed by an ester bond of glycerin and (meth)acrylic acid, and includes glycerin mono(meth)acrylate, glycerin di(meth)acrylate, and ethylene oxide-modified glycerin mono(meth)acrylate.
  • Examples of (meth)acrylic acid esters of polyglycerin in which one or more of the hydroxyl groups of polyglycerin remain unreacted include (meth)acrylic esters of (poly)alkylene oxide-modified polyglycerin.
  • Acrylic acid ester may be included, and the basic compound is a compound formed by an ester bond of diglycerin and (meth)acrylic acid, diglycerin mono(meth)acrylate, diglycerin di(meth)acrylate, diglycerin tri(meth)acrylate ) acrylate, as well as triglycerin mono(meth)acrylate, triglycerin di(meth)acrylate, triglycerin tri(meth)acrylate, triglycerin tetra(meth)acrylate, and alkylene of (meth)acrylic esters of these polyglycerols. It can contain one or more kinds of oxide modified products (adducts) and the like. These (meth)acrylic esters of hydroxyl group-containing polyglycerin may or may not be included in the composition of the present invention.
  • (Meth)acrylic acid esters of trimethylolpropane in which one or more of the hydroxyl groups of trimethylolpropane remain unreacted include (poly)alkylene oxide-modified trimethylolpropane. may include (meth)acrylic acid esters of trimethylolpropane mono(meth)acrylate, trimethylolpropane mono(meth)acrylate, trimethylolpropane di(meth)acrylate, etc.
  • acrylate as well as ethylene oxide-modified trimethylolpropane mono(meth)acrylate, ethylene oxide-modified trimethylolpropane di(meth)acrylate, propylene oxide-modified trimethylolpropane mono(meth)acrylate, propylene oxide-modified trimethylolpropane di(meth)acrylate, ) may contain one or more types of acrylates and the like. These hydroxyl group-containing (meth)acrylic esters of trimethylolpropane may or may not be included in the composition of the present invention.
  • (Meth)acrylic acid esters of polytrimethylolpropane in which one or more of the hydroxyl groups possessed by polytrimethylolpropane remain unreacted include (poly)alkylene oxide-modified polyesters.
  • It may include (meth)acrylic acid ester of trimethylolpropane, and is based on a compound formed by an ester bond of ditrimethylolpropane and (meth)acrylic acid, such as ditrimethylolpropane mono(meth)acrylate, ditrimethylolpropane It can contain one or more of di(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, and alkylene oxide modified products (adducts) of (meth)acrylic acid esters of these polytrimethylolpropanes. These (meth)acrylic esters of hydroxyl group-containing polytrimethylolpropane may or may not be included in the composition of the present invention.
  • the monohydroxyalkyl mono(meth)acrylate contains one or more selected from alkylene glycol mono(meth)acrylate, polyalkylene glycol mono(meth)acrylate, and other hydroxyl group-containing (meth)acrylates. may be included, and may not be included.
  • Alkylene glycol mono(meth)acrylate 2-Hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl ( It can contain one or more of meth)acrylate, hydroxycyclohexyl(meth)acrylate, and the like.
  • These alkylene glycol mono(meth)acrylates may or may not be included in the composition of the present invention.
  • epoxy (meth)acrylate and 4-hydroxybutyl (meth)acrylate may not be contained.
  • polyalkylene glycol mono(meth)acrylate examples include diethylene glycol mono(meth)acrylate, dipropylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and polyethylene glycol-polypropylene glycol.
  • examples include compounds with a block structure such as mono(meth)acrylate, polyoxybutylene-polyoxypropylene mono(meth)acrylate, and compounds with a random structure such as poly(propylene glycol-tetramethylene glycol) mono(meth)acrylate. .
  • These polyalkylene glycol mono(meth)acrylates may or may not be included in the composition of the present invention.
  • hydroxyl group-containing (meth)acrylates include 4-hydroxyphenyl (meth)acrylate, 2-hydroxy-3-chloropropyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-hydroxy -3-allyloxypropyl (meth)acrylate, -2-hydroxy-3-allyloxypropyl (meth)acrylate, 2-(meth)acryloyloxyethyl-2-hydroxypropyl phthalate, 2-ethylhexyl (poly)ethylene oxide (Poly) such as modified (meth)acrylate, o-phenylphenol (poly)ethylene oxide modified (meth)acrylate, p-cumylphenol (poly)ethylene oxide modified (meth)acrylate, nonylphenol (poly)ethylene oxide modified (meth)acrylate, etc. Examples include alkylene glycol-modified (meth)acrylates. These other hydroxyl group-containing (meth)acrylates.
  • the composition of the present invention may or may not contain other compound components having double bonds.
  • Such compounds include those listed in 1. above. ⁇ 7.
  • compounds in which all of the hydroxyl groups are esterified with (meth)acrylic acid, chain alkyl (meth)acrylates, cyclic alkyl (meth)acrylates, and ether group-containing (other than the above) It can contain meth)acrylate, vinyl ether group-containing (meth)acrylate, other (meth)acrylates, and compounds having double bonds other than (meth)acrylates. Moreover, it does not need to be contained. Furthermore, above 1. ⁇ 7. In the hydroxyl group-containing (meth)acrylate described in 1. above, all of the hydroxyl groups are further esterified with (meth)acrylic acid. ⁇ 7. When synthesizing a compound, some compounds may remain as by-products.
  • the composition of the present invention includes the above 1. ⁇ 7.
  • all of the hydroxyl groups are further esterified with (meth)acrylic acid (a polyfunctional (meth)acrylate having two or more (meth)acryloyl groups and no hydroxyl group). compound) may or may not be included. However, this is limited to a range that does not impair the effects of the present invention.
  • Specific compounds include pentaerythritol tetra(meth)acrylate, glycerin tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol (100) di(meth)acrylate, (Poly)ethylene glycol di(meth)acrylate such as polyethylene glycol (400) di(meth)acrylate; (poly)propylene glycol di(meth)acrylate such as tripropylene glycol di(meth)acrylate and tetrapropylene glycol di(meth)acrylate; ) acrylate, cyclohexanedimethanol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, dimethyloloctane di(meth)acrylate, dimethylol-tricyclodecane di(meth)acrylate, 1,3-butylene glycol di( meth)acrylate, 1,4-dimethyl-2,
  • a compound having a double bond other than the hydroxyl group-containing (meth)acrylates may or may not be included.
  • mono(meth)acrylate compounds include the following chain alkyl (meth)acrylates, cyclic alkyl (meth)acrylates, ether group-containing (meth)acrylates other than the above, and vinyl ether group-containing (meth)acrylates. , other (meth)acrylates, and compounds having double bonds other than (meth)acrylates.
  • chain alkyl (meth)acrylate examples include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, t-Butyl acrylate, amyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, isooctyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, isodecyl (meth)acrylate, isomyrist
  • Cyclic alkyl (meth)acrylate Cyclic alkyl (meth)acrylates include cyclohexyl (meth)acrylate, norbornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, 1-adamantyl (meth)acrylate, 3,5 , 5-trimethylcyclohexyl acrylate, 4-t-butylcyclohexyl (meth)acrylate, benzyl (meth)acrylate, and the like.
  • ether group-containing (meth)acrylates other than those listed above examples include 1,3-butylene glycol methyl ether (meth)acrylate, methoxyethylene glycol (meth)acrylate, methoxydiethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, Ethoxyethylene glycol (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, butoxyethylene glycol (meth)acrylate, butoxydiethylene glycol (meth)acrylate, methoxypropylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate, methoxytripropylene Glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, methoxybutylene glycol (meth)acrylate, 2-(2-e
  • vinyl ether group-containing (meth)acrylates examples include 2-vinyloxyethyl (meth)acrylate, 3-vinyloxypropyl (meth)acrylate, 1-methyl-2-vinyloxyethyl (meth)acrylate, and (meth)acrylate.
  • 2-vinyloxypropyl acid 4-vinyloxybutyl (meth)acrylate, 1-methyl-3-vinyloxypropyl (meth)acrylate, 1-vinyloxymethylpropyl (meth)acrylate, (meth)acrylate 2-methyl-3-vinyloxypropyl acrylate, 3-methyl-3-vinyloxypropyl (meth)acrylate, 1,1-dimethyl-2-vinyloxyethyl (meth)acrylate, (meth)acrylic acid -3-vinyloxybutyl, (meth)acrylic acid-1-methyl-2-vinyloxypropyl, (meth)acrylic acid-2-vinyloxybutyl, (meth)acrylic acid-4-vinyloxycyclohexyl, (meth)acrylic acid-5 -vinyloxypentyl, -6-vinyloxyhexyl (meth)acrylate, -4-vinyloxymethylcyclohexylmethyl (meth)acrylate,
  • (Other (meth)acrylates) examples include benzyl (meth)acrylate, phenyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, and morpholinoethyl ( meth)acrylate, trimethylsiloxyethyl (meth)acrylate, diphenyl-2-(meth)acryloyloxyethyl phosphate, 2-(meth)acryloyloxyethyl acid phosphate, caprolactone-modified-2-(meth)acryloyloxyethyl acid phosphate, 2 -Hydroxy-1-(meth)acryloxy-3-methacryloxypropane, acryloxyethyl phthalate, 2-(meth)acryloyloxyethyl-2-hydroxyethyl phthalate, 2-(meth)acryloyloyl, 2-(
  • Compounds having double bonds other than (meth)acrylates may or may not be included in the composition of the present invention.
  • Such compounds include styrene, vinyltoluene, p-hydroxystyrene, p-chlorostyrene, p-bromostyrene, p-methylstyrene, p-methoxystyrene, pt-butoxystyrene, pt-butoxycarbonylstyrene.
  • vinylcyclopropanes 1-phenyl-2-vinylcyclopropanes, 2-phenyl-3-vinyloxiranes, 2,3-divinyloxiranes, etc.
  • cyclic ketene acetals for example, 2-methylene-1, 3-dioxepane, dioxolanes, 2-methylene-4-phenyl-1,3-dioxepane, 4,7-dimethyl-2-methylene-1,3-dioxepane, 5,6-benzo-2-methylene-1,3 -dioxepane, etc.
  • allyl glycidyl ether diallyl phthalate, triallyl trimellitate, isocyanuric acid triarylate, etc.
  • Preferred examples of such resins in the present invention include styrene acrylic oligomers, amine-modified (meth)acrylate oligomers, epoxy (meth)acrylate oligomers, polyester (meth)acrylate oligomers, and polyurethane (meth)acrylate oligomers.
  • the styrene acrylic oligomer is not particularly limited as long as it is an oligomer having at least one (meth)acryloyl group.
  • Examples of the styrene acrylic oligomer include US-1071, X-1, YS-1274, VS-1047, and RS-1191 (Seiko PMC Corporation).
  • the amine-modified (meth)acrylate oligomer is not particularly limited as long as it has at least one amino group and at least one (meth)acryloyl group.
  • the number of (meth)acryloyl groups that the amine-modified (meth)acrylate oligomer has in the molecule is not particularly limited as long as it is one or more, but it is preferably from one to six, and two or more. More preferably, the number is four or less. When the number of (meth)acryloyl groups is within the above range, the amine-modified (meth)acrylate oligomer easily reacts with the polymerizable compound.
  • the amine-modified (meth)acrylate oligomer may be a synthetic product obtained by polymerizing a desired monomer, or may be a commercially available product.
  • Examples of commercially available amine-modified (meth)acrylate oligomers include GENOMER5161, GENOMER5275 (RAHN), CN371, CN371NS, CN373, CN383, CN384, CN386, CN501, CN503, CN550, CN551 (Sartomer), and EB.
  • the epoxy (meth)acrylate oligomer is not particularly limited as long as it is an oligomer having at least one epoxy group such as bisphenol A epoxy diacrylate and at least one (meth)acryloyl group.
  • the epoxy (meth)acrylate oligomer may be a synthetic product obtained by polymerizing a desired monomer, or may be a commercially available product.
  • polyester (meth)acrylate oligomer The polyester (meth)acrylate oligomer is not particularly limited as long as it has a polyester structure and at least one (meth)acryloyl group.
  • the polyurethane (meth)acrylate oligomer is not particularly limited as long as it has a polyurethane structure and at least one (meth)acryloyl group. It may be a polyurethane (meth)acrylate oligomer, a synthetic product obtained by polymerizing a desired monomer, or a commercially available product.
  • oligomers include rosin-modified epoxy (meth)acrylate oligomers, polyether (meth)acrylate oligomers, acrylic resins with unreacted unsaturated groups, unsaturated polyethers, unsaturated polyamides, unsaturated polyurethanes, and acrylic-modified phenols.
  • resins, acrylated amine compound oligomers, etc. can be used.
  • the composition of the present invention can contain a polymerization initiator.
  • a polymerization initiator include the following acylphosphine oxide compounds, triazine compounds, aromatic ketone compounds, aromatic onium salt compounds, organic peroxides, thioxanthone compounds, thiophenyl compounds, and anthracene compounds.
  • composition of the present invention does not need to contain such a polymerization initiator.
  • the adhesive strength can be increased by not containing a polymerization initiator.
  • crosslinking and curing are performed by irradiation with ultraviolet rays, it is necessary to include such a polymerization initiator, thereby increasing the adhesive strength.
  • acylphosphine oxide type compound for example, one selected from the group consisting of 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, etc. There are more than one species.
  • triazine compounds examples include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6 -bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-pipenyl-4,6-bis(trichloromethyl)-s-triazine , 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy- naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine and 2,4-trich
  • the composition of the present invention may contain the following components such as resins, organic solvents, pigments and dyes, and other additives within a range that does not impair the effects of the present invention.
  • surface conditioners, light stabilizers, surface treatment agents, antioxidants, anti-aging agents, crosslinking accelerators, plasticizers, ultraviolet absorbers, fungicides, preservatives, antifoaming agents, humectants, etc. Can be included.
  • a siloxane compound, a wax, a fluorine-containing compound, and other components thereof may or may not be contained.
  • resin As the above-mentioned resin, one or more types can be employed from polymerizable resins having other double bonds and non-polymerizable resins having no double bonds. Moreover, it does not need to be contained.
  • Other polymerizable resins having double bonds, etc. include oligomers, and include resins or oligomers that have one or more of carboxylic acid groups, hydroxyl groups, and urethane groups, and have ethylenically unsaturated groups. Can be adopted.
  • non-polymerizable resins without double bonds examples include acrylic resins (ethylenic unsaturated monomers with carboxyl groups such as acrylic acid and methacrylic acid, and copolymerized with these ethylenically unsaturated monomers).
  • Organic solvent examples include monoalcohols, polyhydric alcohols, lower alkyl ethers of polyhydric alcohols, ketones, ethers, esters, and nitrogen-containing compounds. These may be used alone or in combination of two or more.
  • the monoalcohols include n-propanol, n-butanol, isobutanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, n-nonyl alcohol, n-decanol, or isomers thereof;
  • Examples include cyclopentanol and cyclohexanol, and preferably alcohols having an alkyl group of 1 to 6 carbon atoms can be used.
  • polyhydric alcohols examples include ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,2-pentanediol, 1,5-pentanediol, neopentyl glycol, 1,2- Hexanediol, 1,6-hexanediol, 1,2-cyclohexanediol, heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, glycerin, pentaerythritol, diethylene glycol, dipropylene Glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, polypropylene glycol, thiodiglycol, etc.
  • the lower alkyl ethers of the polyhydric alcohols mentioned above include ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol monopropyl ether, ethylene glycol isopropyl ether, ethylene glycol monobutyl ether, and ethylene glycol Isobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol-n-propyl ether, propylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono -n-butyl ether etc.
  • ketones include methyl butyl ketone, methyl isobutyl ketone, diisopropyl ketone, cyclopentanone, and cyclohexanone.
  • ethers include isopropyl ether, n-butyl ether, tetrahydrofuran, tetrahydropyran, and 1,4-dioxane.
  • esters include propylene carbonate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, amyl acetate, ethyl lactate, ethyl butyrate, dibutyl phthalate, dioctyl phthalate, and cyclic esters such as ⁇ -caprolactone and ⁇ -caprolactam. etc.
  • the content of the organic solvent is preferably as low as possible, and more preferably not included.
  • pigments and dyes In view of its intended use, it is not necessary to incorporate pigments or dyes as coloring agents into the composition of the present invention for active coloring. However, when containing pigments or dyes for purposes other than active coloring or coloring, one or more of the following pigments can be contained in any desired amount. As such pigments and dyes, known organic pigments and inorganic pigments can be used without particular limitation.
  • organic pigments include dye lake pigments, azo pigments, benzimidazolone pigments, phthalocyanine pigments, quinacridone pigments, anthraquinone pigments, dioxazine pigments, indigo pigments, thioindico pigments, perylene pigments, perinone pigments, diketopyrrolopyrrole pigments, Examples include isoindolinone-based, nitro-based, nitroso-based, anthraquinone-based, flavanthrone-based, quinophthalone-based, pyranthrone-based, and indanthrone-based pigments.
  • inorganic pigments include carbon black, titanium oxide, red iron oxide, graphite, iron black, chromium oxide green, aluminum oxide, aluminum hydroxide, and the like.
  • a known pigment dispersant may be contained together with the above pigment.
  • the layers other than the adhesive layer in the laminate of the present invention may be made of different materials or the same material, as long as at least one of the adherends can transmit the active energy rays necessary for curing.
  • two objects to be adhered are bonded and laminated using the active energy ray-curable adhesive composition of the present invention.
  • This material can be selected from papers such as synthetic paper, resin, art paper, coated paper, cast paper, laminated paper, resin-laminated paper, metal-deposited paper, metal oxide-deposited paper, and metals. These objects to be adhered may or may not be subjected to known surface treatment, chemical treatment, printing, painting, vapor deposition, etc. in advance.
  • printing or painting when printing or painting consists of an active energy ray-curable ink composition or coating composition, printing or painting is performed on at least one side of one side of the adherend without irradiation with active energy rays. , or after applying the active energy ray irradiation to a level that causes incomplete curing, apply the active energy ray curable adhesive composition of the present invention on one side, overlap the other adhered object, and then The curing may be completed by irradiating active energy rays. Further, after the layer obtained by printing or painting is completely cured by irradiating with electron beam or UV, the active energy ray-curable adhesive composition of the present invention is applied on one side.
  • the other adherend may be placed on top of the other object, and then active energy rays may be irradiated to complete curing.
  • the amount of electron beam irradiation is preferably 10 kGy or more, more preferably 100 kGy or more. Moreover, 500 kGy or less is preferable, and 300 kGy or less is more preferable. Further, when the composition contains a polymerization initiator, the amount of ultraviolet ray irradiation is preferably 400 mJ/cm 2 or more.
  • the shape of the laminate may be a sheet, a block, or the like, as long as at least one of the objects to be adhered has a shape that allows active energy rays necessary for curing to pass therethrough.
  • those made of resin may be modified or unmodified resins known for use in objects to be adhered.
  • Stretched or unstretched resins can be used as such resins, and these resins include polyolefin resins (polyethylene, polypropylene, ethylene-propylene copolymers, etc.), polyester resins (polyethylene terephthalate, polybutylene terephthalate, etc.), polyamide resins, etc.
  • Resin nylon 6, nylon 66, nylon 11, nylon 12, etc.
  • polyvinyl chloride polyvinyl acetate, polyvinyl alcohol, polystyrene, ABS resin (acrylonitrile-butadiene-styrene copolymer), polycarbonate, polyamideimide, polyimide, epoxy
  • resins such as resins, phenol resins, melamine resins, and urethane resins, laminates of these resins and the above-mentioned papers, and laminates of these resin films and metals or metal oxides.
  • the method for producing a laminate in the present invention includes applying the active energy ray-curable adhesive composition of the present invention to the surface of one adherend by a known coating method (spray coating, roll coating, solid printing, etc.). to form a coating layer.
  • the amount of the active energy ray-curable adhesive composition of the present invention applied to the object to be adhered is preferably 1.50 g/m 2 or more as a solid content in order to obtain excellent adhesive strength. , more preferably 1.80 g/m 2 or more, and still more preferably 2.00 g/m 2 or more.
  • the other adherend is placed on top of this coating layer, and the required active energy rays are irradiated from either side of the adherend to obtain the laminate of the present invention.
  • a step of heating to a constant temperature for a certain period of time there is no need for a step of heating to a constant temperature for a certain period of time as so-called aging after electron beam irradiation. Further, when irradiating ultraviolet rays as active energy rays, a step of heating to a constant temperature for a certain period of time may be provided as aging.
  • the above-mentioned paper or metal may be selected as the adherend, and in that case, adhesion with the above-mentioned resin is preferable for curing with active energy rays.
  • paper it may be either coated paper or coated paper, and is not particularly limited, such as paper with a printed layer or metal layer formed thereon, or paper formed by laminating a resin film.
  • metal film-form aluminum, zinc, copper, iron, tin, etc. are not particularly limited.
  • the laminate of the present invention can be used in the same way as the known use as a sheet having a resin layer, such as a back-printed printed matter having a printing layer between two resin sheet layers, or a laminate of two resin sheet layers.
  • Examples include surface-printed printed matter having a printed layer on the outer surface of the printed material.
  • an ink composition is printed on one side of a film such as polyethylene terephthalate by any means, and the active energy ray-curable adhesive composition of the present invention is applied onto the formed printed layer by a known coating method.
  • a film such as low density polyethylene (LLDPE) is laminated on the active energy ray curable adhesive composition layer, and then active energy rays are irradiated.
