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
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/02—Non-macromolecular additives
  • C09J11/06—Non-macromolecular additives organic
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J201/00—Adhesives based on unspecified macromolecular compounds
• • 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 ultraviolet-curable composition for printing.
• the present invention also relates to a method for producing a laminate using the ultraviolet-curable composition for printing.
• Adhesives are used to bond electronic components inside electronic devices such as smartphones and PCs.
• an adhesive sheet is first produced with separators on both sides of the adhesive, and then the adhesive sheet is cut into the desired shape.
• One separator is then peeled off from the cut adhesive sheet, and one side of the exposed adhesive is bonded to a first adherend, and then the other separator is peeled off, and the other side of the exposed adhesive is bonded to a second adherend.
• part of the adhesive sheet is discarded after cutting, resulting in waste.
• Patent Document 1 discloses an invention for providing a radiation-curable adhesive composition that allows fine patterning and exhibits high adhesion to various adherends such as metals and plastics.
• Patent Document 1 describes a radiation-curable adhesive composition that contains 10 to 70% by weight of an ethylenically unsaturated monomer that does not contain an aromatic ring, 1 to 10% by weight of a photopolymerization initiator, and 10 to 55% by weight of a crosslinking agent.
• Patent Document 2 discloses an invention for providing a photocurable adhesive composition that, even when irradiated with light in the presence of oxygen, gives a laminate having adhesive strength equivalent to that in the absence of oxygen.
• Patent Document 2 describes a photocurable adhesive composition that contains (A) a (meth)acrylate oligomer, (B) a monofunctional (meth)acrylate monomer, (C) a di- to tetrafunctional (meth)acrylate monomer, (D) a photoinitiator, (E) a tackifier having a softening point of 70 to 150°C, and (F) a liquid plasticizer.
• the method of printing the adhesive composition in a desired shape and then laminating it to an adherend without preparing an adhesive sheet can reduce waste generation.
• a method of curing the adhesive composition UV curing is preferable to avoid heating the adherend, but if the adhesive composition is exposed during curing without being covered by a separator, sufficient UV reactivity may not be obtained.
• conventional adhesive compositions have too high adhesive strength, there has been a demand for a UV-curable composition for printing that has excellent removability (reworkability).
• the present invention aims to provide an ultraviolet-curable composition for printing that has excellent printability and removability.
• the present invention also aims to provide a method for producing a laminate using the ultraviolet-curable composition for printing.
• Disclosure 1 relates to a printing ultraviolet-curable composition containing a monofunctional (meth)acrylic monomer, a polyfunctional (meth)acrylic monomer, a photopolymerization initiator, and a thermoplastic resin, the printing ultraviolet-curable composition being coated on a substrate, and the coated surface being unsealed and irradiated with light having a wavelength of 280 nm or more and 480 nm or less under atmospheric conditions at an irradiance of 60 mW/ cm2 and an exposure dose of 900 mJ/ cm2 to obtain a cured product having a thickness of 100 ⁇ m.
• Disclosure 2 relates to the ultraviolet-curable composition for printing of Disclosure 1, in which the above-mentioned ultraviolet-curable composition for printing is coated on a substrate, and the coated surface is not sealed, and in an atmospheric environment, light having a wavelength of 280 nm or more and 480 nm or less is irradiated under conditions of an irradiance of 60 mW/ cm2 and an exposure dose of 900 mJ/ cm2 to obtain a cured product having a thickness of 100 ⁇ m, which is then immersed in tetrahydrofuran , filtered, and the mass measured within 3 minutes after wiping off the tetrahydrofuran on the surface is W1 (g), and the mass measured after drying the cured product at 110°C for 60 minutes is W2 (g), in which the swelling ratio represented by W1 / W2 is
• the present disclosure 3 relates to the ultraviolet ray curable composition for printing according to the present disclosure 1 or 2, in which the content of the polyfunctional (meth)acrylic monomer in the ultraviolet ray curable composition for printing is 3% by mass or more and 99% by mass or less.
• the present disclosure 4 relates to the ultraviolet ray curable composition for printing according to the present disclosure 3, in which the content of the polyfunctional (meth)acrylic monomer in the ultraviolet ray curable composition for printing is 6% by mass or more and 30% by mass or less.
