WO2023188627A1 - Composition adhésive durcissable par des rayons d'énergie active - Google Patents

Composition adhésive durcissable par des rayons d'énergie active 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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English (en)
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/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • 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)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

La présente invention concerne une composition adhésive durcissable par rayonnement d'énergie active qui présente une excellente adhésivité sans vieillissement après adhérence, est facilement disponible, est supérieure en termes de neutralité carbone, a une productivité élevée dans le processus d'adhérence, et est peu coûteuse (économiquement avantageuse) ; un procédé de production d'un stratifié à l'aide de la composition adhésive durcissable par rayonnement d'énergie active ; et un stratifié utilisant la composition adhésive durcissable par rayonnement d'énergie active. L'invention concerne donc une composition adhésive durcissable par rayonnement d'énergie active qui contient 45,0 à 95,0 % en masse d'un (méth)acrylate contenant un groupe hydroxyle dans les composants polymérisables totaux, et qui contient en outre une résine ayant un groupe éthyléniquement insaturé et/ou au moins l'un parmi un groupe acide carboxylique, un groupe hydroxyle et un groupe uréthane, et ayant un poids moléculaire moyen en poids de 500 à 100 000.
PCT/JP2022/047349 2022-03-31 2022-12-22 Composition adhésive durcissable par des rayons d'énergie active WO2023188627A1 (fr)

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JP2012071456A (ja) * 2010-09-28 2012-04-12 Dic Corp 熱転写フィルム及びその製造方法
JP2017197711A (ja) * 2016-04-20 2017-11-02 東洋インキＳｃホールディングス株式会社 活性エネルギー線重合性接着剤および積層体
JP2018131627A (ja) * 2018-03-26 2018-08-23 リンテック株式会社 活性エネルギー線硬化性粘着剤、粘着シートおよび積層体
JP2020106830A (ja) * 2018-12-26 2020-07-09 デクセリアルズ株式会社 光硬化性樹脂組成物及び画像表示装置の製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012071456A (ja) * 2010-09-28 2012-04-12 Dic Corp 熱転写フィルム及びその製造方法
JP2017197711A (ja) * 2016-04-20 2017-11-02 東洋インキＳｃホールディングス株式会社 活性エネルギー線重合性接着剤および積層体
JP2018131627A (ja) * 2018-03-26 2018-08-23 リンテック株式会社 活性エネルギー線硬化性粘着剤、粘着シートおよび積層体
JP2020106830A (ja) * 2018-12-26 2020-07-09 デクセリアルズ株式会社 光硬化性樹脂組成物及び画像表示装置の製造方法

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