  • LLDPE low density polyethylene
  • an ink composition is printed on one side of a film such as polyethylene terephthalate by any means, and the other side of the film such as polyethylene terephthalate having a formed printed layer is cured with active energy rays of the present invention.
  • a type adhesive composition is applied by a known coating means, a film such as low density polyethylene (LLDPE) is laminated on the active energy ray-curable adhesive composition layer, and then active energy rays are irradiated. I can do it.
  • LLDPE low density polyethylene
  • the active energy ray-curable adhesive composition of the present invention may be coated on one side of a film such as polyethylene terephthalate using a known coating method, and the active energy ray-curable adhesive composition layer may be coated with low-density polyethylene (low-density polyethylene).
  • a film such as polyethylene terephthalate
  • low-density polyethylene low-density polyethylene
  • a layer can be formed by providing a cured layer of an active energy ray-curable adhesive composition on both sides of a paper or metal layer.
  • the laminate of the present invention can be used for packaging purposes.
  • any edges of the outermost thermoplastic resin layers of the two laminates may be heated and welded in close contact with each other, or any edges of the outermost surfaces of the two laminates may be bonded with adhesive. It can be made into a packaging bag or the like by adhering it using a method such as the following. Furthermore, a single laminate can be folded in half and the edges of opposing surfaces can be heat-welded or adhered as described above to make a packaging bag or the like.
  • PETA Pentaerythritol triacrylate (HLB10.9, molecular weight 298, hydroxyl value 188mgKOH/g)
  • TMPG Trimethylolpropane diacrylate (HLB8.9, molecular weight 242, hydroxyl value 232mgKOH/g)
  • GGA Glycerin diacrylate (HLB10.4, molecular weight 200, hydroxyl value 281mgKOH/g) 15EO-TMPG: 15 mole ethylene oxide modified trimethylolpropane diacrylate (HLB13.9, molecular weight 902, hydroxyl value 62mgKOH/g)
  • DPTA dipentaerythritol triacrylate (HLB13.6, molecular weight 416, hydroxyl value 135mgKOH/g) (resin)
  • X-1 Styrene acrylic resin, weight average molecular weight 18,000, acid value 110 mgKOH/g (S)
  • Example and comparative example A composition shown in Example 1 in the table below was prepared. This composition was applied onto a plain S46C original fabric in the coating amounts shown in Table 1. Without aging, an LLDPE film (TUX-HC (Mitsui Chemicals Tohcello Co., Ltd.) thickness 50 ⁇ m) (hereinafter referred to as "LLDPE film") or CPP (unoriented polypropylene) film was layered on the coated surface as a sealant. , these films were laminated by irradiating them with electron beams or ultraviolet rays at the irradiation doses shown in Table 1. The equipment used for production was washed with household detergent (weak alkaline). The cured active energy ray-curable adhesive could also be quickly removed.
  • LLDPE film TUX-HC (Mitsui Chemicals Tohcello Co., Ltd.) thickness 50 ⁇ m
  • CPP unoriented polypropylene
  • the composition was applied on plain PTM, P2161, FOR, ONM, and N1102, and an LLDPE film or CPP film was layered on each as a sealant, and active energy rays were irradiated at the dose shown in Table 1. These films were then laminated. Then, instead of plain S46C, PTM, P2161, FOR, ONM, and N1102, the composition was applied to the prints printed and cured with an EB offset ink composition, including those printed areas, and also to areas other than the printed areas. Coated. Next, without aging, an LLDPE film or a CPP film was layered as a sealant on the coated surface, and active energy rays were irradiated at the dose shown in Table 1 to stack these films.
  • Examples and Comparative Examples an electron beam irradiation device manufactured by I-Electron Beam Co., Ltd. was used, the acceleration voltage was set to 90 kV in an atmosphere with an oxygen concentration of 200 ppm, and the irradiation amount of one electron beam irradiation was basically 30 kGy. The irradiation was performed multiple times to achieve the irradiation doses shown in Table 1. Note that Examples 23 and 24 and Comparative Examples 10 and 11, which contained a polymerization initiator, were not aged and were irradiated at 400 mJ/cm 2 .
  • active energy rays can be applied to areas other than the printed areas, including those printed areas, on printed matter printed with solvent-based gravure ink and dried and solidified.
  • a curable adhesive composition was applied.
  • an LLDPE film or a CPP film was layered as a sealant on the coated surface, and active energy rays were irradiated at the dose shown in Table 1 to stack these films. This was similarly carried out for Examples 2 to 15 and Comparative Examples 1 to 13.
  • PTM as a raw material was mixed with an adhesive (polyurethane adhesive mixture (Takelac A-969V)/polyurethane adhesive (Takenate A-5) (both manufactured by Mitsui Chemicals) at a mass ratio of 3/1, and ethyl acetate was added. (adhesive diluted appropriately) was applied so that the adhesive coating amount was 2.0 g/m 2 .
  • the above LLDPE was laminated as a sealant sheet. Thereafter, a peel test was conducted using a sample heated at 40° C. for 24 hours for aging and a sample stored at 0° C. for 24 hours. Peel strength was sufficiently strong.
  • ⁇ Tensile strength> The laminate aged at 40°C for 1 day was cut into 15 mm width pieces, and the film and sealant film were separated using an Orientec Tensilon universal testing machine at an ambient temperature of 25°C and a peeling speed of 300 mm/min.
  • the tensile strength when peeled using the 180 degree peeling method was defined as the laminate strength (N/15 mm).
  • F means film breakage
  • B means peeling from the original fabric side
  • S means peeling from the sealant film side.
  • the above-mentioned peel strength and tensile strength are listed side by side.
  • 7.0F means that the peel strength is 7.0 g/15 mm and the film was broken when the tensile strength was measured.
  • the following application examples are other embodiments in which the active energy ray-curable adhesive composition of the present invention is used.
  • Application example 1 The above active energy ray-curable adhesive was applied to one side of each of plain PTM as the original fabric and LLDPE film (thickness 50 ⁇ m) as the sealant at a coating amount of 2.0 g/ m2. An adhesive layer was formed. Laminate A is created by laminating PTM and aluminum foil sandwiched between them without aging, and an active energy ray-curable adhesive layer is formed between the aluminum foil side of laminate A and the LLDPE film without aging.
  • the side surfaces were laminated together to obtain a laminate B consisting of PTM/adhesive layer/aluminum foil/adhesive layer/LLDPE film.
  • the pasting procedure may be reversed.
  • EB device electron beam irradiation device
  • an electron beam with an irradiation dose of 150 kGy and 90 kV was irradiated from the second transparent film side of the laminate B to bond it.
  • the PTM and LLDPE films adhered to each other with sufficient strength.
  • the equipment used in the production was washed with water using a household detergent (weakly alkaline), and the active energy ray-curable adhesive that had adhered to it was quickly removed.
  • the aluminum foil side of the laminate A that had been irradiated with electron beams was laminated with the LLDPE film to create a laminate B, which was then irradiated using an electron beam irradiation device (EB device) (Iwasaki Electric Co., Ltd.).
  • EB device electron beam irradiation device
  • An electron beam with an irradiation dose of 150 kGy and 90 kV was irradiated from the LLDPE film side to bond the film.
  • the PTM and LLDPE films adhered to each other with sufficient strength.
  • the equipment used in the production was washed with water using a household detergent (weakly alkaline), and the active energy ray-curable adhesive that had adhered to it was quickly removed.
  • the aluminum foil side of the laminate A that was irradiated with the electron beam was laminated with a second transparent film to create a laminate B, and the laminate B was irradiated with an irradiation dose of 150 kGy using an electron beam irradiation device (EB installation) (Iwasaki Electric Co., Ltd.).
  • EB installation electron beam irradiation device
  • 90 kV electron beam was irradiated from the second transparent film side for adhesion.
  • the PTM and LLDPE films adhered to each other with sufficient strength.
  • the equipment used in the production was washed with water using a household detergent (weakly alkaline), and the active energy ray-curable adhesive that had adhered to it was quickly removed.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
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Abstract

The present invention addresses the problem of providing: an active energy ray-curable adhesive composition that exhibits excellent adhesiveness without aging after adhesion, is readily available, is superior in carbon neutrality, has high productivity in the adhesion process, and is inexpensive (economically advantageous); a method for producing a laminate using the active energy ray-curable adhesive composition; and a laminate using the active energy ray-curable adhesive composition. As a means for solving this problem, provided is an active energy ray-curable adhesive composition that contains 45.0-95.0 mass% of a hydroxyl group-containing (meth)acrylate in the total polymerizable components, and that further contains a resin having an ethylenically unsaturated group and/or at least one among a carboxylic acid group, a hydroxyl group and a urethane group, and having a weight-average molecular weight of 500-100000.

Description

活性エネルギー線硬化型接着剤組成物Active energy ray curable adhesive composition
　本発明は、活性エネルギー線硬化型接着剤組成物に関する。 The present invention relates to an active energy ray-curable adhesive composition.
　軟包装材として広く用いられている各種積層フィルムは、ドライラミネーション、押し出しラミネーション、ホットメルトラミネーション等の方法により製造されている。これらのラミネーション方法は、いずれも接着剤層を介して、フィルム、アルミ箔、紙、布等各種基材を積層するものであり、接着剤としては、ウレタン樹脂、エポキシ樹脂、フェノール樹脂、アクリル酸エステル系樹脂、酢酸ビニル系樹脂等の様々な樹脂が使用されている。これらの接着剤の中で、特に高い接着強度及び高い耐熱性を要求されるプラスチックフィルムのラミネートにおいては、通常反応型接着剤が使用されている。反応型接着剤としては、ウレタン系のものが主流であり、この接着剤は接着剤成分のポリオールとポリイソシアネートがウレタン結合を形成し、高分子量化や架橋が起こり、硬化することにより接着するものである。
　中でも２液硬化型ウレタン系接着剤は接着後の多面的な要求性能を充たす優れたものであるが、ラミネート直後は接着強度が低く、所望の性能を得るためには４０～６０℃で２～３日間の加温エージングを必要とする。このため、ラミネート直後フィルムを加工することが出来ず生産性が悪く、更に大きなエージングルームが必要となり設備、光熱費などのコストがかかることが大きな課題である。また、接着剤溶媒として揮発性溶剤（VOC）を使用し、これらは工程内で回収するものの、作業空間やラミネート物への残存が全くのゼロになることはなく、作業環境面で好ましくない。 Various laminated films widely used as flexible packaging materials are manufactured by methods such as dry lamination, extrusion lamination, and hot melt lamination. These lamination methods all laminate various base materials such as film, aluminum foil, paper, and cloth through an adhesive layer, and adhesives include urethane resin, epoxy resin, phenol resin, and acrylic acid. Various resins are used, such as ester resins and vinyl acetate resins. Among these adhesives, reactive adhesives are usually used in laminating plastic films, which particularly require high adhesive strength and high heat resistance. The mainstream of reactive adhesives is urethane-based adhesives, in which the adhesive components polyol and polyisocyanate form a urethane bond, resulting in high molecular weight and crosslinking, which then hardens to form a bond. It is.
Among these, two-component curing urethane adhesives are excellent in meeting the multifaceted performance requirements after adhesion, but the adhesive strength is low immediately after lamination, and in order to obtain the desired performance, it is necessary to Requires heating aging for 3 days. For this reason, it is not possible to process the film immediately after lamination, resulting in poor productivity, and the need for a larger aging room, resulting in increased costs for equipment, utilities, etc., which is a major problem. In addition, volatile solvents (VOCs) are used as adhesive solvents, and although these are recovered during the process, they never remain in the work space or in the laminate, which is unfavorable in terms of the work environment.
　上記の課題に対して、特許文献１～４に示すように、数々の活性エネルギー線硬化型接着剤が提唱されている。これらは分子内にラジカル重合性不飽和結合を有するプレポリマーを用い、活性エネルギー線を照射することによりラジカル重合が進行し瞬時に硬化するものであるが、ラジカル重合に関与しない線状ポリウレタン樹脂も多く含まれているため、２液硬化型ウレタン系接着剤の様な多面的な性能を充たすものではない。また、これを改良したものとして、水酸基含有ラジカル重合性プレポリマー、両末端に水酸基を有する線状ポリマーとイソシアネート基含有ラジカル重合性プレポリマー、ポリイソシアネートを配合して用いる接着剤が提案されている。この系は活性エネルギー線を照射することである程度の接着強度が発現し、ラミネート直後にスリッティング加工が可能とあるが、所望の性能を発現するには、やはり所定の温度に調整して数日のエージングが必要であり、生産性の面では充分とは言えない。
　また、活性エネルギー線硬化型接着剤が水溶性ではない場合には、その接着剤の使用後における清掃時に有機溶媒を使用する必要がある等、簡単な手段による処理を行なうことができなかったりした。 To address the above-mentioned problems, a number of active energy ray-curable adhesives have been proposed, as shown in Patent Documents 1 to 4. These use prepolymers that have radically polymerizable unsaturated bonds in their molecules, and when irradiated with active energy rays, radical polymerization proceeds and instantly cures, but linear polyurethane resins that do not participate in radical polymerization are also used. Since it is contained in a large amount, it does not have the multifaceted performance of two-component urethane adhesives. Furthermore, as an improvement on this, an adhesive has been proposed that uses a combination of a hydroxyl group-containing radically polymerizable prepolymer, a linear polymer having hydroxyl groups at both ends, an isocyanate group-containing radically polymerizable prepolymer, and polyisocyanate. . This system develops a certain degree of adhesive strength by irradiating it with active energy rays, and it is possible to perform slitting immediately after lamination, but it still takes several days to adjust the temperature to the specified temperature in order to achieve the desired performance. aging is required, which cannot be said to be sufficient in terms of productivity.
Furthermore, if the active energy ray-curable adhesive is not water-soluble, it may not be possible to treat it by simple means, such as the need to use an organic solvent when cleaning the adhesive after use. .
特開平６－１８４４９８号公報Japanese Patent Application Publication No. 6-184498 特開２０００－１７２３５号公報Japanese Patent Application Publication No. 2000-17235 特開２０１５－１３９３５号公報Japanese Patent Application Publication No. 2015-13935 特開２０２１－１６５３２９号公報JP 2021-165329 Publication
　本発明が解決する課題は、接着後にエージングしなくとも接着性に優れ、更に入手容易性、カーボンニュートラル優位性、接着工程での高い生産性を有し、活性エネルギー線硬化型接着剤組成物の製造工程や使用工程等において、容器や治具等の物品や装置に付着した場合であっても、揮発性有機溶剤を含有しない水によって、付着物を洗浄除去でき、安価な（経済性に優れる）活性エネルギー線硬化型接着剤組成物、その活性エネルギー線硬化型接着剤組成物を使用した積層体の製造方法及び積層体を得ることである。 The problem to be solved by the present invention is to provide an active energy ray-curable adhesive composition that has excellent adhesion without aging after adhesion, is easily available, has carbon neutrality, and has high productivity in the adhesion process. Even if it adheres to articles or equipment such as containers or jigs during the manufacturing process or usage process, it can be washed away with water that does not contain volatile organic solvents, making it an inexpensive (and highly economical) product. ) An active energy ray-curable adhesive composition, a method for producing a laminate using the active energy ray-curable adhesive composition, and a laminate.
　本発明者らは、上記の課題を解決するため鋭意研究した結果、特定の組成とすることにより、上記課題を解決し得ることを見出し、本発明を完成するに至った。
　すなわち、本発明は以下の通りである。
１．全重合性成分中に、水酸基含有（メタ）アクリレートを４５．０～９５．０質量％含有し、
　更にカルボン酸基、ヒドロキシル基及びウレタン基のうち１種以上、及び／又は、エチレン性不飽和基を有し、重量平均分子量が５００～１０００００の樹脂を含有する、活性エネルギー線硬化型接着剤組成物。
２．水酸基含有（メタ）アクリレートが、１分子中に（メタ）アクリロイル基を１つ以上有し、かつ１分子中に水酸基を１つ以上有する、１に記載の活性エネルギー線硬化型接着剤組成物。
３．水酸基含有（メタ）アクリレートの表面張力値（デイビス法）が８．０～２０．０である１又は２に記載の活性エネルギー線硬化型接着剤組成物。
４．水酸基含有（メタ）アクリレートの平均分子量が１００～２０００である１～３のいずれかに記載の活性エネルギー線硬化型接着剤組成物。
５．水酸基含有（メタ）アクリレートの水酸基価が３０～４００ｍｇＫＯＨ／ｇである１～４のいずれかに記載の活性エネルギー線硬化型接着剤組成物。
６．活性エネルギー線による重合性成分全体の水酸基価が３０ｍｇＫＯＨ／ｇ以上である１～５のいずれかに記載の活性エネルギー線硬化型接着剤組成物。
７．水酸基含有（メタ）アクリレートが、水酸基含有ポリ（メタ）アクリレートを含有し、その水酸基含有ポリ（メタ）アクリレートが、ペンタエリスリトール、ジペンタエリスリトール、グリセリン、ジグリセリン、トリメチロールプロパン、及びジトリメチロールプロパンの１種以上の化合物と、（メタ）アクリル酸が、エステル結合してなる化合物である１～６のいずれかに記載の活性エネルギー線硬化型接着剤組成物。
８．活性エネルギー線硬化型接着剤組成物の含水率が０．０１～５．００質量％である１～７のいずれかに記載の活性エネルギー線硬化型接着剤組成物。
９．水酸基含有ポリ（メタ）アクリレートが、１分子あたり２～４の（メタ）アクリロイル基を有する化合物である１～８のいずれかに記載の活性エネルギー線硬化型接着剤組成物。
１０．水酸基含有ポリ（メタ）アクリレートが、ペンタエリスリトールジ（メタ）アクリレート、及び／又はペンタエリスリトールトリ（メタ）アクリレートを含有する７～９のいずれかに記載の活性エネルギー線硬化型接着剤組成物。
１１．１０～５００ｋＧｙの活性エネルギー線で硬化可能な１～１０のいずれかに記載の活性エネルギー線硬化型接着剤組成物。
１２．一方の被接着物表面に１～１１のいずれかに記載の活性エネルギー線硬化型接着剤組成物を塗布し、その活性エネルギー線硬化型接着剤組成物層の上に他方の被接着物を積層し、次いで、活性エネルギー線硬化型接着剤組成物層に活性エネルギー線を照射する積層体の製造方法。
１３．１～１１のいずれかに記載の活性エネルギー線硬化型接着剤組成物により形成された活性エネルギー線硬化型接着剤層により接着された一方の被接着物層と他方の被接着剤層を有する積層体。 As a result of intensive research to solve the above-mentioned problems, the present inventors discovered that the above-mentioned problems could be solved by using a specific composition, and completed the present invention.
That is, the present invention is as follows.
1. Contains 45.0 to 95.0% by mass of hydroxyl group-containing (meth)acrylate in all polymerizable components,
An active energy ray-curable adhesive composition further comprising a resin having one or more of carboxylic acid groups, hydroxyl groups, and urethane groups and/or ethylenically unsaturated groups and having a weight average molecular weight of 500 to 100,000. thing.
2. 2. The active energy ray-curable adhesive composition according to 1, wherein the hydroxyl group-containing (meth)acrylate has one or more (meth)acryloyl groups in one molecule and one or more hydroxyl groups in one molecule.
3. 3. The active energy ray-curable adhesive composition according to 1 or 2, wherein the hydroxyl group-containing (meth)acrylate has a surface tension value (Davis method) of 8.0 to 20.0.
4. 4. The active energy ray-curable adhesive composition according to any one of 1 to 3, wherein the hydroxyl group-containing (meth)acrylate has an average molecular weight of 100 to 2,000.
5. 5. The active energy ray-curable adhesive composition according to any one of 1 to 4, wherein the hydroxyl group-containing (meth)acrylate has a hydroxyl value of 30 to 400 mgKOH/g.
6. 6. The active energy ray-curable adhesive composition according to any one of 1 to 5, wherein the hydroxyl value of the entire polymerizable component by active energy rays is 30 mgKOH/g or more.
7. The hydroxyl group-containing (meth)acrylate contains a hydroxyl group-containing poly(meth)acrylate, and the hydroxyl group-containing poly(meth)acrylate contains pentaerythritol, dipentaerythritol, glycerin, diglycerin, trimethylolpropane, and ditrimethylolpropane. 7. The active energy ray-curable adhesive composition according to any one of 1 to 6, which is a compound formed by an ester bond between one or more compounds and (meth)acrylic acid.
8. 8. The active energy ray curable adhesive composition according to any one of 1 to 7, wherein the active energy ray curable adhesive composition has a water content of 0.01 to 5.00% by mass.
9. 9. The active energy ray-curable adhesive composition according to any one of 1 to 8, wherein the hydroxyl group-containing poly(meth)acrylate is a compound having 2 to 4 (meth)acryloyl groups per molecule.
10. 10. The active energy ray-curable adhesive composition according to any one of 7 to 9, wherein the hydroxyl group-containing poly(meth)acrylate contains pentaerythritol di(meth)acrylate and/or pentaerythritol tri(meth)acrylate.
11. The active energy ray-curable adhesive composition according to any one of 1 to 10, which is curable with active energy rays of 10 to 500 kGy.
12. The active energy ray-curable adhesive composition according to any one of 1 to 11 is applied to the surface of one adherend, and the other adherend is laminated on the active energy ray-curable adhesive composition layer. and then irradiating the active energy ray curable adhesive composition layer with active energy rays.
13. One adherend layer and the other adherend layer bonded by an active energy ray curable adhesive layer formed from the active energy ray curable adhesive composition according to any one of 1 to 11. Laminated body with.