• the present disclosure 5 is the ultraviolet-curable composition for printing according to the present disclosure 1, 2, 3, or 4, further comprising a polymerizable carbon-carbon double bond-containing nitrogen compound, wherein the content of the polymerizable carbon-carbon double bond-containing nitrogen compound is 0.5 parts by mass or more and 50 parts by mass or less in a total of 100 parts by mass of the ultraviolet-curable composition for printing excluding the thermoplastic resin.
• the present disclosure 6 is the ultraviolet ray curable composition for printing according to the present disclosure 1, 2, 3, 4, or 5, having a viscosity of 0.1 mPa ⁇ s or more and 100,000 mPa ⁇ s or more as measured at 25° C. using an E-type viscometer.
• Disclosure 7 relates to a printing ultraviolet-curable composition containing a monofunctional (meth)acrylic monomer, a polyfunctional (meth)acrylic monomer, a photopolymerization initiator, and a thermoplastic resin, the printing ultraviolet-curable composition being coated on a substrate, and the coated surface being unsealed and irradiated with light having a wavelength of 280 nm or more and 480 nm or less under atmospheric conditions at an irradiance of 60 mW/cm 2 and an exposure dose of 900 mJ/cm 2.
• the composition is immersed in tetrahydrofuran, filtered, and the mass measured within 3 minutes after wiping off the tetrahydrofuran on the surface is W 1 (g), and the cured product for which W 1 was measured is dried at 110° C. for 60 minutes, and the swelling ratio represented by W 1 /W 2 is 1.0 or more and 6.0 or less, and the glass transition temperature is 70° C. or less.
• the present disclosure 8 relates to the ultraviolet ray curable composition for printing according to the present disclosure 7, wherein the content of the polyfunctional (meth)acrylic monomer in the ultraviolet ray curable composition for printing is 1% by mass or more and 99% by mass or less.
• the present disclosure 9 is the ultraviolet ray curable composition for printing according to the present disclosure 8, wherein the content of the polyfunctional (meth)acrylic monomer in the ultraviolet ray curable composition for printing is 3% by mass or more and 45% by mass or less.
• the present disclosure 10 is the ultraviolet-curable composition for printing according to the present disclosure 7, 8, or 9, further comprising a polymerizable carbon-carbon double bond-containing nitrogen compound, wherein the content of the polymerizable carbon-carbon double bond-containing nitrogen compound is 0.5 parts by mass or more and 55 parts by mass or less in a total of 100 parts by mass of the ultraviolet-curable composition for printing excluding the thermoplastic resin.
• the present disclosure 11 is the ultraviolet ray curable composition for printing according to the present disclosure 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, wherein the content of the thermoplastic resin in the ultraviolet ray curable composition for printing is 1 mass % or more and 60 mass % or less.
• the present disclosure 12 is the ultraviolet ray curable composition for printing according to the present disclosure 11, wherein the content of the thermoplastic resin in the ultraviolet ray curable composition for printing is 10% by mass or more and 40% by mass or less.
• the present disclosure 13 is a UV-curable composition for printing according to the present disclosure 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12, which is used for screen printing or flexographic printing.
• Disclosure 14 is a method for producing a laminate, comprising applying a printing ultraviolet-curable composition according to Disclosures 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, or 13 onto a first adherend, exposing the composition to light to form an adhesive layer, and attaching a second adherend onto the adhesive layer to produce a laminate.
• Disclosure 15 relates to the method for producing a laminate according to Disclosure 14, in which a method for applying the ultraviolet-curable composition for printing is screen printing or flexographic printing, and the ultraviolet-curable composition for printing is partially applied onto the first adherend.
• a method for applying the ultraviolet-curable composition for printing is screen printing or flexographic printing
• the ultraviolet-curable composition for printing is partially applied onto the first adherend.
• the UV-curable composition for printing of Disclosure 1 will also be referred to as the "UV-curable composition for printing of Invention 1”
• the UV-curable composition for printing of Disclosure 7 will also be referred to as the "UV-curable composition for printing of Invention 2.”