　本発明の活性エネルギー線硬化型接着剤組成物によれば、接着後にエージングしなくとも接着性に優れ、更に入手容易性、カーボンニュートラル優位性、接着工程での高い生産性を有し、活性エネルギー線硬化型接着剤組成物の製造工程や使用工程等において、容器や治具等の物品や装置に付着した場合であっても、揮発性有機溶剤を含有しない水によって、付着物を洗浄除去でき、安価な（経済性に優れる）活性エネルギー線硬化型接着剤組成物、その活性エネルギー線硬化型接着剤組成物を使用した積層体の製造方法及び積層体を得ることができる。 According to the active energy ray-curable adhesive composition of the present invention, it has excellent adhesion without aging after bonding, is easily available, has carbon neutrality, has high productivity in the bonding process, and has active energy Even if it adheres to objects or equipment such as containers or jigs during the manufacturing or use process of line-curable adhesive compositions, the adhered substances can be washed away with water that does not contain volatile organic solvents. It is possible to obtain an inexpensive (excellent economic efficiency) active energy ray curable adhesive composition, a method for producing a laminate using the active energy ray curable adhesive composition, and a laminate.
　本発明の活性エネルギー線硬化型接着剤組成物は、ラミネート用接着剤としても使用できる。このときには、一方の被接着物表面に活性エネルギー線硬化型接着剤組成物を塗布し、その活性エネルギー線硬化型接着剤組成物層の上に他方の被接着物を積層し、次いで、活性エネルギー線硬化型接着剤組成物層に活性エネルギー線を照射する積層体の製造方法を採用できる。本発明の活性エネルギー線硬化型接着剤組成物、積層体の製造方法、及び得られた積層体について、以下に順に説明する。なお、本発明の活性エネルギー線硬化型接着剤組成物を、単に「組成物」というときがある。そして、本発明における活性エネルギー線とは、電子線や紫外線等のアクリル系モノマー等を硬化させることができるエネルギー線を示す。 The active energy ray-curable adhesive composition of the present invention can also be used as a laminating adhesive. At this time, an active energy ray-curable adhesive composition is applied to the surface of one adherend, the other adherend is laminated on the active energy ray-curable adhesive composition layer, and then the active energy ray-curable adhesive composition is applied to the surface of one adherend. A method for producing a laminate in which the line-curable adhesive composition layer is irradiated with active energy rays can be adopted. The active energy ray-curable adhesive composition of the present invention, the method for producing a laminate, and the obtained laminate will be explained in order below. Note that the active energy ray-curable adhesive composition of the present invention is sometimes simply referred to as a "composition." The active energy rays in the present invention refer to energy rays such as electron beams and ultraviolet rays that can harden acrylic monomers.
＜表面張力値（デイビス法）＞
　本発明の活性エネルギー線硬化型接着剤組成物は、表面張力値ＨＬＢ（デイビス法）は８．０以上が好ましく、８．６以上がより好ましく、９．０以上が更に好ましい。また２０．０以下が好ましく、１６．０以下がより好ましく、１４．０以下が更に好ましい。
　デイビス法により表面張力値を求めるにあたり、予め定められている官能基毎の基数に基づき、ＨＬＢ値＝７＋Σ（親水基の基数）＋Σ（親油基の基数）により求めた。 <Surface tension value (Davis method)>
The active energy ray-curable adhesive composition of the present invention preferably has a surface tension value HLB (Davis method) of 8.0 or more, more preferably 8.6 or more, and still more preferably 9.0 or more. Further, it is preferably 20.0 or less, more preferably 16.0 or less, and even more preferably 14.0 or less.
In determining the surface tension value by the Davis method, the HLB value was determined based on the predetermined number of bases for each functional group, as follows: HLB value = 7 + Σ (number of bases of hydrophilic groups) + Σ (number of bases of lipophilic groups).
＜水酸基価＞
　水酸基価は、ＪＩＳ　Ｋ　００７０：１９９２に規定する方法により求めることができる。試料１ｇをアセチル化させたとき、水酸基と結合した酢酸を中和するのに必要とする水酸化カリウムのｍｇ数を求めて得る。本発明の活性エネルギー線硬化型接着剤組成物が含有する水酸基含有（メタ）アクリレート全体のこのような水酸基価としては３０～４００ｍｇＫＯＨ／ｇが好ましく、中でも５０ｍｇＫＯＨ／ｇ以上がより好ましく、１００ｍｇＫＯＨ／ｇ以上がさらに好ましい。また、３５０ｍｇＫＯＨ／ｇ以下がより好ましく、３００ｍｇＫＯＨ／ｇ以下がさらに好ましい。
　また、水酸基含有（メタ）アクリレート以外の活性エネルギー線による重合性成分を含有する場合、活性エネルギー線による重合性成分全体の水酸基価が３０ｍｇＫＯＨ／ｇ以上であることが好ましい。 <Hydroxyl value>
The hydroxyl value can be determined by the method specified in JIS K 0070:1992. When 1 g of sample is acetylated, the number of mg of potassium hydroxide required to neutralize the acetic acid bonded to the hydroxyl group is determined and obtained. The hydroxyl value of the entire hydroxyl group-containing (meth)acrylate contained in the active energy ray-curable adhesive composition of the present invention is preferably 30 to 400 mgKOH/g, more preferably 50 mgKOH/g or more, and 100 mgKOH/g. The above is more preferable. Moreover, 350 mgKOH/g or less is more preferable, and 300 mgKOH/g or less is even more preferable.
Further, when containing a component other than hydroxyl group-containing (meth)acrylate that is polymerizable by active energy rays, it is preferable that the hydroxyl value of the entire polymerizable component by active energy rays is 30 mgKOH/g or more.
＜水酸基含有（メタ）アクリレート＞
　本発明の組成物に含有される水酸基含有（メタ）アクリレートは、水酸基含有ポリ（メタ）アクリレートを含み、１．ペンタエリスリトールの（メタ）アクリル酸エステルであって、ペンタエリスリトールが有している水酸基のうちの１つ以上が未反応で残っているもの、２．ポリペンタエリスリトールの（メタ）アクリル酸エステルであって、ポリペンタエリスリトールが有している水酸基のうちの１つ以上が未反応で残っているもの、３．グリセリンの（メタ）アクリル酸エステルであって、グリセリンが有している水酸基のうちの１つ以上が未反応で残っているもの、４．ポリグリセリンの（メタ）アクリル酸エステルであって、ポリグリセリンが有している水酸基のうちの１つ以上が未反応で残っているもの、５．トリメチロールプロパンの（メタ）アクリル酸エステルであって、トリメチロールプロパンが有している水酸基のうちの１つ以上が未反応で残っているもの、６．ポリトリメチロールプロパンの（メタ）アクリル酸エステルであって、ポリトリメチロールプロパンが有している水酸基のうちの１つ以上が未反応で残っているもの、７．モノヒドロキシアルキルモノ（メタ）アクリレート等、から１種以上を採用できる。中でも上記１．～６．の水酸基含有（メタ）アクリレートを含有させることが好ましく、上記７．の水酸基含有（メタ）アクリレートを含有させないことがより好ましい。さらに、上記１．～６．の水酸基含有（メタ）アクリレートの中でも（メタ）アクリロイル基を２以上有するものが好ましい。
　水酸基含有（メタ）アクリレート平均分子量は１００～２０００が好ましく、中でも１５０以上がより好ましく、２００以上が更に好ましい。また１０００以下がより好ましく、５００以下が更に好ましい。
　本発明の組成物が含有する重合性成分中に、水酸基含有（メタ）アクリレートを４５．０質量％以上含有することが好ましく、７０．０質量％以上含有することがより好ましく、９０．０質量％以上含有することがさらに好ましく、９５質量％以上含有することが最も好ましい。また不純物として水酸基含有（メタ）アクリレート以外の（メタ）アクリレートを含有することを排除しない。 <Hydroxy group-containing (meth)acrylate>
The hydroxyl group-containing (meth)acrylate contained in the composition of the present invention includes hydroxyl group-containing poly(meth)acrylate, and includes: 1. (meth)acrylic acid ester of pentaerythritol, in which one or more of the hydroxyl groups of pentaerythritol remain unreacted; 2. (meth)acrylic acid ester of polypentaerythritol in which one or more of the hydroxyl groups possessed by polypentaerythritol remain unreacted; 3. (meth)acrylic acid ester of glycerin in which one or more of the hydroxyl groups of glycerin remain unreacted; 4. (meth)acrylic acid ester of polyglycerin, in which one or more of the hydroxyl groups of polyglycerin remain unreacted; 5. (meth)acrylic acid ester of trimethylolpropane, in which one or more of the hydroxyl groups of trimethylolpropane remain unreacted; 6. (meth)acrylic acid ester of polytrimethylolpropane in which one or more of the hydroxyl groups possessed by polytrimethylolpropane remains unreacted;7. One or more types of monohydroxyalkyl mono(meth)acrylates can be employed. Above all, 1. ~6. It is preferable to contain a hydroxyl group-containing (meth)acrylate of 7. above. It is more preferable not to contain the hydroxyl group-containing (meth)acrylate. Furthermore, above 1. ~6. Among the hydroxyl group-containing (meth)acrylates, those having two or more (meth)acryloyl groups are preferred.
The average molecular weight of the hydroxyl group-containing (meth)acrylate is preferably 100 to 2,000, more preferably 150 or more, and even more preferably 200 or more. Moreover, 1000 or less is more preferable, and 500 or less is still more preferable.
The polymerizable component contained in the composition of the present invention preferably contains hydroxyl group-containing (meth)acrylate in an amount of 45.0% by mass or more, more preferably 70.0% by mass or more, and 90.0% by mass. It is more preferable that the content is 95% by mass or more, and most preferably 95% by mass or more. Furthermore, it is not excluded that (meth)acrylates other than hydroxyl group-containing (meth)acrylates may be contained as impurities.
（上記１．について）
　ペンタエリスリトールの（メタ）アクリル酸エステルであって、ペンタエリスリトールが有している水酸基のうちの１つ以上が未反応で残っているものとしては、（ポリ）アルキレンオキサイド変性のペンタエリスリトールの（メタ）アクリル酸エステルを包含しても良く、ペンタエリスリトールと（メタ）アクリル酸が、エステル結合してなる化合物を基本とし、ペンタエリスリトールモノ（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、さらに、エチレンオキサイド変性ペンタエリスリトールモノ（メタ）アクリレート、エチレンオキサイド変性ペンタエリスリトールジ（メタ）アクリレート、エチレンオキサイド変性ペンタエリスリトールトリ（メタ）アクリレート、プロピレンオキサイド変性ペンタエリスリトールモノ（メタ）アクリレート、プロピレンオキサイド変性ペンタエリスリトールジ（メタ）アクリレート、プロピレンオキサイド変性ペンタエリスリトールトリ（メタ）アクリレート等から１種以上を含有できる。これらの水酸基含有ペンタエリスリトールの（メタ）アクリル酸エステルは、本発明の組成物に含有させてもよく、含有させなくてもよい。 (Regarding 1. above)
Examples of (meth)acrylic acid esters of pentaerythritol in which one or more of the hydroxyl groups of pentaerythritol remain unreacted include (meth)acrylates of (poly)alkylene oxide-modified pentaerythritol. ) may include acrylic acid esters, and are based on compounds formed by an ester bond of pentaerythritol and (meth)acrylic acid, such as pentaerythritol mono(meth)acrylate, pentaerythritol di(meth)acrylate, and pentaerythritol triacrylate. (meth)acrylate, as well as ethylene oxide modified pentaerythritol mono(meth)acrylate, ethylene oxide modified pentaerythritol di(meth)acrylate, ethylene oxide modified pentaerythritol tri(meth)acrylate, propylene oxide modified pentaerythritol mono(meth)acrylate , propylene oxide-modified pentaerythritol di(meth)acrylate, propylene oxide-modified pentaerythritol tri(meth)acrylate, and the like. These hydroxyl group-containing (meth)acrylic esters of pentaerythritol may or may not be included in the composition of the present invention.
（上記２．について）
　ポリペンタエリスリトールの（メタ）アクリル酸エステルであって、ポリペンタエリスリトールが有している水酸基のうちの１つ以上が未反応で残っているものとしては、（ポリ）アルキレンオキサイド変性のポリペンタエリスリトールの（メタ）アクリル酸エステルを包含しても良く、ジペンタエリスリトールと（メタ）アクリル酸が、エステル結合してなる化合物を基本とし、ジペンタエリスリトールモノ（メタ）アクリレート、ジペンタエリスリトールジ（メタ）アクリレート、ジ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テトラ（メタ）アクリレート、さらに、トリペンタエリスリトールモノ（メタ）アクリレート、トリペンタエリスリトールジ（メタ）アクリレート、トリペンタエリスリトールトリ（メタ）アクリレート、トリペンタエリスリトールテトラ（メタ）アクリレート、及びこれらのポリペンタエリスリトールの（メタ）アクリル酸エステルのアルキレンオキサイド変性物（付加物）等から１種以上を含有できる。これらの水酸基含有ポリペンタエリスリトールの（メタ）アクリル酸エステルは、本発明の組成物に含有させてもよく、含有させなくてもよい。
　なお、ジペンタエリスリトールペンタ（メタ）アクリレート、トリペンタエリスリトールペンタ（メタ）アクリレート、トリペンタエリスリトールヘキサ（メタ）アクリレート、及びトリペンタエリスリトールヘプタ（メタ）アクリレートを使用すると、それらの化合物の含有比率によっては、接着力が低下する可能性がある。 (Regarding 2. above)
(Meth)acrylic acid esters of polypentaerythritol in which one or more of the hydroxyl groups possessed by polypentaerythritol remain unreacted include (poly)alkylene oxide-modified polypentaerythritol (meth)acrylic acid esters may be included, and dipentaerythritol mono(meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol mono(meth)acrylate, dipentaerythritol di(meth)acrylate, etc. ) acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, tripentaerythritol mono(meth)acrylate, tripentaerythritol di(meth)acrylate, tripentaerythritol tri(meth)acrylate, It can contain one or more of tripentaerythritol tetra(meth)acrylate, alkylene oxide modified products (adducts) of (meth)acrylic acid esters of these polypentaerythritols, and the like. These (meth)acrylic acid esters of hydroxyl group-containing polypentaerythritol may or may not be included in the composition of the present invention.
In addition, when using dipentaerythritol penta(meth)acrylate, tripentaerythritol penta(meth)acrylate, tripentaerythritol hexa(meth)acrylate, and tripentaerythritol hepta(meth)acrylate, depending on the content ratio of those compounds. , adhesive strength may decrease.
（上記３．について）
　グリセリンの（メタ）アクリル酸エステルであって、グリセリンが有している水酸基のうちの１つ以上が未反応で残っているものとしては、（ポリ）アルキレンオキサイド変性のグリセリンの（メタ）アクリル酸エステルを包含しても良く、グリセリンと（メタ）アクリル酸が、エステル結合してなる化合物を基本とし、グリセリンモノ（メタ）アクリレート、グリセリンジ（メタ）アクリレート、さらに、エチレンオキサイド変性グリセリンモノ（メタ）アクリレート、エチレンオキサイド変性グリセリンジ（メタ）アクリレート、プロピレンオキサイド変性グリセリンモノ（メタ）アクリレート、プロピレンオキサイド変性グリセリンジ（メタ）アクリレート等から１種以上を含有できる。これらの水酸基含有グリセリンの（メタ）アクリル酸エステルは、本発明の組成物に含有させてもよく、含有させなくてもよい。 (Regarding 3. above)
Examples of (meth)acrylic acid esters of glycerin in which one or more of the hydroxyl groups of glycerin remain unreacted include (meth)acrylic acid of glycerin modified with (poly)alkylene oxide. The basic compound is a compound formed by an ester bond of glycerin and (meth)acrylic acid, and includes glycerin mono(meth)acrylate, glycerin di(meth)acrylate, and ethylene oxide-modified glycerin mono(meth)acrylate. ) acrylate, ethylene oxide-modified glycerin di(meth)acrylate, propylene oxide-modified glycerin mono(meth)acrylate, propylene oxide-modified glycerin di(meth)acrylate, and the like. These (meth)acrylic acid esters of hydroxyl group-containing glycerin may or may not be included in the composition of the present invention.
（上記４．について）
　ポリグリセリンの（メタ）アクリル酸エステルであって、ポリグリセリンが有している水酸基のうちの１つ以上が未反応で残っているものとしては、（ポリ）アルキレンオキサイド変性のポリグリセリンの（メタ）アクリル酸エステルを包含しても良く、ジグリセリンと（メタ）アクリル酸が、エステル結合してなる化合物を基本とし、ジグリセリンモノ（メタ）アクリレート、ジグリセリンジ（メタ）アクリレート、ジグリセリントリ（メタ）アクリレート、さらに、トリグリセリンモノ（メタ）アクリレート、トリグリセリンジ（メタ）アクリレート、トリグリセリントリ（メタ）アクリレート、トリグリセリンテトラ（メタ）アクリレート及びこれらのポリグリセリンの（メタ）アクリル酸エステルのアルキレンオキサイド変性物（付加物）等から１種以上を含有できる。
　これらの水酸基含有ポリグリセリンの（メタ）アクリル酸エステルは、本発明の組成物に含有させてもよく、含有させなくてもよい。 (Regarding 4. above)
Examples of (meth)acrylic acid esters of polyglycerin in which one or more of the hydroxyl groups of polyglycerin remain unreacted include (meth)acrylic esters of (poly)alkylene oxide-modified polyglycerin. ) Acrylic acid ester may be included, and the basic compound is a compound formed by an ester bond of diglycerin and (meth)acrylic acid, diglycerin mono(meth)acrylate, diglycerin di(meth)acrylate, diglycerin tri(meth)acrylate ) acrylate, as well as triglycerin mono(meth)acrylate, triglycerin di(meth)acrylate, triglycerin tri(meth)acrylate, triglycerin tetra(meth)acrylate, and alkylene of (meth)acrylic esters of these polyglycerols. It can contain one or more kinds of oxide modified products (adducts) and the like.
These (meth)acrylic esters of hydroxyl group-containing polyglycerin may or may not be included in the composition of the present invention.
（上記５．について）
　トリメチロールプロパンの（メタ）アクリル酸エステルであって、トリメチロールプロパンが有している水酸基のうちの１つ以上が未反応で残っているものとしては、（ポリ）アルキレンオキサイド変性のトリメチロールプロパンの（メタ）アクリル酸エステルを包含しても良く、トリメチロールプロパンと（メタ）アクリル酸が、エステル結合してなる化合物を基本とし、トリメチロールプロパンモノ（メタ）アクリレート、トリメチロールプロパンジ（メタ）アクリレート、さらに、エチレンオキサイド変性トリメチロールプロパンモノ（メタ）アクリレート、エチレンオキサイド変性トリメチロールプロパンジ（メタ）アクリレート、プロピレンオキサイド変性トリメチロールプロパンモノ（メタ）アクリレート、プロピレンオキサイド変性トリメチロールプロパンジ（メタ）アクリレート等から１種以上を含有できる。これらの水酸基含有トリメチロールプロパンの（メタ）アクリル酸エステルは、本発明の組成物に含有させてもよく、含有させなくてもよい。 (Regarding 5. above)
(Meth)acrylic acid esters of trimethylolpropane in which one or more of the hydroxyl groups of trimethylolpropane remain unreacted include (poly)alkylene oxide-modified trimethylolpropane. may include (meth)acrylic acid esters of trimethylolpropane mono(meth)acrylate, trimethylolpropane mono(meth)acrylate, trimethylolpropane di(meth)acrylate, etc. ) acrylate, as well as ethylene oxide-modified trimethylolpropane mono(meth)acrylate, ethylene oxide-modified trimethylolpropane di(meth)acrylate, propylene oxide-modified trimethylolpropane mono(meth)acrylate, propylene oxide-modified trimethylolpropane di(meth)acrylate, ) may contain one or more types of acrylates and the like. These hydroxyl group-containing (meth)acrylic esters of trimethylolpropane may or may not be included in the composition of the present invention.
（上記６．について）
　ポリトリメチロールプロパンの（メタ）アクリル酸エステルであって、ポリトリメチロールプロパンが有している水酸基のうちの１つ以上が未反応で残っているものとしては、（ポリ）アルキレンオキサイド変性のポリトリメチロールプロパンの（メタ）アクリル酸エステルを包含しても良く、ジトリメチロールプロパンと（メタ）アクリル酸が、エステル結合してなる化合物を基本とし、ジトリメチロールプロパンモノ（メタ）アクリレート、ジトリメチロールプロパンジ（メタ）アクリレート、ジトリメチロールプロパントリ（メタ）アクリレート、及びこれらのポリトリメチロールプロパンの（メタ）アクリル酸エステルのアルキレンオキサイド変性物（付加物）等から１種以上を含有できる。これらの水酸基含有ポリトリメチロールプロパンの（メタ）アクリル酸エステルは、本発明の組成物に含有させてもよく、含有させなくてもよい。 (Regarding 6. above)
(Meth)acrylic acid esters of polytrimethylolpropane in which one or more of the hydroxyl groups possessed by polytrimethylolpropane remain unreacted include (poly)alkylene oxide-modified polyesters. It may include (meth)acrylic acid ester of trimethylolpropane, and is based on a compound formed by an ester bond of ditrimethylolpropane and (meth)acrylic acid, such as ditrimethylolpropane mono(meth)acrylate, ditrimethylolpropane It can contain one or more of di(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, and alkylene oxide modified products (adducts) of (meth)acrylic acid esters of these polytrimethylolpropanes. These (meth)acrylic esters of hydroxyl group-containing polytrimethylolpropane may or may not be included in the composition of the present invention.
（上記７．について）
　モノヒドロキシアルキルモノ（メタ）アクリレートとしては、アルキレングリコ－ルモノ（メタ）アクリレート、ポリアルキレングリコ－ルモノ（メタ）アクリレート及びその他の水酸基含有（メタ）アクリレート類から選ばれた１種以上を含有しても良く、含有しなくても良い。 (Regarding 7. above)
The monohydroxyalkyl mono(meth)acrylate contains one or more selected from alkylene glycol mono(meth)acrylate, polyalkylene glycol mono(meth)acrylate, and other hydroxyl group-containing (meth)acrylates. may be included, and may not be included.
（アルキレングリコ－ルモノ（メタ）アクリレート）
　２－ヒドロキシエチル（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、２－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、３－ヒドロキシブチル（メタ）アクリレート、ヒドロキシシクロヘキシル（メタ）アクリレート等から１種以上を含有できる。これらのアルキレングリコ－ルモノ（メタ）アクリレートは、本発明の組成物に含有させてもよく、含有させなくてもよい。特にエポキシ（メタ）アクリレート及び４－ヒドロキシブチル（メタ）アクリレートは含有させなくてもよい。 (Alkylene glycol mono(meth)acrylate)
2-Hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl ( It can contain one or more of meth)acrylate, hydroxycyclohexyl(meth)acrylate, and the like. These alkylene glycol mono(meth)acrylates may or may not be included in the composition of the present invention. In particular, epoxy (meth)acrylate and 4-hydroxybutyl (meth)acrylate may not be contained.
（ポリアルキレングリコ－ルモノ（メタ）アクリレート）
　ポリアルキレングリコ－ルモノ（メタ）アクリレートとしては、ジエチレングリコールモノ（メタ）アクリレート、ジプロピレングリコールモノ（メタ）アクリレート、ポリエチレングリコールモノ（メタ）アクリレート、ポリプロピレングリコールモノ（メタ）アクリレートや、ポリエチレングリコール－ポリプロピレングリコールモノ（メタ）アクリレート、ポリオキシブチレン－ポリオキシプロピレンモノ（メタ）アクリレート等のブロック構造を有する化合物、ポリ（プロピレングリコール－テトラメチレングリコール）モノ（メタ）アクリレート等のランダム構造を有する化合物が挙げられる。これらのポリアルキレングリコ－ルモノ（メタ）アクリレートは、本発明の組成物に含有させてもよく、含有させなくてもよい。 (Polyalkylene glycol mono(meth)acrylate)
Examples of polyalkylene glycol mono(meth)acrylate include diethylene glycol mono(meth)acrylate, dipropylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and polyethylene glycol-polypropylene glycol. Examples include compounds with a block structure such as mono(meth)acrylate, polyoxybutylene-polyoxypropylene mono(meth)acrylate, and compounds with a random structure such as poly(propylene glycol-tetramethylene glycol) mono(meth)acrylate. . These polyalkylene glycol mono(meth)acrylates may or may not be included in the composition of the present invention.
（その他の水酸基含有（メタ）アクリレート類）
　その他の水酸基含有（メタ）アクリレート類としては、４－ヒドロキシフェニル（メタ）アクリレート、２－ヒドロキシ－３－クロロプロピル（メタ）アクリレート、２－ヒドロキシ－３－フェノキシプロピル（メタ）アクリレート、２－ヒドロキシ－３－アリルオキシプロピル（メタ）アクリレート、（メタ）アクリル酸－２－ヒドロキシ－３－アリルオキシプロピル、２－（メタ）アクリロイルオキシエチル－２－ヒドロキシプロピルフタレート、２－エチルヘキシル（ポリ）エチレンオキサイド変性（メタ）アクリレート、ｏ－フェニルフェノール（ポリ）エチレンオキサイド変性アクリレート、ｐ－クミルフェノール（ポリ）エチレンオキサイド変性（メタ）アクリレート、ノニルフェノール（ポリ）エチレンオキサイド変性（メタ）アクリレート等の（ポリ）アルキレングリコール変性（メタ）アクリレート類等が挙げられる。これらのその他の水酸基含有（メタ）アクリレート類は、本発明の組成物に含有させてもよく、含有させなくてもよい。 (Other hydroxyl group-containing (meth)acrylates)
Other hydroxyl group-containing (meth)acrylates include 4-hydroxyphenyl (meth)acrylate, 2-hydroxy-3-chloropropyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-hydroxy -3-allyloxypropyl (meth)acrylate, -2-hydroxy-3-allyloxypropyl (meth)acrylate, 2-(meth)acryloyloxyethyl-2-hydroxypropyl phthalate, 2-ethylhexyl (poly)ethylene oxide (Poly) such as modified (meth)acrylate, o-phenylphenol (poly)ethylene oxide modified (meth)acrylate, p-cumylphenol (poly)ethylene oxide modified (meth)acrylate, nonylphenol (poly)ethylene oxide modified (meth)acrylate, etc. Examples include alkylene glycol-modified (meth)acrylates. These other hydroxyl group-containing (meth)acrylates may or may not be included in the composition of the present invention.
＜その他の二重結合を有する化合物成分＞
　本発明の組成物には、その他の二重結合を有する化合物成分を含有させても良く、含有させなくても良い。そのような化合物としては、上記１．～７．に記載の水酸基含有（メタ）アクリレートにおいて、更に水酸基の全てが（メタ）アクリル酸によりエステル化された化合物、鎖状アルキル（メタ）アクリレート、環状アルキル（メタ）アクリレート、上記以外のエーテル基含有（メタ）アクリレート、ビニルエーテル基含有（メタ）アクリレート、その他の（メタ）アクリレート、（メタ）アクリレート類以外の二重結合を有する化合物、を含有することができる。また含有しなくても良い。更に、上記１．～７．に記載の水酸基含有（メタ）アクリレートにおいて、更に水酸基の全てが（メタ）アクリル酸によりエステル化された化合物としては、上記１．～７．の化合物を合成する際に、副生成物として得られる化合物が残っている場合のものがある。 <Other compound components having double bonds>
The composition of the present invention may or may not contain other compound components having double bonds. Such compounds include those listed in 1. above. ~7. In the hydroxyl group-containing (meth)acrylates described in , compounds in which all of the hydroxyl groups are esterified with (meth)acrylic acid, chain alkyl (meth)acrylates, cyclic alkyl (meth)acrylates, and ether group-containing (other than the above) It can contain meth)acrylate, vinyl ether group-containing (meth)acrylate, other (meth)acrylates, and compounds having double bonds other than (meth)acrylates. Moreover, it does not need to be contained. Furthermore, above 1. ~7. In the hydroxyl group-containing (meth)acrylate described in 1. above, all of the hydroxyl groups are further esterified with (meth)acrylic acid. ~7. When synthesizing a compound, some compounds may remain as by-products.
（上記１．～７．に記載の水酸基含有（メタ）アクリレートにおいて、更に水酸基の全てが（メタ）アクリル酸によりエステル化された化合物）
　本発明の組成物には、上記１．～７．に記載の水酸基含有（メタ）アクリレートにおいて、更に水酸基の全てが（メタ）アクリル酸によりエステル化された化合物（２以上の（メタ）アクリロイル基を有し、水酸基を有しない多官能（メタ）アクリレート化合物）を含有させても良く、含有させなくても良い。但し、本発明による効果を毀損しない範囲に限られる。具体的な化合物として、ペンタエリスリトールテトラ（メタ）アクリレート、グリセリントリ（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、トリエチレングリコールジ（メタ）アクリレート、ポリエチレングリコール（１００）ジ（メタ）アクリレート、ポリエチレングリコール（４００）ジ（メタ）アクリレート等の（ポリ）エチレングリコールジ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート、テトラプロピレングリコールジ（メタ）アクリレート等の（ポリ）プロピレングリコールジ（メタ）アクリレート、シクロヘキサンジメタノールジ（メタ）アクリレート、ジシクロペンタニルジ（メタ）アクリレート、ジメチロールオクタンジ（メタ）アクリレート、ジメチロール－トリシクロデカンジ（メタ）アクリレート、１，３－ブチレングリコールジ（メタ）アクリレート、１，４－ジメチル－２，４－ペンタンジオールジ（メタ）アクリレート、１，５－ジメチル－２，５－ヘキサンジオールジ（メタ）アクリレート、１，５－ペンタンジオールジ（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、１，７－ヘプタンジオールジ（メタ）アクリレート、１，８－オクタンジオールジ（メタ）アクリレート等のアルキレンジオールジ（メタ）アクリレート等が挙げられる。 (A compound in which all of the hydroxyl groups in the hydroxyl group-containing (meth)acrylates described in 1. to 7. above are further esterified with (meth)acrylic acid)
The composition of the present invention includes the above 1. ~7. In the hydroxyl group-containing (meth)acrylate described in , all of the hydroxyl groups are further esterified with (meth)acrylic acid (a polyfunctional (meth)acrylate having two or more (meth)acryloyl groups and no hydroxyl group). compound) may or may not be included. However, this is limited to a range that does not impair the effects of the present invention. Specific compounds include pentaerythritol tetra(meth)acrylate, glycerin tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol (100) di(meth)acrylate, (Poly)ethylene glycol di(meth)acrylate such as polyethylene glycol (400) di(meth)acrylate; (poly)propylene glycol di(meth)acrylate such as tripropylene glycol di(meth)acrylate and tetrapropylene glycol di(meth)acrylate; ) acrylate, cyclohexanedimethanol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, dimethyloloctane di(meth)acrylate, dimethylol-tricyclodecane di(meth)acrylate, 1,3-butylene glycol di( meth)acrylate, 1,4-dimethyl-2,4-pentanediol di(meth)acrylate, 1,5-dimethyl-2,5-hexanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate Examples include alkylene diol di(meth)acrylates such as acrylate, 1,6-hexanediol di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, and 1,8-octanediol di(meth)acrylate. .
　更に、別の水酸基含有（メタ）アクリレート類以外の二重結合を有する化合物を含有させても良く、含有させなくても良い。そのような化合物として、モノ（メタ）アクリレート化合物として、以下の、鎖状アルキル（メタ）アクリレート、環状アルキル（メタ）アクリレート、上記以外のエーテル基含有（メタ）アクリレート、ビニルエーテル基含有（メタ）アクリレート、その他の（メタ）アクリレート、（メタ）アクリレート類以外の二重結合を有する化合物等が挙げられる。 Further, a compound having a double bond other than the hydroxyl group-containing (meth)acrylates may or may not be included. As such compounds, mono(meth)acrylate compounds include the following chain alkyl (meth)acrylates, cyclic alkyl (meth)acrylates, ether group-containing (meth)acrylates other than the above, and vinyl ether group-containing (meth)acrylates. , other (meth)acrylates, and compounds having double bonds other than (meth)acrylates.
（鎖状アルキル（メタ）アクリレート）
　鎖状アルキル（メタ）アクリレートとしては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、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、ｎ－ブチル（メタ）アクリレート、ｉ－ブチル（メタ）アクリレート、ｔ－ブチルアクリレート、アミル（メタ）アクリレート、イソアミル（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、オクチル（メタ）アクリレート、デシル（メタ）アクリレート、ドデシル（メタ）アクリレート、イソオクチル（メタ）アクリレート、ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート、イソステアリル（メタ）アクリレート、イソデシル（メタ）アクリレート、イソミリスチル（メタ）アクリレート、オクタデシル（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、トリデシル（メタ）アクリレート、ノニル（メタ）アクリレート、ヘキサデシル（メタ）アクリレート、ミリスチル（メタ）アクリレート、イソボルニル（メタ）アクリレートが挙げられる。 (chain alkyl (meth)acrylate)
Examples of chain alkyl (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, t-Butyl acrylate, amyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, isooctyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, isodecyl (meth)acrylate, isomyristyl (meth)acrylate, octadecyl (meth)acrylate, dicyclopentanyl (meth)acrylate Examples include acrylate, tridecyl (meth)acrylate, nonyl (meth)acrylate, hexadecyl (meth)acrylate, myristyl (meth)acrylate, and isobornyl (meth)acrylate.
（環状アルキル（メタ）アクリレート）
　環状アルキル（メタ）アクリレートとしては、シクロヘキシル（メタ）アクリレート、ノルボルニル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、ジシクロペンテニルオキシエチル（メタ）アクリレート、１－アダマンチル（メタ）アクリレート、３，５，５－トリメチルシクロヘキシルアクリレート、４－ｔ－ブチルシクロヘキシル（メタ）アクリレート、ベンジル（メタ）アクリレート等が挙げられる。 (Cyclic alkyl (meth)acrylate)
Cyclic alkyl (meth)acrylates include cyclohexyl (meth)acrylate, norbornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, 1-adamantyl (meth)acrylate, 3,5 , 5-trimethylcyclohexyl acrylate, 4-t-butylcyclohexyl (meth)acrylate, benzyl (meth)acrylate, and the like.
（上記以外のエーテル基含有（メタ）アクリレート）
　上記以外のエーテル基含有（メタ）アクリレートとしては、１，３－ブチレングリコールメチルエーテル（メタ）アクリレート、メトキシエチレングリコール（メタ）アクリレート、メトキシジエチレングリコール（メタ）アクリレート、メトキシトリエチレングリコール（メタ）アクリレート、エトキシエチレングリコール（メタ）アクリレート、エトキシジエチレングリコール（メタ）アクリレート、ブトキシエチレングリコール（メタ）アクリレート、ブトキシジエチレングリコール（メタ）アクリレート、メトキシプロピレングリコール（メタ）アクリレート、メトキシジプロピレングリコール（メタ）アクリレート、メトキシトリプロピレングリコール（メタ）アクリレート、メトキシポリプロピレングリコール（メタ）アクリレート、エトキシジエチレングリコール（メタ）アクリレート、メトキシブチレングリコール（メタ）アクリレート、２－（２－エトキシエトキシ）エチル（メタ）アクリレート、メトキシポリエチレングリコール（メタ）アクリレート（ＥＯ繰返し単位数４００、７００等）、エチルカルビトール（メタ）アクリレート、２－エチルヘキシルカルビトール（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、クレジルポリエチレングリコール（メタ）アクリレート、（メタ）アクリル酸－２－（ビニロキシエトキシ）エチル、フェノキシエチル（メタ）アクリレート、ｐ－ノニルフェノキシエチル（メタ）アクリレート、ｐ－ノニルフェノキシポリエチレングリコール（メタ）アクリレート、グリシジル（メタ）アクリレート、フェノキシジエチレングリコール（メタ）アクリレート、フェノキシ－ポリエチレングリコール（メタ）アクリレート、ヘキサエチレングリコールモノフェニルエーテルモノ（メタ）アクリレート、アルコキシ化２－フェノキシエチル（メタ）アクリレート（エトキシ化２－フェノキシエチル（メタ）アクリレート、プロポキシ化２－フェノキシエチル（メタ）アクリレート等）、アルコキシ化ノニルフェニル（メタ）アクリレート（エトキシ化（４）ノニルフェノールアクリレート等）、２－フェノキシエチル（メタ）アクリレート、パラクミルフェノキシエチレングリコール（メタ）アクリレート、メチルフェノキシエチルアクリレート、エトキシ化コハク酸（メタ）アクリレート、エトキシ化トリブロモフェニルアクリレート、エトキシ化ノニルフェニル（メタ）アクリレート、等のアルコキシ及び又はフェノキシ系（メタ）アクリレート類等が挙げられる。 (Ether group-containing (meth)acrylates other than those listed above)
Examples of ether group-containing (meth)acrylates other than those listed above include 1,3-butylene glycol methyl ether (meth)acrylate, methoxyethylene glycol (meth)acrylate, methoxydiethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, Ethoxyethylene glycol (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, butoxyethylene glycol (meth)acrylate, butoxydiethylene glycol (meth)acrylate, methoxypropylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate, methoxytripropylene Glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, methoxybutylene glycol (meth)acrylate, 2-(2-ethoxyethoxy)ethyl (meth)acrylate, methoxypolyethylene glycol (meth)acrylate (EO repeating unit number 400, 700, etc.), ethyl carbitol (meth)acrylate, 2-ethylhexyl carbitol (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, cresyl polyethylene glycol (meth)acrylate, (meth)acrylic Acid-2-(vinyloxyethoxy)ethyl, phenoxyethyl (meth)acrylate, p-nonylphenoxyethyl (meth)acrylate, p-nonylphenoxypolyethylene glycol (meth)acrylate, glycidyl (meth)acrylate, phenoxydiethylene glycol (meth) Acrylate, Phenoxy-polyethylene glycol (meth)acrylate, Hexaethylene glycol monophenyl ether mono(meth)acrylate, Alkoxylated 2-phenoxyethyl (meth)acrylate (Ethoxylated 2-phenoxyethyl (meth)acrylate, Propoxylated 2-phenoxy ethyl (meth)acrylate, etc.), alkoxylated nonylphenyl (meth)acrylate (ethoxylated (4) nonylphenol acrylate, etc.), 2-phenoxyethyl (meth)acrylate, paracumylphenoxyethylene glycol (meth)acrylate, methylphenoxyethyl acrylate , ethoxylated succinic (meth)acrylate, ethoxylated tribromophenyl acrylate, ethoxylated nonylphenyl (meth)acrylate, and alkoxy and/or phenoxy (meth)acrylates.
（ビニルエーテル基含有（メタ）アクリレート）
　ビニルエーテル基含有（メタ）アクリレートとしては、（メタ）アクリル酸－２－ビニロキシエチル、（メタ）アクリル酸－３－ビニロキシプロピル、（メタ）アクリル酸－１－メチル－２－ビニロキシエチル、（メタ）アクリル酸－２－ビニロキシプロピル、（メタ）アクリル酸－４－ビニロキシブチル、（メタ）アクリル酸－１－メチル－３－ビニロキシプロピル、（メタ）アクリル酸－１－ビニロキシメチルプロピル、（メタ）アクリル酸－２－メチル－３－ビニロキシプロピル、（メタ）アクリル酸－３－メチル－３－ビニロキシプロピル、（メタ）アクリル酸－１，１－ジメチル－２－ビニロキシエチル、（メタ）アクリル酸－３－ビニロキシブチル、（メタ）アクリル酸－１－メチル－２－ビニロキシプロピル、（メタ）アクリル酸－２－ビニロキシブチル、（メタ）アクリル酸－４－ビニロキシシクロヘキシル、（メタ）アクリル酸－５－ビニロキシペンチル、（メタ）アクリル酸－６－ビニロキシヘキシル、（メタ）アクリル酸－４－ビニロキシメチルシクロヘキシルメチル、（メタ）アクリル酸－３－ビニロキシメチルシクロヘキシルメチル、（メタ）アクリル酸－２－ビニロキシメチルシクロヘキシルメチル、（メタ）アクリル酸－ｐ－ビニロキシメチルフェニルメチル、（メタ）アクリル酸－ｍ－ビニロキシメチルフェニルメチル、（メタ）アクリル酸－ｏ－ビニロキシメチルフェニルメチル、（メタ）アクリル酸－２－（ビニロキシイソプロポキシ）エチル、（メタ）アクリル酸－２－（ビニロキシエトキシ）プロピル、（メタ）アクリル酸－２－（ビニロキシエトキシ）イソプロピル、（メタ）アクリル酸－２－（ビニロキシイソプロポキシ）プロピル、（メタ）アクリル酸－２－（ビニロキシイソプロポキシ）イソプロピル、（メタ）アクリル酸－２－（ビニロキシエトキシエトキシ）エチル、（メタ）アクリル酸－２－（ビニロキシエトキシイソプロポキシ）エチル、（メタ）アクリル酸－２－（ビニロキシイソプロポキシエトキシ）エチル、（メタ）アクリル酸－２－（ビニロキシイソプロポキシイソプロポキシ）エチル等が挙げられる。 ((Meth)acrylate containing vinyl ether group)
Examples of vinyl ether group-containing (meth)acrylates include 2-vinyloxyethyl (meth)acrylate, 3-vinyloxypropyl (meth)acrylate, 1-methyl-2-vinyloxyethyl (meth)acrylate, and (meth)acrylate. 2-vinyloxypropyl acid, 4-vinyloxybutyl (meth)acrylate, 1-methyl-3-vinyloxypropyl (meth)acrylate, 1-vinyloxymethylpropyl (meth)acrylate, (meth)acrylate 2-methyl-3-vinyloxypropyl acrylate, 3-methyl-3-vinyloxypropyl (meth)acrylate, 1,1-dimethyl-2-vinyloxyethyl (meth)acrylate, (meth)acrylic acid -3-vinyloxybutyl, (meth)acrylic acid-1-methyl-2-vinyloxypropyl, (meth)acrylic acid-2-vinyloxybutyl, (meth)acrylic acid-4-vinyloxycyclohexyl, (meth)acrylic acid-5 -vinyloxypentyl, -6-vinyloxyhexyl (meth)acrylate, -4-vinyloxymethylcyclohexylmethyl (meth)acrylate, -3-vinyloxymethylcyclohexylmethyl (meth)acrylate, (meth)acrylic acid -2-vinyloxymethylcyclohexylmethyl, p-vinyloxymethylphenylmethyl (meth)acrylate, m-vinyloxymethylphenylmethyl (meth)acrylate, o-vinyloxymethylphenylmethyl (meth)acrylate , 2-(vinyloxyisopropoxy)ethyl (meth)acrylate, 2-(vinyloxyethoxy)propyl (meth)acrylate, 2-(vinyloxyethoxy)isopropyl (meth)acrylate, (meth) 2-(vinyloxyisopropoxy)propyl acrylate, 2-(vinyloxyisopropoxy)isopropyl (meth)acrylate, 2-(vinyloxyethoxyethoxy)ethyl (meth)acrylate, (meth)acrylic acid -2-(vinyloxyethoxyisopropoxy)ethyl, (meth)acrylic acid-2-(vinyloxyisopropoxyethoxy)ethyl, (meth)acrylic acid-2-(vinyloxyisopropoxyisopropoxy)ethyl, etc. .