• matters common to the UV-curable composition for printing of Invention 1 and the UV-curable composition for printing of Invention 2 will be described as the "UV-curable composition for printing of the present invention.”
• the present inventors have investigated how to obtain an ultraviolet-curable composition for printing containing a monofunctional (meth)acrylic monomer, a polyfunctional (meth)acrylic monomer, a photopolymerization initiator, and a thermoplastic resin, and how to obtain a cured product obtained by curing the composition under specific conditions, so as to have a shear storage modulus at 150° C.
• the present inventors also investigated how to make the UV-curable composition for printing contain a monofunctional (meth)acrylic monomer, a polyfunctional (meth)acrylic monomer, a photopolymerization initiator, and a thermoplastic resin, and how to set the swelling ratio and glass transition temperature of the cured product obtained by curing the composition under specific conditions, when immersed in tetrahydrofuran, within specific ranges. As a result, they found that it is possible to obtain a UV-curable composition for printing that is excellent in printability and removability, and thus completed the present invention 2.
• the ultraviolet-curable composition for printing of the present invention contains a monofunctional (meth)acrylic monomer.
• the ultraviolet-curable composition for printing of the present invention has excellent adhesion to various substrates.
• (meth)acrylic means acrylic or methacrylic
• the term "monofunctional (meth)acrylic monomer” means a monomer having one (meth)acryloyl group in one molecule
• the term "(meth)acryloyl” means acryloyl or methacryloyl.
• Examples of the monofunctional (meth)acrylic monomer include monofunctional (meth)acrylic acid ester compounds, monofunctional (meth)acrylamide compounds, etc.
• Examples of the monofunctional (meth)acrylic acid ester compounds include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, n-heptyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, isomyristyl (meth)acrylate, stearyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-hydroxybutyl (meth)
• Examples of the monofunctional (meth)acrylamide compounds include N,N-dimethyl(meth)acrylamide, N-(meth)acryloylmorpholine, N-hydroxyethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, and N,N-dimethylaminopropyl(meth)acrylamide.
• the preferred lower limit of the content of the monofunctional (meth)acrylic monomer in the UV-curable composition for printing of the present invention is 10% by mass, and the preferred upper limit is 80% by mass. When the content of the monofunctional (meth)acrylic monomer is within this range, the resulting UV-curable composition for printing has better printability and adhesion to various substrates.
• the more preferred lower limit of the content of the monofunctional (meth)acrylic monomer is 20% by mass, and the more preferred upper limit is 60% by mass.
• polyfunctional (meth)acrylic monomer examples include polyfunctional urethane (meth)acrylates, polyfunctional (meth)acrylic acid ester compounds, and polyfunctional epoxy (meth)acrylates.
• (meth)acrylate means acrylate or methacrylate
• epoxy (meth)acrylate refers to a compound in which all epoxy groups in an epoxy compound have been reacted with (meth)acrylic acid.
• the above-mentioned polyfunctional urethane (meth)acrylate can be obtained, for example, by reacting a (meth)acrylic acid derivative having a hydroxyl group with an isocyanate compound in the presence of a catalytic amount of a tin-based compound.
• MDI diphenylmethane-4,4'-
• isocyanate compound serving as a raw material for the polyfunctional urethane (meth)acrylate a chain-extended isocyanate compound obtained by reacting a polyol with an excess of an isocyanate compound can also be used.
• the polyol include ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, and polycaprolactone diol.
• Examples of the (meth)acrylic acid derivative having a hydroxyl group include hydroxyalkyl mono(meth)acrylates, mono(meth)acrylates of dihydric alcohols, and mono(meth)acrylates or di(meth)acrylates of trihydric alcohols.
• Examples of the hydroxyalkyl mono(meth)acrylate include 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, 2-hydroxybutyl(meth)acrylate, and 4-hydroxybutyl(meth)acrylate.
• Examples of the dihydric alcohol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and polyethylene glycol.
• Examples of the trihydric alcohol include trimethylolethane, trimethylolpropane, and glycerin.