（その他の（メタ）アクリレート）
　その他の（メタ）アクリレートとしては、例えば、ベンジル（メタ）アクリレート、フェニル（メタ）アクリレート、Ｎ，Ｎ－ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ－ジメチルアミノプロピル（メタ）アクリレート、モルホリノエチル（メタ）アクリレート、トリメチルシロキシエチル（メタ）アクリレート、ジフェニル－２－（メタ）アクリロイルオキシエチルホスフェート、２－（メタ）アクリロイルオキシエチルアシッドホスフェート、カプロラクトン変性－２－（メタ）アクリロイルオキシエチルアシッドホスフェート、２－ヒドロキシ－１－（メタ）アクリロキシ－３－メタクリロキシプロパン、アクリロキシエチルフタレート、２－（メタ）アクリロイロキシエチル－２－ヒドロキシエチルフタレート、２－（メタ）アクリロイロキシプロピルフタレート、トリシクロデカンモノメチロール（メタ）アクリレート、（メタ）アクリル酸ダイマー、ジエチルアミノエチル（メタ）アクリレート、２－（メタ）アクリロイロキシエチルコハク酸、２－（メタ）アクリロイロキシエチルヘキサヒドロフタル酸、２－エチルヘキシル－ジグリコール（メタ）アクリレート、アミノエチル（メタ）アクリレート、エチルカルビトールアクリレート、エチルジグリコールアクリレート、ジメチルアミノエチルアクリレートベンジルクロライド４級塩、トリブロモフェニル（メタ）アクリレート、１，４－シクロヘキサンジメタノールモノ（メタ）アクリレート、クレゾール（メタ）アクリレート、トリメチロールプロパンフォルマル（メタ）アクリレート、ネオペンチルグリコール（メタ）アクリル酸安息香酸エステル、（２－メチル－２－エチル－１，３－ジオキソラン－４－イル）メチル（メタ）アクリレート、１－（メタ）アクリロイルピペリジン－２－オン、２－（メタ）アクリル酸－１，４－ジオキサスピロ［４，５］デシ－２－イルメチル、Ｎ－（メタ）アクリロイルオキシエチルヘキサヒドロフタルイミド、γ－ブチロラクトン（メタ）アクリレート、カプロラクトン変性テトラヒドロフルフリルアクリレート、イミドアクリレート、（メタ）アクリル酸ビニル、マレイミド等が挙げられる。 (Other (meth)acrylates)
Examples of other (meth)acrylates include benzyl (meth)acrylate, phenyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, and morpholinoethyl ( meth)acrylate, trimethylsiloxyethyl (meth)acrylate, diphenyl-2-(meth)acryloyloxyethyl phosphate, 2-(meth)acryloyloxyethyl acid phosphate, caprolactone-modified-2-(meth)acryloyloxyethyl acid phosphate, 2 -Hydroxy-1-(meth)acryloxy-3-methacryloxypropane, acryloxyethyl phthalate, 2-(meth)acryloyloxyethyl-2-hydroxyethyl phthalate, 2-(meth)acryloyloxypropyl phthalate, tricyclo Decane monomethylol (meth)acrylate, (meth)acrylic acid dimer, diethylaminoethyl (meth)acrylate, 2-(meth)acryloyloxyethylsuccinic acid, 2-(meth)acryloyloxyethylhexahydrophthalic acid, 2- Ethylhexyl diglycol (meth)acrylate, aminoethyl (meth)acrylate, ethyl carbitol acrylate, ethyl diglycol acrylate, dimethylaminoethyl acrylate benzyl chloride quaternary salt, tribromophenyl (meth)acrylate, 1,4-cyclohexane di Methanol mono(meth)acrylate, cresol (meth)acrylate, trimethylolpropane formal(meth)acrylate, neopentyl glycol(meth)acrylic acid benzoate, (2-methyl-2-ethyl-1,3-dioxolane) 4-yl)methyl(meth)acrylate, 1-(meth)acryloylpiperidin-2-one, 2-(meth)acrylic acid-1,4-dioxaspiro[4,5]dec-2-ylmethyl, N-(meth)acrylate ) Acryloyloxyethylhexahydrophthalimide, γ-butyrolactone (meth)acrylate, caprolactone-modified tetrahydrofurfuryl acrylate, imide acrylate, vinyl (meth)acrylate, maleimide, and the like.
（（メタ）アクリレート類以外の二重結合を有する低分子化合物）
　（メタ）アクリレート類以外の二重結合を有する化合物は、本発明の組成物に含有させてもよく、含有させなくてもよい。
　このような化合物として、スチレン、ビニルトルエン、ｐ－ヒドロキシスチレン、ｐ－クロロスチレン、ｐ－ブロモスチレン、ｐ－メチルスチレン、ｐ－メトキシスチレン、ｐ－ｔ－ブトキシスチレン、ｐ－ｔ－ブトキシカルボニルスチレン、ｐ－ｔ－ブトキシカルボニルオキシスチレン、２，４－ジフェニル－４－メチル－１－ペンテン、ジビニルベンゼン、窒素含有化合物として、（メタ）アクリルアミド、アクリロイルモルホリン、Ｎ－ビニルホルムアミド、Ｎ－ビニルアセトアミド、Ｎ－ビニルピロリドン、Ｎ－ビニルカプロラクタム、Ｎ－ビニルカルバゾール等が挙げられる。
　その他の化合物としては、酢酸ビニル、モノクロロ酢酸ビニル、安息香酸ビニル、ピバル酸ビニル、酪酸ビニル、ラウリン酸ビニル、アジピン酸ジビニル、クロトン酸ビニル、２－エチルヘキサン酸ビニル、三員環化合物類（例えば、ビニルシクロプロパン類、１－フェニル－２－ビニルシクロプロパン類、２－フェニル－３－ビニルオキシラン類、２，３－ジビニルオキシラン類等）、環状ケテンアセタール類（例えば、２－メチレン－１，３－ジオキセパン、ジオキソラン類、２－メチレン－４－フェニル－１，３－ジオキセパン、４，７－ジメチル－２－メチレン－１，３－ジオキセパン、５，６－ベンゾ－２－メチレン－１，３－ジオキセパン等）、アリルグリシジルエーテル、ジアリルフタレート、トリアリルトリメリテート、イソシアヌル酸トリアリレート等が挙げられる。 (Low molecular compounds with double bonds other than (meth)acrylates)
Compounds having double bonds other than (meth)acrylates may or may not be included in the composition of the present invention.
Such compounds include styrene, vinyltoluene, p-hydroxystyrene, p-chlorostyrene, p-bromostyrene, p-methylstyrene, p-methoxystyrene, pt-butoxystyrene, pt-butoxycarbonylstyrene. , pt-butoxycarbonyloxystyrene, 2,4-diphenyl-4-methyl-1-pentene, divinylbenzene, nitrogen-containing compounds such as (meth)acrylamide, acryloylmorpholine, N-vinylformamide, N-vinylacetamide, Examples include N-vinylpyrrolidone, N-vinylcaprolactam, and N-vinylcarbazole.
Other compounds include vinyl acetate, monochlorovinyl acetate, vinyl benzoate, vinyl pivalate, vinyl butyrate, vinyl laurate, divinyl adipate, vinyl crotonate, vinyl 2-ethylhexanoate, three-membered ring compounds (e.g. , vinylcyclopropanes, 1-phenyl-2-vinylcyclopropanes, 2-phenyl-3-vinyloxiranes, 2,3-divinyloxiranes, etc.), cyclic ketene acetals (for example, 2-methylene-1, 3-dioxepane, dioxolanes, 2-methylene-4-phenyl-1,3-dioxepane, 4,7-dimethyl-2-methylene-1,3-dioxepane, 5,6-benzo-2-methylene-1,3 -dioxepane, etc.), allyl glycidyl ether, diallyl phthalate, triallyl trimellitate, isocyanuric acid triarylate, etc.
＜カルボン酸基、ヒドロキシル基及びウレタン基のうち１種以上を有し、及び／又は、エチレン性不飽和基を有して、重量平均分子量が５００～１０００００の樹脂＞
　本発明におけるこのような樹脂として、スチレンアクリルオリゴマー、アミン変性（メタ）アクリレートオリゴマー、エポキシ（メタ）アクリレートオリゴマー、ポリエステル（メタ）アクリレートオリゴマー、ポリウレタン（メタ）アクリレートオリゴマー等が好ましい。 <Resin having one or more of carboxylic acid groups, hydroxyl groups, and urethane groups and/or having ethylenically unsaturated groups and having a weight average molecular weight of 500 to 100,000>
Preferred examples of such resins in the present invention include styrene acrylic oligomers, amine-modified (meth)acrylate oligomers, epoxy (meth)acrylate oligomers, polyester (meth)acrylate oligomers, and polyurethane (meth)acrylate oligomers.
（スチレンアクリルオリゴマー）
　スチレンアクリルオリゴマーとしては、少なくとも１つの（メタ）アクリロイル基を有するオリゴマーであれば特に制限されない。
　スチレンアクリルオリゴマーは、例えば、ＵＳ－１０７１、Ｘ－１、ＹＳ－１２７４、ＶＳ－１０４７、ＲＳ－１１９１（星光ＰＭＣ社）が挙げられる。 (Styrene acrylic oligomer)
The styrene acrylic oligomer is not particularly limited as long as it is an oligomer having at least one (meth)acryloyl group.
Examples of the styrene acrylic oligomer include US-1071, X-1, YS-1274, VS-1047, and RS-1191 (Seiko PMC Corporation).
（アミン変性（メタ）アクリレートオリゴマー）
　アミン変性（メタ）アクリレートオリゴマーとしては、少なくとも１つのアミノ基と、少なくとも１つの（メタ）アクリロイル基を有するオリゴマーであれば特に制限されない。一方、前記アミン変性（メタ）アクリレートオリゴマーが分子中に有する（メタ）アクリロイル基の数は、１つ以上であれば特に制限されないが、１つ以上６つ以下であることが好ましく、２つ以上４つ以下であることがより好ましい。（メタ）アクリロイル基の数が上記範囲であると、アミン変性（メタ）アクリレートオリゴマーが重合性化合物と反応しやすくなる。
　前記アミン変性（メタ）アクリレートオリゴマーは、所望のモノマーを重合した合成品であってもよく、市販品であってもよい。前記アミン変性（メタ）アクリレートオリゴマーの市販品としては、例えば、ＧＥＮＯＭＥＲ５１６１、ＧＥＮＯＭＥＲ５２７５（ＲＡＨＮ社）、ＣＮ３７１、ＣＮ３７１ＮＳ、ＣＮ３７３、ＣＮ３８３、ＣＮ３８４、ＣＮ３８６、ＣＮ５０１、ＣＮ５０３、ＣＮ５５０、ＣＮ５５１（サートマー社）、ＥＢＥＣＲＹＬ８０、ＥＢＥＣＲＹＬ８１、ＥＢＥＣＲＹＬ８３、ＥＢＥＣＲＹＬ７１００、ＥＢＥＣＲＹＬ８４、ＥＢＥＣＲＹＬＰ１１５（ダイセル・オルネクス社）、Ｌａｒｏｍｅｒ　ＰＯ　８３Ｆ、Ｌａｒｏｍｅｒ　ＰＯ　８４Ｆ、Ｌａｒｏｍｅｒ　ＬＲ８９４６、Ｌａｒｏｍｅｒ　ＬＲ８９５６、Ｌａｒｏｍｅｒ ＬＲ８９９６、Ｌａｒｏｍｅｒ　ＬＲ８８９４（ＢＡＳＦ社）、ＡｇｉＳｙｎ００１、ＡｇｉＳｙｎ００２、Ａｇｉｓｙｎ００３、Ａｇｉｓｙｎ００８（ＤＳＭ　Ｃｏａｔｉｎｇ　Ｒｅｓｉｎ社）、Ｐｈｏｔｏｍｅｒ４７７１、Ｐｈｏｔｏｍｅｒ４７７５、Ｐｈｏｔｏｍｅｒ４９６７、Ｐｈｏｔｏｍｅｒ５０９６、Ｐｈｏｔｏｍｅｒ５６６２、Ｐｈｏｔｏｍｅｒ５９３０（コグニス社）、ＤｏｕｂｌｅｃｕｒｅＥＰＤ、ＤｏｕｂｌｅｃｕｒｅＯＰＤ、Ｄｏｕｂｌｅｃｕｒｅ１１５、Ｄｏｕｂｌｅｃｕｒｅ２２５、Ｄｏｕｂｌｅｃｕｒｅ６４５、ＰｏｌｙＱ２２２、ＰｏｌｙＱ２２６、ＰｏｌｙＱ２２４、ＰｏｌｙＱ１０１（ＤｏｕｂｌｅＢｏｎｄＣｈｅｍｉｃａｌｓ社）が挙げられる。なかでも、分子内に２個の光重合性官能基を有するオリゴマーが好ましく、光重合性官能基が（メタ）アクリロイル基であることがより好ましい。 (Amine-modified (meth)acrylate oligomer)
The amine-modified (meth)acrylate oligomer is not particularly limited as long as it has at least one amino group and at least one (meth)acryloyl group. On the other hand, the number of (meth)acryloyl groups that the amine-modified (meth)acrylate oligomer has in the molecule is not particularly limited as long as it is one or more, but it is preferably from one to six, and two or more. More preferably, the number is four or less. When the number of (meth)acryloyl groups is within the above range, the amine-modified (meth)acrylate oligomer easily reacts with the polymerizable compound.
The amine-modified (meth)acrylate oligomer may be a synthetic product obtained by polymerizing a desired monomer, or may be a commercially available product. Examples of commercially available amine-modified (meth)acrylate oligomers include GENOMER5161, GENOMER5275 (RAHN), CN371, CN371NS, CN373, CN383, CN384, CN386, CN501, CN503, CN550, CN551 (Sartomer), and EB. ECRYL80, EBECRYL81, EBECRYL83, EBECRYL7100, EBECRYL84, EBECRYLP115 (Daicel Allnex), Laromer PO 83F, Laromer PO 84F, Laromer LR8946, Laromer LR895 6, Laromer LR8996, Laromer LR8894 (BASF), AgiSyn001, AgiSyn002, Agisyn003, Agisyn008 (DSM Coating Resin), Photomer4771, Photomer4775, Photomer4967, Photomer5096, Photomer5662, Photomer5930 (Cognis), DoublecureEPD, DoublecureOPD, D Examples include doublecure 115, doublecure 225, doublecure 645, PolyQ222, PolyQ226, PolyQ224, and PolyQ101 (DoubleBond Chemicals). Among these, oligomers having two photopolymerizable functional groups in the molecule are preferable, and it is more preferable that the photopolymerizable functional groups are (meth)acryloyl groups.
（エポキシ（メタ）アクリレートオリゴマー）
　エポキシ（メタ）アクリレートオリゴマーとしては、ビスフェノールＡエポキシジアクリレート等の少なくとも１つのエポキシ基と、少なくとも１つの（メタ）アクリロイル基を有するオリゴマーであれば特に制限されない。エポキシ（メタ）アクリレートオリゴマーは、所望のモノマーを重合した合成品であってもよく、市販品であってもよい。例えば、ＥＢＥＣＲＹＬ６００、ＥＢＥＣＲＹＬ６０５、ＥＢＥＣＲＹＬ３６０６、ＥＢＥＣＲＹＬ３５００、ＥＢＥＣＲＹＬ８６０（ダイセル・オルネクス社）、ＣＮ１１６、ＣＮ１２０Ｂ６０、ＣＮ１２０Ｍ５０、ＣＮ１３１Ｂ、ＣＮ１３２、ＣＮ１３７、ＣＮ１５２、ＣＮ１５３、ＣＮ２１０２Ｅ、ＣＮ２００３（サートマー社）、Ｍｉｒａｍｅｒ　ＰＵ２１００、Ｍｉｒａｍｅｒ　ＰＥ２１０（ＭＩＷＯＮ社）等が挙げられる。 (Epoxy (meth)acrylate oligomer)
The epoxy (meth)acrylate oligomer is not particularly limited as long as it is an oligomer having at least one epoxy group such as bisphenol A epoxy diacrylate and at least one (meth)acryloyl group. The epoxy (meth)acrylate oligomer may be a synthetic product obtained by polymerizing a desired monomer, or may be a commercially available product. For example, EBECRYL600, EBECRYL605, EBECRYL3606, EBECRYL3500, EBECRYL860 (Daicel Allnex), CN116, CN120B60, CN120M50, CN131B, CN132, CN137, CN152, CN153 , CN2102E, CN2003 (Sartmer), Miramer PU2100, Miramer PE210 (MIWON) ) etc.
（ポリエステル（メタ）アクリレートオリゴマー）
　ポリエステル（メタ）アクリレートオリゴマーとしては、ポリエステル構造と、少なくとも１つの（メタ）アクリロイル基を有するオリゴマーであれば特に制限されない。ＥＢＥＣＲＹＬ８１１、ＥＢＥＣＲＹＬ８８４、ＥＢＥＣＲＹＬ８８５、ＥＢＥＣＲＹＬ８１２、ＥＢＥＣＲＹＬ８００、ＥＢＥＣＲＹＬ８１０、ＥＢＥＣＲＹＬ４５０、ＥＢＥＣＲＹＬ８７０、ＥＢＥＣＲＹＬ１８３０、ＯＴＡ４８０、ＰＥＴＲＡ（ダイセル・オルネクス社）や、トール油脂肪酸変性６官能ポリエステルアクリレート（例えば、ＡｇｉＳｙｎ７１６（ＤＳＭ　Ｃｏａｔｉｎｇ　Ｒｅｓｉｎ社）等）、Ｍｉｒａｍｅｒ　ＰＳ４２０（ＭＩＷＯＮ社）等が挙げられる。 (Polyester (meth)acrylate oligomer)
The polyester (meth)acrylate oligomer is not particularly limited as long as it has a polyester structure and at least one (meth)acryloyl group. EBECRYL811, EBECRYL884, EBECRYL885, EBECRYL812, EBECRYL800, EBECRYL810, EBECRYL450, EBECRYL870, EBECRYL1830, OTA480, PETRA (Daicel Allnex) , tall oil fatty acid modified hexafunctional polyester acrylate (for example, AgiSyn716 (DSM Coating Resin), etc.), Examples include Miramer PS420 (MIWON).
（ポリウレタン（メタ）アクリレートオリゴマー）
　ポリウレタン（メタ）アクリレートオリゴマーとしてはポリウレタン構造と少なくとも１つの（メタ）アクリロイル基を有するオリゴマーであれば特に制限されない。ポリウレタン（メタ）アクリレートオリゴマー、所望のモノマーを重合した合成品であってもよく、市販品であってもよい。例えば、ＥＢＥＣＲＹＬ２３０、ＥＢＥＣＲＹＬ２７０、ＥＢＥＣＲＹＬ４８５８、ＥＢＥＣＲＹＬ８４０２、ＥＢＥＣＲＹＬ８８０４、ＥＢＥＣＲＹＬ４５１３、ＥＢＥＣＲＹＬ４７３８、ＥＢＥＣＲＹＬ４７４０、ＥＢＥＣＲＹＬ８４６５、ＥＢＥＣＲＹＬ９２６０、ＥＢＥＣＲＹＬ４６６６、ＥＢＥＣＲＹＬ８２１０、ＥＢＥＣＲＹＬ８６０６、ＥＢＥＣＲＹＬ１２９０、ＥＢＥＣＲＹＬ５１２９、ＥＢＥＣＲＹＬ８３０１Ｒ、ＫＲＭ８２００、ＥＢＥＣＲＹＬ２１０、ＥＢＥＣＲＹＬ２２０等（ダイセル・オルネクス社）、Ｍｉｒａｍｅｒ　ＰＵ２１００、Ｍｉｒａｍｅｒ　ＷＳ２６００、Ｍｉｒａｍｅｒ　ＷＳ４０００（ＭＩＷＯＮ社）等が挙げられる。 (Polyurethane (meth)acrylate oligomer)
The polyurethane (meth)acrylate oligomer is not particularly limited as long as it has a polyurethane structure and at least one (meth)acryloyl group. It may be a polyurethane (meth)acrylate oligomer, a synthetic product obtained by polymerizing a desired monomer, or a commercially available product. For example, EBECRYL230, EBECRYL270, EBECRYL4858, EBECRYL8402, EBECRYL8804, EBECRYL4513, EBECRYL4738, EBECRYL4740, EBECRYL8465, EBECRYL9260, EB ECRYL4666, EBECRYL8210, EBECRYL8606, EBECRYL1290, EBECRYL5129, EBECRYL8301R, KRM8200, EBECRYL210, EBECRYL220, etc. (Daicel Allnex), Miramer PU21 00, Examples include Miramer WS2600 and Miramer WS4000 (MIWON).
　（その他のオリゴマー）
　その他のオリゴマーとして、ロジン変性エポキシ（メタ）アクリレートオリゴマー、ポリエーテル（メタ）アクリレートオリゴマー、未反応の不飽和基を備えたアクリル樹脂、不飽和ポリエーテル、不飽和ポリアミド、不飽和ポリウレタン、アクリル変性フェノール系樹脂、アクリル化アミン化合物オリゴマー等からなる群より選ばれる１種以上を用いることができる。 (Other oligomers)
Other oligomers include rosin-modified epoxy (meth)acrylate oligomers, polyether (meth)acrylate oligomers, acrylic resins with unreacted unsaturated groups, unsaturated polyethers, unsaturated polyamides, unsaturated polyurethanes, and acrylic-modified phenols. One or more types selected from the group consisting of resins, acrylated amine compound oligomers, etc. can be used.
（重合開始剤）
　本発明の組成物には重合開始剤を含有できる。その重合開始剤としては、例えば、以下の、アシルフォスフィンオキサイド系化合物、トリアジン系化合物、芳香族ケトン系化合物、芳香族オニウム塩系化合物、有機過酸化物、チオキサントン系化合物、チオフェニル系化合物、アントラセン系化合物、ヘキサアリールビスイミダゾール系化合物、ケトオキシムエステル系化合物、ボレート系化合物、アジニウム系化合物、メタロセン系化合物、活性エステル系化合物、ハロゲン化炭化水素系化合物及びアルキルアミン系化合物、ヨードニウム塩系化合物及びスルフォニウム塩系化合物等からなる群より選ばれる１種以上を用いることができる。
　但し、電子線照射により架橋・硬化を行うときには、本発明の組成物は、このような重合開始剤を含有させなくても良い。重合開始剤を含有しないほうが、接着力を高くすることができる。また紫外線照射により架橋・硬化を行うときには、このような重合開始剤を含有させることが必要であり、それによって、接着力を高くすることができる。 (Polymerization initiator)
The composition of the present invention can contain a polymerization initiator. Examples of the polymerization initiator include the following acylphosphine oxide compounds, triazine compounds, aromatic ketone compounds, aromatic onium salt compounds, organic peroxides, thioxanthone compounds, thiophenyl compounds, and anthracene compounds. -based compounds, hexaarylbisimidazole-based compounds, ketoxime ester-based compounds, borate-based compounds, azinium-based compounds, metallocene-based compounds, active ester-based compounds, halogenated hydrocarbon-based compounds and alkylamine-based compounds, iodonium salt-based compounds, and One or more types selected from the group consisting of sulfonium salt compounds and the like can be used.
However, when crosslinking and curing are performed by electron beam irradiation, the composition of the present invention does not need to contain such a polymerization initiator. The adhesive strength can be increased by not containing a polymerization initiator. Furthermore, when crosslinking and curing are performed by irradiation with ultraviolet rays, it is necessary to include such a polymerization initiator, thereby increasing the adhesive strength.
　アシルフォスフィンオキサイド系化合物としては、例えば、２，４，６－トリメチルベンゾイル－ジフェニル－フォスフィンオキサイドやビス（２，４，６－トリメチルベンゾイル）－フェニルフォスフィンオキサイド等からなる群より選ばれる１種以上が挙げられる。 As the acylphosphine oxide type compound, for example, one selected from the group consisting of 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, etc. There are more than one species.
　トリアジン系化合物としては、例えば、２，４，６－トリクロロ－ｓ－トリアジン、２－フェニル－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（ｐ－メトキシフェニル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（ｐ－トリル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－ピペニル－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２，４－ビス（トリクロロメチル）－６－スチリル－ｓ－トリアジン、２－（ナフト－１－イル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（４－メトキシ－ナフト－１－イル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２，４－トリクロロメチル－（ピペロニル）－６－トリアジン及び２，４－トリクロロメチル（４’－メトキシスチリル）－６－トリアジン等からなる群より選ばれる１種以上が挙げられる。 Examples of triazine compounds include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6 -bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-pipenyl-4,6-bis(trichloromethyl)-s-triazine , 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy- naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine and 2,4-trichloromethyl(4'-methoxystyryl)- One or more types selected from the group consisting of 6-triazine and the like can be mentioned.
　更に、例えば、ベンゾフェノン、ジエチルチオキサントン、２－メチル－１－（４－メチルチオ）フェニル－２－モルフォリノプロパン－１－オン、４－ベンゾイル－４’－メチルジフェニルサルファイド、１－クロロ－４－プロポキシチオキサントン、イソプロピルチオキサントン、２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オン、１－ヒドロキシシクロヘキシルフェニルケトン、１－［４－（２－ヒドロキシエトキシ）－フェニル］－２－ヒドロキシ－２－メチル－１－プロパン－１－オン、２，２－ジメチル－２－ヒドロキシアセトフェノン、２，２－ジメトキシ－２－フェニルアセトフェノン、２－ベンジル－２－ジメチルアミノ－１－（モルホリノフェニル）－ブタン－１－オン等からなる群より選ばれる１種以上が挙げられる。 Furthermore, for example, benzophenone, diethylthioxanthone, 2-methyl-1-(4-methylthio)phenyl-2-morpholinopropan-1-one, 4-benzoyl-4'-methyldiphenyl sulfide, 1-chloro-4-propoxy Thioxanthone, isopropylthioxanthone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenylketone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2- Methyl-1-propan-1-one, 2,2-dimethyl-2-hydroxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-benzyl-2-dimethylamino-1-(morpholinophenyl)-butane- One or more types selected from the group consisting of 1-one and the like can be mentioned.
＜その他の成分＞
　本発明の組成物は、以下の樹脂、有機溶剤、顔料及び染料、その他の添加剤等の成分を本発明による効果を毀損しない範囲において含有できる。その他に、表面調整剤、光安定化剤、表面処理剤、酸化防止剤、老化防止剤、架橋促進剤、可塑剤、紫外線吸収剤、防黴剤、防腐剤、消泡剤、保湿剤等を含有できる。また含有させなくても良い。なお、シロキサン系化合物、ワックス、ふっ素含有化合物、これらのその他の成分を含有させても良く、含有させないこともできる。 <Other ingredients>
The composition of the present invention may contain the following components such as resins, organic solvents, pigments and dyes, and other additives within a range that does not impair the effects of the present invention. In addition, surface conditioners, light stabilizers, surface treatment agents, antioxidants, anti-aging agents, crosslinking accelerators, plasticizers, ultraviolet absorbers, fungicides, preservatives, antifoaming agents, humectants, etc. Can be included. Moreover, it is not necessary to contain it. Note that a siloxane compound, a wax, a fluorine-containing compound, and other components thereof may or may not be contained.
（樹脂）
　上記の樹脂としては、その他の二重結合等を有する重合性樹脂、及び、二重結合等を有しない非重合性樹脂から１種以上を採用できる。また含有しなくても良い。
　その他の二重結合等を有する重合性樹脂はオリゴマーを含み、カルボン酸基、ヒドロキシル基及びウレタン基のうち１種以上を有し、かつ、エチレン性不飽和基を有する樹脂又はオリゴマー以外のものを採用できる。
　二重結合等を有しない非重合性樹脂としては、アクリル系樹脂（アクリル酸、メタクリル酸等のカルボキシル基を有するエチレン性不飽和単量体と、これらのエチレン性不飽和単量体と共重合可能なスチレン、２－ヒドロキシエチルアクリレート、２－ヒドロキシエチルメタクリレート、アリルアクリレート、アリルメタクリレート、ベンジルアクリレート、ベンジルメタクリレート、シクロヘキシルアクリレート、シクロヘキシルメタクリレート、グリセロールモノアクリレート、グリセロールメタクリレート、Ｎ－フェニルマレイミド、ポリスチレンマクロモノマー及びポリメチルメタクリレートマクロモノマーからなる群より選択される少なくとも１種のエチレン性不飽和単量体との共重合体）、ポリウレタン系樹脂（ヘキサメチレンジイソシアネート、２，２，４－トリメチルヘキサメチレンジイソシアネートなどの脂肪族ジイソシアネート化合物；イソホロンジイソシアネート、水添キシリレンジイソシアネートなどの脂環族ジイソシアネート化合物；キシリレンジイソシアネート、α，α，α’，α’－テトラメチルキシリレンジイソシアネートなどの芳香脂肪族ジイソシアネート化合物；トルイレンジイソシアネート、ジフェニルメタンジイソシアネートなどの芳香族ジイソシアネート化合物等のジイソシアネート化合物と、ポリエステルジオール化合物、ポリエーテルジオール化合物、ポリカーボネート化合物、ポリブタジエングリコール化合物などの高分子ジオール等のジオール化合物を反応させて得られたウレタンプレポリマーに、さらに、鎖伸長剤および反応停止剤を反応させて得られる樹脂）、その他にポリエステル系樹脂、セルロース誘導体等の公知の樹脂を配合できる。
　但し、ロジン変性ポリエステル、アクリル樹脂、ジアリルフタレート樹脂を含有してもしなくても良い。 (resin)
As the above-mentioned resin, one or more types can be employed from polymerizable resins having other double bonds and non-polymerizable resins having no double bonds. Moreover, it does not need to be contained.
Other polymerizable resins having double bonds, etc. include oligomers, and include resins or oligomers that have one or more of carboxylic acid groups, hydroxyl groups, and urethane groups, and have ethylenically unsaturated groups. Can be adopted.
Examples of non-polymerizable resins without double bonds include acrylic resins (ethylenic unsaturated monomers with carboxyl groups such as acrylic acid and methacrylic acid, and copolymerized with these ethylenically unsaturated monomers). Possible styrene, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, glycerol monoacrylate, glycerol methacrylate, N-phenylmaleimide, polystyrene macromonomer and Copolymers with at least one ethylenically unsaturated monomer selected from the group consisting of polymethyl methacrylate macromonomers), polyurethane resins (such as hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, etc.) Aliphatic diisocyanate compounds; alicyclic diisocyanate compounds such as isophorone diisocyanate and hydrogenated xylylene diisocyanate; aromatic aliphatic diisocyanate compounds such as xylylene diisocyanate and α,α,α',α'-tetramethylxylylene diisocyanate; toluylene diisocyanate; Urethane prepolymer obtained by reacting diisocyanate compounds such as aromatic diisocyanate compounds such as isocyanate and diphenylmethane diisocyanate with diol compounds such as polymeric diols such as polyester diol compounds, polyether diol compounds, polycarbonate compounds, and polybutadiene glycol compounds. In addition, known resins such as polyester resins and cellulose derivatives can be blended.
However, it may or may not contain rosin-modified polyester, acrylic resin, or diallyl phthalate resin.
（有機溶剤）
　含有させても良い有機溶剤としては、例えば、モノアルコール類、多価アルコール類、多価アルコールの低級アルキルエーテル類、ケトン類、エーテル類、エステル類、窒素含有化合物類等を挙げることができる。これらは単独で用いてもよく、２種以上を併用してもよい。
　上記モノアルコール類としては、ｎ－プロパノール、ｎ－ブタノール、イソブタノール、ｎ－ペンタノール、ｎ－ヘキサノール、ｎ－ヘプタノール、ｎ－オクタノール、ｎ－ノニルアルコール、ｎ－デカノール、又はこれらの異性体、シクロペンタノール、シクロヘキサノール等が挙げられ、好ましくはアルキル基の炭素数が１～６のアルコールを使用できる。
　上記多価アルコール類としては、エチレングリコール、プロピレングリコール、１，３－ブチレングリコール、１，４－ブチレングリコール、１，２－ペンタンジオール、１，５－ペンタンジオール、ネオペンチルグリコール、１，２－ヘキサンジオール、１，６－ヘキサンジオール、１，２－シクロヘキサンジオール、ヘプタンジオール、１，８－オクタンジオール、１，９－ノナンジオール、１，１０－デカンジオール、グリセリン、ペンタエリスリトール、ジエチレングリコール、ジプロピレングリコール、トリエチレングリコール、テトラエチレングリコール、ポリエチレングリコール、ポリプロピレングリコール、チオジグリコール等を使用できる。
　上記多価アルコールの低級アルキルエーテル類としては、エチレングリコールモノメチルエーテル、エチレングリコールジメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールジエチルエーテル、エチレングリコールモノプロピルエーテル、エチレングリコールイソプロピルエーテル、エチレングリコールモノブチルエーテル、エチレングリコールイソブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコール－ｎ－プロピルエーテル、プロピレングリコールモノブチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジプロピレングリコールモノ－ｎ－プロピルエーテル、ジプロピレングリコールモノ－ｎ－ブチルエーテル等を使用できる。
　上記ケトン類の具体例としては、メチルブチルケトン、メチルイソブチルケトン、ジイソプロピルケトン、シクロペンタノン、シクロヘキサノン等が挙げられる。
　上記エーテル類の具体例としては、イソプロピルエーテル、ｎ－ブチルエーテル、テトラヒドロフラン、テトラヒドロピラン、１，４－ジオキサン等である。
　上記エステル類としては、プロピレンカルボネート、酢酸プロピル、酢酸イソプロピル、酢酸ブチル、酢酸イソブチル、酢酸アミル、乳酸エチル、酪酸エチル、ジブチルフタレート、ジオクチルフタレート、及び、ε－カプロラクトン、ε－カプロラクタム等の環状エステル等がある。
　上記有機溶剤の含有量としては、極力少なくすることが好ましく、配合しないことがより好ましい。 (Organic solvent)
Examples of organic solvents that may be included include monoalcohols, polyhydric alcohols, lower alkyl ethers of polyhydric alcohols, ketones, ethers, esters, and nitrogen-containing compounds. These may be used alone or in combination of two or more.
The monoalcohols include n-propanol, n-butanol, isobutanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, n-nonyl alcohol, n-decanol, or isomers thereof; Examples include cyclopentanol and cyclohexanol, and preferably alcohols having an alkyl group of 1 to 6 carbon atoms can be used.
Examples of the polyhydric alcohols include ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,2-pentanediol, 1,5-pentanediol, neopentyl glycol, 1,2- Hexanediol, 1,6-hexanediol, 1,2-cyclohexanediol, heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, glycerin, pentaerythritol, diethylene glycol, dipropylene Glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, polypropylene glycol, thiodiglycol, etc. can be used.
The lower alkyl ethers of the polyhydric alcohols mentioned above include ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol monopropyl ether, ethylene glycol isopropyl ether, ethylene glycol monobutyl ether, and ethylene glycol Isobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol-n-propyl ether, propylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono -n-butyl ether etc. can be used.
Specific examples of the ketones include methyl butyl ketone, methyl isobutyl ketone, diisopropyl ketone, cyclopentanone, and cyclohexanone.
Specific examples of the above ethers include isopropyl ether, n-butyl ether, tetrahydrofuran, tetrahydropyran, and 1,4-dioxane.
The above esters include propylene carbonate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, amyl acetate, ethyl lactate, ethyl butyrate, dibutyl phthalate, dioctyl phthalate, and cyclic esters such as ε-caprolactone and ε-caprolactam. etc.
The content of the organic solvent is preferably as low as possible, and more preferably not included.
（顔料及び染料）
　本発明の組成物には、その用途からみて、積極的な着色のために着色材として顔料や染料を配合することは必要ではない。但し積極的な着色又は着色以外の目的で顔料や染料を含有させる際には、以下の顔料から１種以上を任意の含有量で含有させることができる。
　このような顔料及び染料としては、公知の有機顔料や無機顔料を特に制限なく使用できる。
　そして有機顔料としては、例えば、染料レーキ顔料、アゾ系、ベンズイミダゾロン系、フタロシアニン系、キナクリドン系、アントラキノン系、ジオキサジン系、インジゴ系、チオインジコ系、ペリレン系、ペリノン系、ジケトピロロピロール系、イソインドリノン系、ニトロ系、ニトロソ系、アンスラキノン系、フラバンスロン系、キノフタロン系、ピランスロン系、インダンスロン系の顔料等が挙げられる。無機顔料としては、カーボンブラック、酸化チタン、ベンガラ、黒鉛、鉄黒、酸化クロムグリーン、酸化アルミニウム、水酸化アルミニウム等が挙げられる。
　なお、上記顔料と共に公知の顔料分散剤を含有していてもよい。 (pigments and dyes)
In view of its intended use, it is not necessary to incorporate pigments or dyes as coloring agents into the composition of the present invention for active coloring. However, when containing pigments or dyes for purposes other than active coloring or coloring, one or more of the following pigments can be contained in any desired amount.
As such pigments and dyes, known organic pigments and inorganic pigments can be used without particular limitation.
Examples of organic pigments include dye lake pigments, azo pigments, benzimidazolone pigments, phthalocyanine pigments, quinacridone pigments, anthraquinone pigments, dioxazine pigments, indigo pigments, thioindico pigments, perylene pigments, perinone pigments, diketopyrrolopyrrole pigments, Examples include isoindolinone-based, nitro-based, nitroso-based, anthraquinone-based, flavanthrone-based, quinophthalone-based, pyranthrone-based, and indanthrone-based pigments. Examples of inorganic pigments include carbon black, titanium oxide, red iron oxide, graphite, iron black, chromium oxide green, aluminum oxide, aluminum hydroxide, and the like.
In addition, a known pigment dispersant may be contained together with the above pigment.
＜積層体及び積層体の製造方法＞
　本発明における積層体における接着剤層以外の層は、互いに異なる材料からなっても良く、同じ材料からなっても良く、少なくも一方の被接着物が硬化に必要な活性エネルギー線を透過できれば良く、２つの被接着物を、本発明の活性エネルギー線硬化型接着剤組成物によって接着して積層したものである。この材料としては合成紙、樹脂、アート紙、コート紙、キャスト紙、更紙、樹脂ラミネート紙、金属蒸着紙、金属酸化物蒸着紙等の紙及び金属等から選択できる。そしてこれらの被接着物は、予め公知の表面処理や化学的処理、印刷、塗装、蒸着等がなされていても良く、なされていなくても良い。この中で、印刷や塗装が活性エネルギー線硬化型のインキ組成物や塗料組成物からなるときには、一方の被接着物の片面の少なくとも１部に印刷又は塗装をし、活性エネルギー線を照射せず、又は硬化が不完全な状態となる程度の活性エネルギー線照射に留めた後に、片面上に本発明の活性エネルギー線硬化型接着剤組成物を塗布して他方の被接着物を重ねて、その後に活性エネルギー線を照射して硬化を完了しても良い。また該印刷又は塗装を行って得た層に対して、電子線やＵＶを照射する等して完全に硬化した後に、片面上に本発明の活性エネルギー線硬化型接着剤組成物を塗布して他方の被接着物を重ねて、その後に活性エネルギー線を照射して硬化を完了しても良い。
　電子線の照射量としては１０ｋＧｙ以上が好ましく、１００ｋＧｙ以上がより好ましい。また５００ｋＧｙ以下が好ましく、３００ｋＧｙ以下がより好ましい。また、組成物が重合開始剤を含有するとき、紫外線の照射量としては、４００ｍＪ／ｃｍ２以上が好ましい。 <Laminated body and method for manufacturing the laminate>
The layers other than the adhesive layer in the laminate of the present invention may be made of different materials or the same material, as long as at least one of the adherends can transmit the active energy rays necessary for curing. , two objects to be adhered are bonded and laminated using the active energy ray-curable adhesive composition of the present invention. This material can be selected from papers such as synthetic paper, resin, art paper, coated paper, cast paper, laminated paper, resin-laminated paper, metal-deposited paper, metal oxide-deposited paper, and metals. These objects to be adhered may or may not be subjected to known surface treatment, chemical treatment, printing, painting, vapor deposition, etc. in advance. In this case, when printing or painting consists of an active energy ray-curable ink composition or coating composition, printing or painting is performed on at least one side of one side of the adherend without irradiation with active energy rays. , or after applying the active energy ray irradiation to a level that causes incomplete curing, apply the active energy ray curable adhesive composition of the present invention on one side, overlap the other adhered object, and then The curing may be completed by irradiating active energy rays. Further, after the layer obtained by printing or painting is completely cured by irradiating with electron beam or UV, the active energy ray-curable adhesive composition of the present invention is applied on one side. The other adherend may be placed on top of the other object, and then active energy rays may be irradiated to complete curing.
The amount of electron beam irradiation is preferably 10 kGy or more, more preferably 100 kGy or more. Moreover, 500 kGy or less is preferable, and 300 kGy or less is more preferable. Further, when the composition contains a polymerization initiator, the amount of ultraviolet ray irradiation is preferably 400 mJ/cm 2 or more.