• polyfunctional (meth)acrylic acid ester compounds examples include 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 2-n-butyl-2-ethyl-1,3-propanediol di(meth)acrylate, acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene glyco
• polyfunctional epoxy (meth)acrylate examples include bisphenol A type epoxy (meth)acrylate, bisphenol F type epoxy (meth)acrylate, bisphenol E type epoxy (meth)acrylate, and caprolactone modified versions of these.
• the polyfunctional (meth)acrylic monomer has a preferred lower limit of 4.0 mol% double bond concentration.
• the double bond concentration of 4.0 mol% or more improves the crosslink density, so that the printing ultraviolet-curable composition has better removability.
• the more preferred lower limit of the double bond concentration is 8.0 mol%.
• the double bond concentration is a value obtained by dividing the sum of the molecular weights of the carbon-carbon double bonds contained in the polyfunctional (meth)acrylic monomer by the molecular weight of the polyfunctional (meth)acrylic monomer.
• the molecular weight of the carbon-carbon double bond means the sum of the atomic weights of the carbon atoms constituting the carbon-carbon double bond and the hydrogen atoms bonded to the carbon atoms.
• the preferred and more preferred lower limits of the double bond concentration mean the mass average value.
• the preferred lower limit of the content of the polyfunctional (meth)acrylic monomer in the UV-curable composition for printing of the present invention 1 is 3% by mass, and the preferred upper limit is 99% by mass.
• the content of the polyfunctional (meth)acrylic monomer in the UV-curable composition for printing of the present invention 1 is within this range, the resulting UV-curable composition for printing has better printability and removability.
• the more preferred lower limit of the content of the polyfunctional (meth)acrylic monomer in the UV-curable composition for printing of the present invention 1 is 6% by mass, and the more preferred upper limit is 30% by mass.
• the preferred lower limit of the content of the polyfunctional (meth)acrylic monomer in the UV-curable composition for printing of the present invention 2 is 1% by mass, and the preferred upper limit is 99% by mass.
• the content of the polyfunctional (meth)acrylic monomer in the UV-curable composition for printing of the present invention 2 is within this range, the resulting UV-curable composition for printing has better printability and removability.
• the more preferred lower limit of the content of the polyfunctional (meth)acrylic monomer in the UV-curable composition for printing of the present invention 2 is 3% by mass, and the more preferred upper limit is 45% by mass.
• the UV-curable composition for printing of the present invention preferably further contains a polymerizable carbon-carbon double bond-containing nitrogen compound.
• a polymerizable carbon-carbon double bond-containing nitrogen compound By containing the above-mentioned polymerizable carbon-carbon double bond-containing nitrogen compound, the obtained UV-curable composition for printing has better reactivity in the presence of oxygen.
• the nitrogen compound having a (meth)acryloyl group is not regarded as the above-mentioned nitrogen compound containing a polymerizable carbon-carbon double bond, but as the above-mentioned monofunctional (meth)acrylic monomer or polyfunctional (meth)acrylic monomer.
• nitrogen-containing polymerizable carbon-carbon double bond-containing compound examples include nitrogen-containing vinyl compounds and maleimide compounds.
• an amide compound having a vinyl group is preferred, and a cyclic amide compound having a vinyl group is more preferred.
• the cyclic amide compound having a vinyl group preferably has a lactam structure, and more preferably is a compound represented by the following formula (1):
• n represents an integer from 2 to 6.
• Examples of the compound represented by the above formula (1) include N-vinyl-2-pyrrolidone and N-vinyl- ⁇ -caprolactam. Of these, N-vinyl- ⁇ -caprolactam is preferred.
• examples other than the above-mentioned cyclic amide compounds having a vinyl group include N-vinylacetamide, etc.
• maleimide compounds include N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, N-(2-methylphenyl)maleimide, N-(4-methylphenyl)maleimide, N-(2,6-diethylphenyl)maleimide, N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-benzylmaleimide, N-phenylmethylmaleimide, N-octadecenylmaleimide, N-dodecenylmaleimide, N-(4-carboxycyclohexylmethyl)maleimide, 4-hydroxyphenylmaleimide, and N-(4-anilinophenyl)maleimide.
• the preferred lower limit of the content of the polymerizable carbon-carbon double bond-containing nitrogen compound in a total of 100 parts by mass of the UV-curable composition for printing excluding the thermoplastic resin described below is 0.1 parts by mass, and the preferred upper limit is 90 parts by mass.
• the content of the polymerizable carbon-carbon double bond-containing nitrogen compound is within this range, the obtained UV-curable composition for printing has superior reactivity in the presence of oxygen and adhesion to various substrates.
• the more preferred lower limit of the content of the polymerizable carbon-carbon double bond-containing nitrogen compound is 0.5 parts by mass, and the more preferred upper limit is 55 parts by mass.
• the ultraviolet-curable composition for printing contains a photopolymerization initiator.
• a photopolymerization initiator a photoradical polymerization initiator is preferably used.
• the photopolymerization initiator may be used alone or in combination of two or more kinds.
• Examples of the photoradical polymerization initiator include benzophenone compounds, alkylphenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, and thioxanthone compounds.
• Examples of the alkylphenone compounds include acetophenone compounds.
• photoradical polymerization initiator examples include 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-(dimethylamino)-1-(4-(morpholino)phenyl)-1-butanone, 2-(dimethylamino)-2-((4-methylphenyl)methyl)-1-(4-(4-morpholinyl)phenyl)-1-butanone, 2,2-dimethoxy-1,2-diphenylethan-1-one, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2- Examples include methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 1-(4-(2-hydroxyethoxy)-phenyl)-2-hydroxy-2-methyl-1-propan-1-one, 1-(4-(phenylthio)phenyl)-1,2-octanedione 2-(O-benzoyloxime), 2,4,6-trimethylbenzoyldipheny
• the preferred lower limit of the content of the photopolymerization initiator in the UV-curable composition for printing of the present invention is 0.2 parts by mass, and the preferred upper limit is 10 parts by mass.
• the resulting UV-curable composition for printing has better storage stability, curability, and adhesion to various substrates.
• a more preferred lower limit of the content of the photopolymerization initiator is 0.4 parts by mass, and a more preferred upper limit is 8 parts by mass.
• the UV-curable composition for printing of the present invention contains a thermoplastic resin. By containing the above-mentioned thermoplastic resin, the UV-curable composition for printing of the present invention has excellent printability.
• thermoplastic resin may or may not be photoreactive.
• the thermoplastic resin may be, for example, a solvent-free acrylic polymer.
• the solvent-free acrylic polymer include a polymer of at least one monomer selected from (meth)acrylic acid alkyl esters having an alkyl group with 1 to 20 carbon atoms, and a copolymer of the monomer and another copolymerizable monomer.
• commercially available ones include, for example, the ARUFON-UP1000 series, UH2000 series, UC3000 series (all manufactured by Toagosei Co., Ltd.), the Clarity LA series, and the Clarity LK series (all manufactured by Kuraray Co., Ltd.).
• the preferred lower limit of the content of the thermoplastic resin in the UV-curable composition for printing of the present invention is 1% by mass, and the preferred upper limit is 60% by mass.
• the content of the thermoplastic resin in this range By having the content of the thermoplastic resin in this range, the viscosity of the obtained UV-curable composition for printing is improved, a thick coating film can be formed, the printability is superior, and the decrease in adhesion at high temperatures can be suppressed.
• a more preferred lower limit of the content of the thermoplastic resin is 10% by mass, and a more preferred upper limit is 40% by mass.
• the UV-curable composition for printing of the present invention may contain a thermosetting resin or a moisture-curable resin, and may therefore be reactive to triggers such as heat and moisture.
• the ultraviolet-curable composition for printing of the present invention may further contain a tackifier within the range not impairing the object of the present invention.
• a tackifier include rosin-based resins and terpene-based resins.
• the ultraviolet ray curable composition for printing of the present invention may contain a plasticizer.
• the plasticizer include organic acid esters, organic phosphates, and organic phosphites.
• Examples of the organic acid ester include monobasic organic acid esters and polybasic organic acid esters.
• Examples of the monobasic organic acid ester include glycol esters obtained by reacting a monobasic organic acid such as butyric acid, isobutyric acid, caproic acid, 2-ethylbutyric acid, heptyl acid, n-octylic acid, 2-ethylhexyl acid, pelargonic acid (n-nonylic acid), or decylic acid with a glycol such as triethylene glycol, tetraethylene glycol, or tripropylene glycol.