　また積層体の形状は、シート状や塊状等であり、少なくとも一方の被接着物が硬化に必要な活性エネルギー線を透過できる程度の形状であれば良い。
　このような積層体を構成する被接着物の材料のうち、樹脂からなるものとしては、被接着物用として公知の変性又は未変性の樹脂でよい。このような樹脂として延伸又は無延伸のものを使用でき、それらの樹脂としては、ポリオレフィン樹脂（ポリエチレン、ポリプロピレン、エチレン－プロピレン共重合体等）、ポリエステル樹脂（ポリエチレンテレフタレート、ポリブチレンテレフタレート等）、ポリアミド樹脂（ナイロン６、ナイロン６６、ナイロン１１、ナイロン１２等）、ポリ塩化ビニル、ポリ酢酸ビニル、ポリビニルアルコール、ポリスチレン、ＡＢＳ樹脂（アクリロニトリル－ブタジエン－スチレン共重合体）、ポリカーボネート、ポリアミドイミド、ポリイミド、エポキシ樹脂、フェノール樹脂、メラミン樹脂、ウレタン樹脂等の公知の樹脂や、これらの樹脂と上記の紙との積層体、これらの樹脂フィルムと金属や金属酸化物の積層体が挙げられる。
　本発明における積層体の製造方法としては、一方の被接着物の表面に本発明の活性エネルギー線硬化型接着剤組成物を公知の塗布手段（スプレー塗布、ロール塗布、ベタ印刷等）により塗布して塗布層を形成する。このとき、被接着物への本発明の活性エネルギー線硬化型接着剤組成物の塗布量としては、優れた接着強度を得るために、固形分の塗布量として１．５０ｇ／ｍ２以上が好ましく、１．８０ｇ／ｍ２以上がより好ましく、２．００ｇ／ｍ２以上が更に好ましい。
　次いで、この塗布層の上に、もう一方の被接着物を重ねて、いずれかの被接着物の側から必要な活性エネルギー線を照射して、本発明の積層体を得ることができる。そして、電子線を照射した後にいわゆるエージングとして、一定時間、一定の温度に加温する工程を必要としない。また、活性エネルギー線として紫外線を照射する際には、エージングとして、一定時間、一定の温度に加温等する工程を設けても良い。 The shape of the laminate may be a sheet, a block, or the like, as long as at least one of the objects to be adhered has a shape that allows active energy rays necessary for curing to pass therethrough.
Among the materials of the objects to be adhered constituting such a laminate, those made of resin may be modified or unmodified resins known for use in objects to be adhered. Stretched or unstretched resins can be used as such resins, and these resins include polyolefin resins (polyethylene, polypropylene, ethylene-propylene copolymers, etc.), polyester resins (polyethylene terephthalate, polybutylene terephthalate, etc.), polyamide resins, etc. Resin (nylon 6, nylon 66, nylon 11, nylon 12, etc.), polyvinyl chloride, polyvinyl acetate, polyvinyl alcohol, polystyrene, ABS resin (acrylonitrile-butadiene-styrene copolymer), polycarbonate, polyamideimide, polyimide, epoxy Examples include well-known resins such as resins, phenol resins, melamine resins, and urethane resins, laminates of these resins and the above-mentioned papers, and laminates of these resin films and metals or metal oxides.
The method for producing a laminate in the present invention includes applying the active energy ray-curable adhesive composition of the present invention to the surface of one adherend by a known coating method (spray coating, roll coating, solid printing, etc.). to form a coating layer. At this time, the amount of the active energy ray-curable adhesive composition of the present invention applied to the object to be adhered is preferably 1.50 g/m 2 or more as a solid content in order to obtain excellent adhesive strength. , more preferably 1.80 g/m 2 or more, and still more preferably 2.00 g/m 2 or more.
Next, the other adherend is placed on top of this coating layer, and the required active energy rays are irradiated from either side of the adherend to obtain the laminate of the present invention. Furthermore, there is no need for a step of heating to a constant temperature for a certain period of time as so-called aging after electron beam irradiation. Further, when irradiating ultraviolet rays as active energy rays, a step of heating to a constant temperature for a certain period of time may be provided as aging.
　樹脂以外のものとして、上記の紙や金属を被接着物として選択してもよく、その場合には、上記の樹脂との間で接着させることが、活性エネルギー線による硬化を行なう上で好ましい。紙の場合には塗工紙及び被塗工紙のいずれでも良く、印刷層や金属層を形成した紙、あるいは樹脂フィルムを積層させてなる紙等、特に限定されない。金属の場合には、フィルム状のアルミニウム、亜鉛、銅、鉄、スズ等特に限定されない。
　本発明の積層体の用途としては、樹脂層を有するシート状としての公知の用途と共通し、２つの樹脂シート層の間に印刷層を有する裏刷り印刷物や、２つの樹脂シート層の積層物の外面に印刷層を有する表刷り印刷物等が挙げられる。
　裏刷り印刷物としては、例えばポリエチレンテレフタレート等のフィルムの片面に、インキ組成物を任意の手段で印刷し、形成した印刷層上に本発明の活性エネルギー線硬化型接着剤組成物を公知の塗布手段で塗布し、その活性エネルギー線硬化型接着剤組成物層上に低密度ポリエチレン（ＬＬＤＰＥ）等のフィルムを積層し、次いで活性エネルギー線を照射して得ることができる。
　表刷り印刷物としては、例えばポリエチレンテレフタレート等のフィルムの片面に、インキ組成物を任意の手段で印刷し、形成した印刷層を有するポリエチレンテレフタレート等のフィルムの他面に、本発明の活性エネルギー線硬化型接着剤組成物を公知の塗布手段で塗布し、その活性エネルギー線硬化型接着剤組成物層上に低密度ポリエチレン（ＬＬＤＰＥ）等のフィルムを積層し、次いで活性エネルギー線を照射して得ることができる。また、例えばポリエチレンテレフタレート等のフィルムの片面に、本発明の活性エネルギー線硬化型接着剤組成物を公知の塗布手段で塗布し、その活性エネルギー線硬化型接着剤組成物層上に低密度ポリエチレン（ＬＬＤＰＥ）等のフィルムを積層し、次いで活性エネルギー線を照射して２つのフィルムを接着した後に、得られた積層フィルムの片面にインキ組成物を任意の手段で印刷して印刷層を形成して得ることができる。
　更に、紙や金属を積層させる際には、例えば、上記表刷り印刷物において、ポリエチレンテレフタレート等フィルムと低密度ポリエチレン等のフィルムの間にある活性エネルギー線硬化型接着剤組成物の硬化層に代えて、紙や金属層の両面に活性エネルギー線硬化型接着剤組成物の硬化層を設けてなる層を形成させることができる。 In addition to the resin, the above-mentioned paper or metal may be selected as the adherend, and in that case, adhesion with the above-mentioned resin is preferable for curing with active energy rays. In the case of paper, it may be either coated paper or coated paper, and is not particularly limited, such as paper with a printed layer or metal layer formed thereon, or paper formed by laminating a resin film. In the case of metal, film-form aluminum, zinc, copper, iron, tin, etc. are not particularly limited.
The laminate of the present invention can be used in the same way as the known use as a sheet having a resin layer, such as a back-printed printed matter having a printing layer between two resin sheet layers, or a laminate of two resin sheet layers. Examples include surface-printed printed matter having a printed layer on the outer surface of the printed material.
For back-printed printed matter, for example, an ink composition is printed on one side of a film such as polyethylene terephthalate by any means, and the active energy ray-curable adhesive composition of the present invention is applied onto the formed printed layer by a known coating method. A film such as low density polyethylene (LLDPE) is laminated on the active energy ray curable adhesive composition layer, and then active energy rays are irradiated.
For front-printed printed matter, for example, an ink composition is printed on one side of a film such as polyethylene terephthalate by any means, and the other side of the film such as polyethylene terephthalate having a formed printed layer is cured with active energy rays of the present invention. A type adhesive composition is applied by a known coating means, a film such as low density polyethylene (LLDPE) is laminated on the active energy ray-curable adhesive composition layer, and then active energy rays are irradiated. I can do it. Alternatively, the active energy ray-curable adhesive composition of the present invention may be coated on one side of a film such as polyethylene terephthalate using a known coating method, and the active energy ray-curable adhesive composition layer may be coated with low-density polyethylene (low-density polyethylene). After laminating films such as LLDPE) and then bonding the two films by irradiating active energy rays, an ink composition is printed on one side of the obtained laminated film by any means to form a printed layer. Obtainable.
Furthermore, when laminating paper or metal, for example, in the above printed matter, instead of a cured layer of an active energy ray-curable adhesive composition between a film such as polyethylene terephthalate and a film such as low density polyethylene. A layer can be formed by providing a cured layer of an active energy ray-curable adhesive composition on both sides of a paper or metal layer.
＜積層体の用途＞
　本発明の積層体は包装用途に使用できる。この場合には、２枚の積層体の最外面の熱可塑性樹脂層の任意の縁同士を密着させた状態で加熱溶着したり、２枚の積層体の最外面の任意の縁同士を接着剤等により接着させたりして包装用袋等にすることができる。また１枚の積層体を二つ折りにして、対向する面の縁同士を上記のようにして加熱溶着したり、接着したりして包装用袋等にすることができる。 <Applications of laminate>
The laminate of the present invention can be used for packaging purposes. In this case, any edges of the outermost thermoplastic resin layers of the two laminates may be heated and welded in close contact with each other, or any edges of the outermost surfaces of the two laminates may be bonded with adhesive. It can be made into a packaging bag or the like by adhering it using a method such as the following. Furthermore, a single laminate can be folded in half and the edges of opposing surfaces can be heat-welded or adhered as described above to make a packaging bag or the like.
　以下に、実施例を挙げて本発明を更に詳細に説明するが、本発明はこれらの実施例のみに限定されるものではない。なお、特に断りのない限り、「％」は「質量％」を意味し、「部」は「質量部」を意味するものである。また、表中の各材料の分量の数字についても「質量部」である。
　下記表１に記載の組成になるように、各実施例及び各比較例の活性エネルギー線硬化型接着剤組成物を調製し、その硬化について示した。なお、活性エネルギー線硬化型接着剤組成物を調製に使用した容器等の器具等を下記のアルカリ水で洗浄した。実施例１及び２の活性エネルギー線硬化型接着剤組成物の調製に使用した器具を溶解させて効率よく、かつ揮発性有機溶媒を使用せずに、好ましい環境にて洗浄できた。比較例に使用した器具に関しては、下記のアルカリ水により洗浄できず、揮発性有機溶媒を使用して洗浄した。 EXAMPLES The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to these Examples. In addition, unless otherwise specified, "%" means "% by mass" and "parts" means "parts by mass." In addition, the numbers for the quantities of each material in the table are also "parts by mass."
Active energy ray-curable adhesive compositions of each Example and each Comparative Example were prepared to have the compositions shown in Table 1 below, and their curing was shown. Note that the containers and other equipment used to prepare the active energy ray-curable adhesive composition were washed with the following alkaline water. The instruments used to prepare the active energy ray-curable adhesive compositions of Examples 1 and 2 were dissolved and cleaned efficiently in a favorable environment without using volatile organic solvents. Regarding the instruments used in the comparative example, they could not be cleaned with the alkaline water described below, but were cleaned using a volatile organic solvent.
（水酸基含有（メタ）アクリレート）
　ＰＥＴＡ：ペンタエリスリトールトリアクリレート（ＨＬＢ１０．９、分子量２９８、水酸基価１８８ｍｇＫＯＨ／ｇ）
　ＴＭＰＧ：トリメチロールプロパンジアクリレート（ＨＬＢ８．９、分子量２４２、水酸基価２３２ｍｇＫＯＨ／ｇ）
　ＧＧＡ：グリセリンジアクリレート（ＨＬＢ１０．４、分子量２００、水酸基価２８１ｍｇＫＯＨ／ｇ）
　１５ＥＯ－ＴＭＰＧ：１５モルエチレンオキサイド変性トリメチロールプロパンジアクリレート（ＨＬＢ１３．９、分子量９０２、水酸基価６２ｍｇＫＯＨ／ｇ）
　ＤＰＴＡ：ジペンタエリスリトールトリアクリレート（ＨＬＢ１３．６、分子量４１６、水酸基価１３５ｍｇＫＯＨ／ｇ）
（樹脂）
　Ｘ－１　：　スチレンアクリル樹脂、重量平均分子量１８，０００、酸価１１０ｍｇＫＯＨ／ｇ（星光ＰＭＣ社）（カルボン酸基含有）
　ＹＳ－１２７４　：　スチレンアクリル樹脂、重量平均分子量１９，０００、酸価２００ｍｇＫＯＨ／ｇ（星光ＰＭＣ社）（カルボン酸基含有）
　Ｍｉｒａｍｅｒ　ＰＵ２１００　：　２官能ウレタンアクリレート、分子量１，４００（ＭＩＷＯＮ社）
　Ｍｉｒａｍｅｒ　ＰＥ２１０　：　２官能ビスフェノールＡエポキシジアクリレート、分子量５２０（ＭＩＷＯＮ社）
　Ｍｉｒａｍｅｒ　ＰＳ４２０　：　４官能ポリエステルアクリレート、重量平均分子量３，８００（ＭＩＷＯＮ社）
（水酸基を含有しない（メタ）アクリレート）
　ＴＭＰＴＡ：トリメチロールプロパントリアクリレート（ＨＬＢ８．５、分子量２９６）
　６ＥＯ－ＴＭＰＴＡ：６モルエチレンオキサイド変性トリメチロールプロパントリアクリレート（ＨＬＢ１０．４８、分子量５６０）
　１５ＥＯ－ＴＭＰＴＡ：１５モルエチレンオキサイド変性トリメチロールプロパントリアクリレート（ＨＬＢ１３．４５、分子量９５６）
　ＧＰＴＡ：３モルＰＯ変性グリセリントリアクリレート（ＨＬＢ９．４８、分子量４２８）
　ＤＩ－ＴＭＰＴＡ：ジトリメチロールプロパンテトラクリレート（ＨＬＢ８．４、分子量４６６）
（重合禁止剤）
　ＢＨＴ：２，６―ジ－ｔｅｒｔ―ブチル―ｐ－クレゾール
（光重合開始剤）
　Ｉｒｕｇａｃｕｒｅ１８４：１－ヒドロキシシクロヘキシル－フェニルケトン (Hydroxy group-containing (meth)acrylate)
PETA: Pentaerythritol triacrylate (HLB10.9, molecular weight 298, hydroxyl value 188mgKOH/g)
TMPG: Trimethylolpropane diacrylate (HLB8.9, molecular weight 242, hydroxyl value 232mgKOH/g)
GGA: Glycerin diacrylate (HLB10.4, molecular weight 200, hydroxyl value 281mgKOH/g)
15EO-TMPG: 15 mole ethylene oxide modified trimethylolpropane diacrylate (HLB13.9, molecular weight 902, hydroxyl value 62mgKOH/g)
DPTA: dipentaerythritol triacrylate (HLB13.6, molecular weight 416, hydroxyl value 135mgKOH/g)
(resin)
X-1: Styrene acrylic resin, weight average molecular weight 18,000, acid value 110 mgKOH/g (Seiko PMC Co., Ltd.) (contains carboxylic acid group)
YS-1274: Styrene acrylic resin, weight average molecular weight 19,000, acid value 200mgKOH/g (Seiko PMC) (contains carboxylic acid group)
Miramer PU2100: Bifunctional urethane acrylate, molecular weight 1,400 (MIWON)
Miramer PE210: Bifunctional bisphenol A epoxy diacrylate, molecular weight 520 (MIWON)
Miramer PS420: Tetrafunctional polyester acrylate, weight average molecular weight 3,800 (MIWON)
((meth)acrylate that does not contain hydroxyl groups)
TMPTA: Trimethylolpropane triacrylate (HLB8.5, molecular weight 296)
6EO-TMPTA: 6 mole ethylene oxide modified trimethylolpropane triacrylate (HLB10.48, molecular weight 560)
15EO-TMPTA: 15 mole ethylene oxide modified trimethylolpropane triacrylate (HLB13.45, molecular weight 956)
GPTA: 3M PO modified glycerin triacrylate (HLB9.48, molecular weight 428)
DI-TMPTA: ditrimethylolpropane tetraacrylate (HLB8.4, molecular weight 466)
(Polymerization inhibitor)
BHT: 2,6-di-tert-butyl-p-cresol (photopolymerization initiator)
Irugacure184: 1-hydroxycyclohexyl-phenyl ketone
＜積層体の作成＞
　（原反）（化学処理された面を有するときには、その面を組成物の塗布面とした。化学処理された面がなく、コロナ等による放電処理された面があるときには、その面を組成物の塗布面とした。）
　Ｓ４６Ｃ：易接着ポリエチレンテレフタレート、厚さ１２μｍ、ＰＯＬＹＰＬＥＸ社
　ＰＴＭ：易接着２軸延伸ポリエチレンテレフタレート、厚さ１２μｍ、ユニチカ社
　Ｐ２１６１：２軸延伸ポリプロピレン、厚さ２０μｍ、東洋紡社
　ＦＯＲ：コロナ表面処理２軸延伸ポリプロピレン、厚さ２０μｍ、フタムラ化学社
　ＯＮＭ：コロナ表面処理易接着２軸延伸ナイロン、厚さ１５μｍ、ユニチカ社
　Ｎ１１０２：コロナ表面処理ナイロン、厚さ１５μｍ、東洋紡社
　（シーラント（接着されるフィルム））
　ＬＬＤＰＥ：ＴＵＸ－ＨＣ（低密度ポリエチレン）厚さ５０μｍ、三井化学東セロ社
　ＣＰＰ：無延伸ポリプロピレン、Ｐ－１１２８、厚さ２５μｍ、東洋紡社 <Creation of laminate>
(Original fabric) (When it has a chemically treated side, that side was used as the side to which the composition was applied. When there is no chemically treated side and there is a side that has been subjected to discharge treatment by corona etc., that side is used as the side to which the composition is applied. )
S46C: Easy-adhesion polyethylene terephthalate, thickness 12 μm, POLYPLEX Co., Ltd. PTM: Easy-adhesion biaxially stretched polyethylene terephthalate, thickness 12 μm, Unitika P2161: Biaxially stretched polypropylene, thickness 20 μm, Toyobo Co., Ltd. FOR: Corona surface treatment biaxial stretching Polypropylene, 20 μm thick, Futamura Chemical Co., Ltd. ONM: Corona surface treated biaxially stretched nylon for easy adhesion, 15 μm thick, Unitika N1102: Corona surface treated nylon, 15 μm thick, Toyobo Co., Ltd. (Sealant (film to be bonded))
LLDPE: TUX-HC (low-density polyethylene), thickness 50 μm, Mitsui Chemicals Tohcello Co., Ltd. CPP: Unoriented polypropylene, P-1128, thickness 25 μm, Toyobo Co., Ltd.
　（実施例及び比較例）
　下記表中の実施例１に示す組成物を調製した。この組成物を原反である無地のＳ４６Ｃ上に、表１中の塗布量になるように組成物を塗布した。エージングを行なうこと無く、次いで、その塗布面上にシーラントとしてＬＬＤＰＥフィルム（ＴＵＸ－ＨＣ（三井化学東セロ社）厚さ５０μｍ）（以下「ＬＬＤＰＥフィルム」という）又はＣＰＰ（無延伸ポリプロピレン）フィルムを重ねて、表１中の照射量で電子線または紫外線を照射して、これらのフィルムを積層させた。製造に使用した器具類は、家庭用洗剤（弱アルカリ）を用いて水洗浄をした。硬化した活性エネルギー線硬化型接着剤も速やかに除去できた。
　同様にして、無地のＰＴＭ、Ｐ２１６１、ＦＯＲ、ＯＮＭ、Ｎ１１０２上に組成物を塗布し、それぞれに対してシーラントとしてＬＬＤＰＥフィルム又はＣＰＰフィルムを重ねて、表１中の照射量で活性エネルギー線を照射して、これらのフィルムを積層させた。
　そして無地のＳ４６Ｃ、ＰＴＭ、Ｐ２１６１、ＦＯＲ、ＯＮＭ、Ｎ１１０２に代えて、ＥＢオフセットインキ組成物で印刷し硬化させた印刷物上に、それらの印刷箇所を含み、印刷箇所以外の部位にも組成物を塗布した。次いで、エージングを行なうこと無く、その塗布面上にシーラントとしてＬＬＤＰＥフィルム又はＣＰＰフィルムを重ねて、表１中の照射量で活性エネルギー線を照射して、これらのフィルムを積層させた。
　実施例及び比較例においては、アイ・エレクトロンビーム社の電子線照射装置を用い、酸素濃度が２００ｐｐｍの雰囲気下で、加速電圧を９０ｋＶとし、１回の電子線の照射の照射量は３０ｋＧｙを基本として、表１中の照射量になるように複数回照射した。なお、重合開始剤を含有した実施例２３及び２４と比較例１０及び１１については、エージングを行わず、いずれも４００ｍＪ／ｃｍ２になるように照射した。
　また、無地のＳ４６Ｃ、ＰＴＭ、Ｐ２１６１、ＦＯＲ、ＯＮＭ、Ｎ１１０２に代えて、溶剤性グラビアインキにより印刷し乾燥固化した印刷物上に、それらの印刷箇所を含み、印刷箇所以外の部位にも活性エネルギー線硬化型接着剤組成物を塗布した。次いで、エージングを行なうこと無く、その塗布面上にシーラントとしてＬＬＤＰＥフィルム又はＣＰＰフィルムを重ねて、表１中の照射量で活性エネルギー線を照射して、これらのフィルムを積層させた。
　これを、同様にして実施例２～１５、及び比較例１～１３についても行った。 (Example and comparative example)
A composition shown in Example 1 in the table below was prepared. This composition was applied onto a plain S46C original fabric in the coating amounts shown in Table 1. Without aging, an LLDPE film (TUX-HC (Mitsui Chemicals Tohcello Co., Ltd.) thickness 50 μm) (hereinafter referred to as "LLDPE film") or CPP (unoriented polypropylene) film was layered on the coated surface as a sealant. , these films were laminated by irradiating them with electron beams or ultraviolet rays at the irradiation doses shown in Table 1. The equipment used for production was washed with household detergent (weak alkaline). The cured active energy ray-curable adhesive could also be quickly removed.
In the same way, the composition was applied on plain PTM, P2161, FOR, ONM, and N1102, and an LLDPE film or CPP film was layered on each as a sealant, and active energy rays were irradiated at the dose shown in Table 1. These films were then laminated.