• a monobasic organic acid such as butyric acid, isobutyric acid, caproic acid, 2-ethylbutyric acid, heptyl acid, n-octylic acid, 2-ethylhexyl acid, pelargonic acid (n-nonylic acid), or decylic acid with a glycol such as triethylene glycol
• polybasic organic acid ester examples include ester compounds obtained by reacting a polybasic organic acid such as adipic acid, sebacic acid, or azelaic acid with an alcohol having a linear or branched structure having 4 to 8 carbon atoms.
• organic acid esters include triethylene glycol di-2-ethylbutyrate (3GH), triethylene glycol di-2-ethylhexanoate (3GO), triethylene glycol dicaprylate, triethylene glycol di-n-octanoate, and triethylene glycol di-n-heptanoate (3G7).
• tetraethylene glycol di-n-heptanoate (4G7) tetraethylene glycol di-2-ethylhexanoate, dibutyl sebacate, dioctyl azelate, dibutyl carbitol adipate, ethylene glycol di-2-ethylbutyrate, and 1,3-propylene glycol di-2-ethylbutyrate.
• 1,4-butylene glycol di-2-ethylbutyrate, diethylene glycol di-2-ethylbutyrate, diethylene glycol di-2-ethylhexanoate, and dipropylene glycol di-2-ethylbutyrate are also included.
• Examples include triethylene glycol di-2-ethylpentanoate, tetraethylene glycol di-2-ethylbutyrate (4GH), diethylene glycol dicapryate, dihexyl adipate (DHA), dioctyl adipate, hexylcyclohexyl adipate, diisononyl adipate, heptylnonyl adipate, etc.
• Other examples include oil-modified sebacic acid alkyd, a mixture of a phosphate ester and an adipate ester, and a mixed adipate ester made from an alkyl alcohol having 4 to 9 carbon atoms and a cyclic alcohol having 4 to 9 carbon atoms.
• the organic phosphate or organic phosphite may be a compound obtained by a condensation reaction between phosphoric acid or phosphorous acid and an alcohol.
• a compound obtained by a condensation reaction between an alcohol having 1 to 12 carbon atoms and phosphoric acid or phosphorous acid is preferable.
• the alcohol having 1 to 12 carbon atoms include methanol, ethanol, butanol, hexanol, 2-ethylbutanol, heptanol, octanol, 2-ethylhexanol, decanol, dodecanol, butoxyethanol, butoxyethoxyethanol, and benzyl alcohol.
• organic phosphate ester or organic phosphite ester examples include trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tri(2-ethylhexyl) phosphate, tri(butoxyethyl) phosphate, tri(2-ethylhexyl) phosphite, isodecylphenyl phosphate, and triisopropyl phosphate.
• the ultraviolet-curable composition for printing of the present invention may contain a defoaming agent.
• the defoaming agent include silicone-based defoaming agents, acrylic polymer-based defoaming agents, vinyl ether polymer-based defoaming agents, and olefin polymer-based defoaming agents.
• the ultraviolet-curable composition for printing of the present invention may further contain various known additives, such as a viscosity modifier, a silane coupling agent, a sensitizer, a heat curing agent, a curing retarder, an antioxidant, a storage stabilizer, a dispersant, and a filler, within a range that does not impair the object of the present invention.
• various known additives such as a viscosity modifier, a silane coupling agent, a sensitizer, a heat curing agent, a curing retarder, an antioxidant, a storage stabilizer, a dispersant, and a filler.
• the UV-curable composition for printing of the present invention is substantially free of organic solvents.
• the content of organic solvents is 1.5 mass % or less relative to 100 mass % of the UV-curable composition for printing.
• the method for preparing the UV-curable composition for printing of the present invention can be, for example, a method in which the monofunctional (meth)acrylic monomer, the polyfunctional (meth)acrylic monomer, the photopolymerization initiator, the thermoplastic resin, and additives to be added as necessary are mixed using a mixer.
• the mixer include a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, and a three-roll mixer.
• the printing UV-curable composition of the present invention 1 is coated on a substrate, and the coated surface is not sealed, and the coated surface is irradiated with light having a wavelength of 280 nm to 480 nm in an atmospheric environment at an irradiance of 60 mW/cm 2 and an exposure dose of 900 mJ/cm 2.
• the lower limit of the shear storage modulus at 150°C is 5.0 x 10 4 Pa.
• the UV-curable composition for printing of the first invention has a high crosslink density and low interfacial adhesive strength, and therefore has excellent removability.
• the lower limit of the shear storage modulus of the cured product at 150° C. is preferably 7.0 ⁇ 10 4 Pa, and more preferably 8.0 ⁇ 10 4 Pa.
• the upper limit of the shear storage modulus of the cured product at 150° C. is preferably 5.0 ⁇ 10 6 Pa, and more preferably 1.0 ⁇ 10 6 Pa.
• the shear storage modulus of the cured product at 150° C. can be measured, specifically, by the following procedure, for example. That is, first, the printing UV-curable composition is coated on a release PET film as a substrate.
• the printing UV-curable composition is cured by irradiating the composition with light having a wavelength of 280 nm to 480 nm, preferably 315 nm to 480 nm, at an irradiance of 60 mW/cm 2 and an exposure dose of 900 mJ/cm 2 under atmospheric conditions using a light irradiation device, thereby obtaining a cured product having a thickness of 100 ⁇ m.
• a light irradiation device for example, M UVBA (manufactured by ITEC Co., Ltd.) can be used.
• the shear storage modulus at 150°C can be determined by performing dynamic viscoelasticity measurement on the obtained cured product using a dynamic viscoelasticity measuring device under the conditions of a shear method, a measurement temperature of -100°C to 200°C, a heating rate of 5°C/min, a strain of 1.0%, and a frequency of 1 Hz.
• the shear storage modulus of the cured product at 150°C can be increased by increasing the content of the polyfunctional (meth)acrylic monomer.
• the shear storage modulus of the cured product at 150°C can also be increased by using a polyfunctional (meth)acrylic monomer having a large number of (meth)acryloyl groups in one molecule.
• the composition for printing is applied to a substrate, and the upper surface of the coating is not sealed and is irradiated with light having a wavelength of 280 nm or more and 480 nm or less under atmospheric conditions at an irradiance of 60 mW/ cm2 and an exposure dose of 900 mJ/ cm2 .
• W1 mass of the cured product having a thickness of 100 ⁇ m obtained by immersing the composition in tetrahydrofuran, filtering the composition, and wiping off the tetrahydrofuran on the surface
• W1 mass of the cured product for which W1 was measured is measured after drying the product at 110 ° C.
• the lower limit of the swelling ratio represented by W1 / W2 is 1.0 and the upper limit is 6.0.
• the printing ultraviolet curable composition of the present invention 1 is coated on a substrate, and the coated surface is not sealed, and in an atmospheric environment, light having a wavelength of 280 nm to 480 nm is irradiated under conditions of irradiance 60 mW/cm 2 and dose 900 mJ/cm 2.
• the cured product having a thickness of 100 ⁇ m is immersed in tetrahydrofuran, filtered, and the mass measured within 3 minutes after wiping off the tetrahydrofuran on the surface is W 1 (g), and the mass measured after drying for 60 minutes at 110 ° C.
• the swelling ratio represented by W 1 /W 2 has a preferred lower limit of 1.0 and a preferred upper limit of 6.0, as long as the total irradiance is 60 mW/cm 2 and the dose is 900 mJ/cm 2 , light of multiple wavelengths in the wavelength range of 280 nm to 480 nm may be irradiated (the same applies to the glass transition temperature of the cured product described later).
• a PET film having a release treatment applied to its surface is suitably used as the substrate.
• the ultraviolet-curable composition for printing of the present invention has excellent removability.
• a preferred upper limit of the swelling ratio of the cured product in the ultraviolet-curable composition for printing of the second invention is 10.
• a more preferred upper limit of the swelling ratio of the cured product in the ultraviolet-curable composition for printing of the first invention is 10.
• the swelling ratio of the cured product can be measured, specifically, for example, according to the following procedure. That is, first, the printing UV-curable composition is coated on a release PET film as a substrate.