Then, instead of plain S46C, PTM, P2161, FOR, ONM, and N1102, the composition was applied to the prints printed and cured with an EB offset ink composition, including those printed areas, and also to areas other than the printed areas. Coated. Next, without aging, an LLDPE film or a CPP film was layered as a sealant on the coated surface, and active energy rays were irradiated at the dose shown in Table 1 to stack these films.
In the Examples and Comparative Examples, an electron beam irradiation device manufactured by I-Electron Beam Co., Ltd. was used, the acceleration voltage was set to 90 kV in an atmosphere with an oxygen concentration of 200 ppm, and the irradiation amount of one electron beam irradiation was basically 30 kGy. The irradiation was performed multiple times to achieve the irradiation doses shown in Table 1. Note that Examples 23 and 24 and Comparative Examples 10 and 11, which contained a polymerization initiator, were not aged and were irradiated at 400 mJ/cm 2 .
In addition, instead of plain S46C, PTM, P2161, FOR, ONM, N1102, active energy rays can be applied to areas other than the printed areas, including those printed areas, on printed matter printed with solvent-based gravure ink and dried and solidified. A curable adhesive composition was applied. Next, without aging, an LLDPE film or a CPP film was layered as a sealant on the coated surface, and active energy rays were irradiated at the dose shown in Table 1 to stack these films.
This was similarly carried out for Examples 2 to 15 and Comparative Examples 1 to 13.
（参考例１）
　原反としてＰＴＭに、接着剤（ポリウレタン系接着剤混合物（タケラックＡ－９６９Ｖ）／ポリウレタン系接着剤（タケネートＡ－５）（いずれも三井化学社）を質量比３／１で配合し、酢酸エチルで適宜希釈した接着剤）を接着剤塗布量が２．０ｇ／ｍ２となるように塗工した。シーラントのシートとして、上記ＬＬＤＰＥをラミネートした。その後、エージングとして４０℃で２４時間加熱したサンプル、及び０℃で２４時間保存したサンプルを用いて剥離試験を行った。剥離強度は十分に強かった。 (Reference example 1)
PTM as a raw material was mixed with an adhesive (polyurethane adhesive mixture (Takelac A-969V)/polyurethane adhesive (Takenate A-5) (both manufactured by Mitsui Chemicals) at a mass ratio of 3/1, and ethyl acetate was added. (adhesive diluted appropriately) was applied so that the adhesive coating amount was 2.0 g/m 2 . The above LLDPE was laminated as a sealant sheet. Thereafter, a peel test was conducted using a sample heated at 40° C. for 24 hours for aging and a sample stored at 0° C. for 24 hours. Peel strength was sufficiently strong.
（参考例２）
　参考例１と同様にして上記ＬＬＤＰＥをラミネートした。その後、エージングしないサンプルを用いて剥離試験を行った。剥離強度は極めて弱かった。 (Reference example 2)
The above LLDPE was laminated in the same manner as in Reference Example 1. Thereafter, a peel test was conducted using the non-aged sample. Peel strength was extremely weak.
＜アルカリ水への浸漬結果＞
　実施例及び比較例の活性エネルギー線硬化型接着剤組成物を、マジックリン（花王社）を１．０質量％の濃度になるように水に溶解して得た２５℃のアルカリ水に浸漬した結果は以下のとおりであった。
　全ての実施例にて接着剤層が溶解した。
　全ての比較例にて接着剤層が溶解しなかった。 <Results of immersion in alkaline water>
The active energy ray-curable adhesive compositions of Examples and Comparative Examples were immersed in 25°C alkaline water obtained by dissolving Magiclin (Kao Corporation) in water to a concentration of 1.0% by mass. The results were as follows.
The adhesive layer dissolved in all examples.
In all comparative examples, the adhesive layer did not dissolve.
＜剥離強度の測定＞
　実施例及び比較例の積層体について、電子線照射後又は紫外線照射後、直ちに、引張試験機（安田精機製作所社）を用いて、測定温度２５℃、引張速度２００ｍｍ／ｍｉｎで得られた樹脂フィルムを引張り、破断した時の強度を求めた。
　４０℃で１日経時した積層体を１５ｍｍ幅に切断し、剥離試験機（安田精機製作所社）を用いて、ラミネート強度としてＴ型剥離強度（ｇ／１５ｍｍ）を測定した。
＜引張強度＞
　４０℃で１日経時した積層体を１５ｍｍ幅に切断し、原反とシーラントのフィルムとの間を、オリエンテック社テンシロン万能試験機を用いて、雰囲気温度２５℃、剥離速度を３００ｍｍ／分に設定し、１８０度剥離方法で剥離した際の引っ張り強度をラミネート強度（Ｎ／１５ｍｍ）とした。表中のラミネート強度を示す数値の後に記載した記号について、Ｆはフィルム破断、Ｂは原反側からの剥離、Ｓはシーラントフィルム側からの剥離を意味する。
　なお、下記表中には、上記剥離強度と引張強度を並べて記載した。例えば７．０Ｆは、剥離強度が７．０ｇ／１５ｍｍであり、かつ、引張強度の測定によりフィルム破断したことを意味する。 <Measurement of peel strength>
Resin films obtained for the laminates of Examples and Comparative Examples immediately after electron beam irradiation or ultraviolet ray irradiation using a tensile tester (Yasuda Seiki Seisakusho Co., Ltd.) at a measurement temperature of 25° C. and a tensile speed of 200 mm/min. was pulled and the strength at break was determined.
The laminate aged at 40° C. for 1 day was cut into 15 mm width pieces, and the T-peel strength (g/15 mm) was measured as the laminate strength using a peel tester (Yasuda Seiki Seisakusho Co., Ltd.).
<Tensile strength>
The laminate aged at 40°C for 1 day was cut into 15 mm width pieces, and the film and sealant film were separated using an Orientec Tensilon universal testing machine at an ambient temperature of 25°C and a peeling speed of 300 mm/min. The tensile strength when peeled using the 180 degree peeling method was defined as the laminate strength (N/15 mm). Regarding the symbols written after the numerical values indicating laminate strength in the table, F means film breakage, B means peeling from the original fabric side, and S means peeling from the sealant film side.
In addition, in the table below, the above-mentioned peel strength and tensile strength are listed side by side. For example, 7.0F means that the peel strength is 7.0 g/15 mm and the film was broken when the tensile strength was measured.
　以下の応用実施例は、本発明の活性エネルギー線硬化型接着剤組成物を使用する他の態様である。
（応用実施例１）
　原反である無地のＰＴＭ及びシーラントとしてＬＬＤＰＥフィルム（厚さ５０μｍ）のそれぞれの片面に、塗布量が２．０ｇ／ｍ２となるように上記の活性エネルギー線硬化型接着剤を塗工して接着剤層を形成した。エージングをすること無く、ＰＴＭと中間に挟むアルミニウム箔を重ね張り合わせ積層体Ａを作成し、さらにエージングをすること無く、積層体Ａのアルミニウム箔側とＬＬＤＰＥフィルムの活性エネルギー線硬化型接着剤層形成側の面を重ね張り合わせ、ＰＴＭ／接着層／アルミニウム箔／接着層／ＬＬＤＰＥフィルムからなる積層体Ｂを得た。張り合わせ手順は逆でもよい。電子線照射装置(ＥＢ装置)（岩崎電気社）を用いて照射線量１５０ｋＧｙ、９０ｋＶの電子線を積層体Ｂの第２の透明フィルム側から照射して接着させた。
　ＰＴＭ及びＬＬＤＰＥフィルムは互いに十分な強度で接着をしていた。また、製造に使用した器具類は、家庭用洗剤（弱アルカリ）を用いて水洗浄をし、付着していた活性エネルギー線硬化型接着剤も速やかに除去できた。 The following application examples are other embodiments in which the active energy ray-curable adhesive composition of the present invention is used.
(Application example 1)
The above active energy ray-curable adhesive was applied to one side of each of plain PTM as the original fabric and LLDPE film (thickness 50 μm) as the sealant at a coating amount of 2.0 g/ m2. An adhesive layer was formed. Laminate A is created by laminating PTM and aluminum foil sandwiched between them without aging, and an active energy ray-curable adhesive layer is formed between the aluminum foil side of laminate A and the LLDPE film without aging. The side surfaces were laminated together to obtain a laminate B consisting of PTM/adhesive layer/aluminum foil/adhesive layer/LLDPE film. The pasting procedure may be reversed. Using an electron beam irradiation device (EB device) (Iwasaki Electric Co., Ltd.), an electron beam with an irradiation dose of 150 kGy and 90 kV was irradiated from the second transparent film side of the laminate B to bond it.
The PTM and LLDPE films adhered to each other with sufficient strength. In addition, the equipment used in the production was washed with water using a household detergent (weakly alkaline), and the active energy ray-curable adhesive that had adhered to it was quickly removed.
（応用実施例２）
　原反である無地のＰＴＭ及びシーラントとしてＬＬＤＰＥフィルム（厚さ５０μｍ）のそれぞれの片面に、塗布量が２．０ｇ／ｍ２となるように上記の活性エネルギー線硬化型接着剤を塗工して接着剤層を形成した。そして、エージングをすること無く、ＰＴＭと中間に挟むアルミニウム箔を重ね張り合わせ積層体Ａを作成し、電子線照射装置(ＥＢ装置)（岩崎電気社）を用いて照射線量１５０ｋＧｙ、９０ｋＶの電子線をＰＴＭ側から照射して接着させた（アルミニウム箔側からでもよい）。
　次に、エージングをすること無く、電子線照射した積層体Ａのアルミニウム箔側と、ＬＬＤＰＥフィルムを張り合わせ、積層体Ｂを作成し、電子線照射装置(ＥＢ装置)（岩崎電気社）を用いて照射線量１５０ｋＧｙ、９０ｋＶの電子線をＬＬＤＰＥフィルム側から照射して接着させた。
　ＰＴＭ及びＬＬＤＰＥフィルムは互いに十分な強度で接着をしていた。また、製造に使用した器具類は、家庭用洗剤（弱アルカリ）を用いて水洗浄をし、付着していた活性エネルギー線硬化型接着剤も速やかに除去できた。 (Application example 2)
The above active energy ray-curable adhesive was applied to one side of each of plain PTM as the original fabric and LLDPE film (thickness 50 μm) as the sealant at a coating amount of 2.0 g/ m2. An adhesive layer was formed. Then, without aging, a laminate A was created by laminating the PTM and aluminum foil sandwiched in between, and irradiated with an electron beam of 150 kGy and 90 kV using an electron beam irradiation device (EB device) (Iwasaki Electric Co., Ltd.). Adhesion was performed by irradiating from the PTM side (or from the aluminum foil side).
Next, without aging, the aluminum foil side of the laminate A that had been irradiated with electron beams was laminated with the LLDPE film to create a laminate B, which was then irradiated using an electron beam irradiation device (EB device) (Iwasaki Electric Co., Ltd.). An electron beam with an irradiation dose of 150 kGy and 90 kV was irradiated from the LLDPE film side to bond the film.
The PTM and LLDPE films adhered to each other with sufficient strength. In addition, the equipment used in the production was washed with water using a household detergent (weakly alkaline), and the active energy ray-curable adhesive that had adhered to it was quickly removed.
（応用実施例３）
　原反である印刷済のＰＴＭの印刷側面及びシーラントとしてＬＬＤＰＥフィルム（厚さ５０μｍ）の片面に、塗布量が２．０ｇ／ｍ２となるように上記の活性エネルギー線硬化型接着剤を塗工して接着剤層を形成した。エージングをすること無く、ＰＴＭとアルミニウム箔を重ね張り合わせ積層体Ａを作成し、電子線照射装置(ＥＢ装置)（岩崎電気社）を用いて照射線量１５０ｋＧｙ、９０ｋＶの電子線をＰＴＭ側から照射して接着させた（アルミニウム箔側からでもよい）。次に、電子線照射した積層体Ａのアルミニウム箔側と、第２の透明フィルムを張り合わせ、積層体Ｂを作成し、電子線照射装置(ＥＢ置)（岩崎電気社）を用いて照射線量１５０ｋＧｙ、９０ｋＶの電子線を第２の透明フィルム側から照射して接着させた。
　ＰＴＭ及びＬＬＤＰＥフィルムは互いに十分な強度で接着をしていた。また、製造に使用した器具類は、家庭用洗剤（弱アルカリ）を用いて水洗浄をし、付着していた活性エネルギー線硬化型接着剤も速やかに除去できた。 (Application example 3)
The above active energy ray-curable adhesive was applied to the printing side of the printed PTM as the original film and to one side of the LLDPE film (thickness 50 μm) as a sealant at a coating amount of 2.0 g/ m2 . An adhesive layer was formed. A laminate A was created by laminating PTM and aluminum foil without aging, and an electron beam of 150 kGy and 90 kV was irradiated from the PTM side using an electron beam irradiation device (EB device) (Iwasaki Electric Co., Ltd.). (You can also do this from the aluminum foil side.) Next, the aluminum foil side of the laminate A that was irradiated with the electron beam was laminated with a second transparent film to create a laminate B, and the laminate B was irradiated with an irradiation dose of 150 kGy using an electron beam irradiation device (EB installation) (Iwasaki Electric Co., Ltd.). , 90 kV electron beam was irradiated from the second transparent film side for adhesion.
The PTM and LLDPE films adhered to each other with sufficient strength. In addition, the equipment used in the production was washed with water using a household detergent (weakly alkaline), and the active energy ray-curable adhesive that had adhered to it was quickly removed.
　本発明に沿った例である各実施例によれば、十分に高い接着性を発揮できた。そのため、引張強度を測定する際には、フィルムの破断を起こすほどであった。
　しかしながら、水酸基含有（メタ）アクリレートを含有しない活性エネルギー線硬化型接着剤組成物を使用した各比較例によれば、弱い接着力を呈するに留まった。
　しかしながら、水酸基含有（メタ）アクリレートを含有しない活性エネルギー線硬化型接着剤組成物を使用した場合には、原反側から剥離するほどに十分な引張強度を示さなかった。
　また、本発明の活性エネルギー線硬化型接着剤組成物はアルカリ水に溶解除去された。 According to each example that is an example in accordance with the present invention, sufficiently high adhesiveness could be exhibited. Therefore, when measuring the tensile strength, the film was even broken.
However, the comparative examples using active energy ray-curable adhesive compositions that do not contain hydroxyl group-containing (meth)acrylate only exhibited weak adhesive strength.
However, when an active energy ray-curable adhesive composition containing no hydroxyl group-containing (meth)acrylate was used, it did not exhibit sufficient tensile strength to peel from the original fabric side.
Further, the active energy ray-curable adhesive composition of the present invention was dissolved and removed in alkaline water.

Claims (13)

  1. 　全重合性成分中に、水酸基含有（メタ）アクリレートを４５．０～９５．０質量％含有し、
    　更にカルボン酸基、ヒドロキシル基及びウレタン基のうち１種以上、及び／又は、エチレン性不飽和基を有し、重量平均分子量が５００～１０００００の樹脂を含有する、活性エネルギー線硬化型接着剤組成物。     Contains 45.0 to 95.0% by mass of hydroxyl group-containing (meth)acrylate in all polymerizable components,
    An active energy ray-curable adhesive composition further comprising a resin having one or more of carboxylic acid groups, hydroxyl groups, and urethane groups and/or ethylenically unsaturated groups and having a weight average molecular weight of 500 to 100,000. thing.
  2. 　水酸基含有（メタ）アクリレートが、１分子中に（メタ）アクリロイル基を１つ以上有し、かつ１分子中に水酸基を１つ以上有する、請求項１に記載の活性エネルギー線硬化型接着剤組成物。 The active energy ray-curable adhesive composition according to claim 1, wherein the hydroxyl group-containing (meth)acrylate has one or more (meth)acryloyl groups in one molecule, and one or more hydroxyl groups in one molecule. thing.
  3. 　水酸基含有（メタ）アクリレートの表面張力値（デイビス法）が８．０～２０．０である請求項１又は２に記載の活性エネルギー線硬化型接着剤組成物。 The active energy ray-curable adhesive composition according to claim 1 or 2, wherein the hydroxyl group-containing (meth)acrylate has a surface tension value (Davis method) of 8.0 to 20.0.
  4. 　水酸基含有（メタ）アクリレートの平均分子量が１００～２０００である請求項１～３のいずれかに記載の活性エネルギー線硬化型接着剤組成物。 The active energy ray-curable adhesive composition according to any one of claims 1 to 3, wherein the hydroxyl group-containing (meth)acrylate has an average molecular weight of 100 to 2,000.
  5. 　水酸基含有（メタ）アクリレートの水酸基価が３０～４００ｍｇＫＯＨ／ｇである請求項１～４のいずれかに記載の活性エネルギー線硬化型接着剤組成物。 The active energy ray-curable adhesive composition according to any one of claims 1 to 4, wherein the hydroxyl group-containing (meth)acrylate has a hydroxyl value of 30 to 400 mgKOH/g.
  6. 　活性エネルギー線による重合性成分全体の水酸基価が３０ｍｇＫＯＨ／ｇ以上である請求項１～５のいずれかに記載の活性エネルギー線硬化型接着剤組成物。 The active energy ray-curable adhesive composition according to any one of claims 1 to 5, wherein the hydroxyl value of the entire polymerizable component by active energy rays is 30 mgKOH/g or more.
  7. 　水酸基含有（メタ）アクリレートが、水酸基含有ポリ（メタ）アクリレートを含有し、その水酸基含有ポリ（メタ）アクリレートが、ペンタエリスリトール、ジペンタエリスリトール、グリセリン、ジグリセリン、トリメチロールプロパン、及びジトリメチロールプロパンの１種以上の化合物と、（メタ）アクリル酸が、エステル結合してなる化合物である請求項１～６のいずれかに記載の活性エネルギー線硬化型接着剤組成物。 The hydroxyl group-containing (meth)acrylate contains a hydroxyl group-containing poly(meth)acrylate, and the hydroxyl group-containing poly(meth)acrylate contains pentaerythritol, dipentaerythritol, glycerin, diglycerin, trimethylolpropane, and ditrimethylolpropane. The active energy ray-curable adhesive composition according to any one of claims 1 to 6, which is a compound formed by an ester bond between one or more compounds and (meth)acrylic acid.
  8. 　活性エネルギー線硬化型接着剤組成物の含水率が０．０１～５．００質量％である請求項１～７のいずれかに記載の活性エネルギー線硬化型接着剤組成物。 The active energy ray curable adhesive composition according to any one of claims 1 to 7, wherein the active energy ray curable adhesive composition has a water content of 0.01 to 5.00% by mass.
  9. 　水酸基含有ポリ（メタ）アクリレートが、１分子あたり２～４の（メタ）アクリロイル基を有する化合物である請求項１～８のいずれかに記載の活性エネルギー線硬化型接着剤組成物。 The active energy ray-curable adhesive composition according to any one of claims 1 to 8, wherein the hydroxyl group-containing poly(meth)acrylate is a compound having 2 to 4 (meth)acryloyl groups per molecule.
  10. 　水酸基含有ポリ（メタ）アクリレートが、ペンタエリスリトールジ（メタ）アクリレート、及び／又はペンタエリスリトールトリ（メタ）アクリレートを含有する請求項７～９のいずれかに記載の活性エネルギー線硬化型接着剤組成物。 The active energy ray-curable adhesive composition according to any one of claims 7 to 9, wherein the hydroxyl group-containing poly(meth)acrylate contains pentaerythritol di(meth)acrylate and/or pentaerythritol tri(meth)acrylate. .
  11. 　１０～５００ｋＧｙの活性エネルギー線で硬化可能な請求項１～１０のいずれかに記載の活性エネルギー線硬化型接着剤組成物。 The active energy ray-curable adhesive composition according to any one of claims 1 to 10, which is curable with active energy rays of 10 to 500 kGy.
  12. 　一方の被接着物表面に請求項１～１１のいずれかに記載の活性エネルギー線硬化型接着剤組成物を塗布し、その活性エネルギー線硬化型接着剤組成物層の上に他方の被接着物を積層し、次いで、活性エネルギー線硬化型接着剤組成物層に活性エネルギー線を照射する積層体の製造方法。 The active energy ray-curable adhesive composition according to any one of claims 1 to 11 is applied to the surface of one adherend, and the active energy ray-curable adhesive composition layer is applied to the surface of the other adherend. A method for producing a laminate, which comprises laminating the active energy ray-curable adhesive composition layers, and then irradiating the active energy ray-curable adhesive composition layer with active energy rays.
  13. 　請求項１～１１のいずれかに記載の活性エネルギー線硬化型接着剤組成物により形成された活性エネルギー線硬化型接着剤層により接着された一方の被接着物層と他方の被接着剤層を有する積層体。 One adherend layer and the other adherend layer bonded by an active energy ray curable adhesive layer formed from the active energy ray curable adhesive composition according to any one of claims 1 to 11. Laminated body with.
PCT/JP2022/047349 2022-03-31 2022-12-22 Active energy ray-curable adhesive composition WO2023188627A1 (en)

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JP2012071456A (en) * 2010-09-28 2012-04-12 Dic Corp Thermal transfer film and method for manufacturing the same
JP2017197711A (en) * 2016-04-20 2017-11-02 東洋インキＳｃホールディングス株式会社 Active energy ray-polymerizable adhesive and laminate
JP2018131627A (en) * 2018-03-26 2018-08-23 リンテック株式会社 Active energy ray-curable adhesive, adhesive sheet and laminate
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JP2012071456A (en) * 2010-09-28 2012-04-12 Dic Corp Thermal transfer film and method for manufacturing the same
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