• the printing UV-curable composition is cured by irradiating the composition with light having a wavelength of 280 nm to 480 nm, preferably 315 nm to 480 nm, at an irradiance of 60 mW/cm 2 and an exposure dose of 900 mJ/cm 2 under atmospheric conditions using a light irradiation device, thereby obtaining a cured product having a thickness of 100 ⁇ m.
• a light irradiation device for example, M UVBA (manufactured by ITEC Co., Ltd.) can be used. Approximately 0.1 g of the resulting cured product is weighed out and immersed in tetrahydrofuran at 23° C.
• the swelling ratio of the cured product can be obtained by dividing W 1 by W 2 .
• the swelling ratio of the cured product can be reduced by increasing the content of the polyfunctional (meth)acrylic monomer.
• the swelling ratio of the cured product can also be reduced by using a polyfunctional (meth)acrylic monomer having a large number of (meth)acryloyl groups in one molecule.
• the printing UV-curable composition of the second invention has a glass transition temperature of 70° C. in a cured product having a thickness of 100 ⁇ m obtained by applying the printing UV-curable composition on a substrate and irradiating the coated surface with light having a wavelength of 280 nm or more and 480 nm or less at an irradiance of 60 mW/cm 2 and an exposure dose of 900 mJ/cm 2 in an atmospheric environment without sealing the coated surface.
• the printing UV-curable composition of the first ... present invention has a glass transition temperature of 70° C. or less, and thus has excellent removability.
• the cured product has a glass transition temperature of 55° C. in a cured product.
• the lower limit of the glass transition temperature of the cured product is preferably -30°C, and more preferably -20°C.
• the glass transition temperature of the cured product can be measured, specifically, for example, according to the following procedure. That is, first, the printing UV-curable composition is coated on a release PET film as a substrate.
• the printing UV-curable composition is cured by irradiating the composition with light having a wavelength of 280 nm to 480 nm, preferably 315 nm to 480 nm, at an irradiance of 60 mW/cm 2 and an exposure dose of 900 mJ/cm 2 under atmospheric conditions using a light irradiation device, thereby obtaining a cured product having a thickness of 100 ⁇ m.
• a light irradiation device for example, M UVBA (manufactured by ITEC Co., Ltd.) can be used.
• the resulting cured product is subjected to dynamic viscoelasticity measurement using a dynamic viscoelasticity measuring device under the conditions of a shear method, a measurement temperature of ⁇ 100° C. to 200° C., a heating rate of 5° C./min, a strain of 1.0%, and a frequency of 1 Hz.
• the tan ⁇ peak temperature when the dynamic viscoelasticity measurement is performed can be determined as the glass transition temperature.
• the higher the proportion of monomer components with a higher glass transition temperature the higher the glass transition temperature of the cured product.
• the higher the proportion of monomer components with a lower glass transition temperature the lower the glass transition temperature of the cured product. Therefore, by adjusting the blending ratio of these monomer components, the glass transition temperature of the cured product can be adjusted.
• the ultraviolet-curable composition for printing of the present invention 1 has a viscosity measured at 25° C. using an E-type viscometer, with a preferred lower limit of 0.1 mPa ⁇ s and a preferred upper limit of 100,000 mPa ⁇ s. When the viscosity is within this range, the ultraviolet-curable composition for printing of the present invention 1 can be suitably applied by screen printing or flexographic printing.
• the more preferred lower limit of the viscosity of the ultraviolet-curable composition for printing of the present invention 1 is 0.5 mPa ⁇ s and a more preferred upper limit is 50,000 mPa ⁇ s.
• the viscosity of the ultraviolet-curable composition for printing of present invention 2 is not limited and is adjusted depending on the application method.
• the preferred lower limit of the viscosity at 25° C. is 3.5 Pa s and the preferred upper limit is 100 Pa s
• the preferred lower limit of the viscosity at 25° C. is 0.5 Pa s and the preferred upper limit is 1.5 Pa s.
• the viscosity can be measured, for example, by using a VISCOMETER TV-22 (manufactured by Toki Sangyo Co., Ltd.) as an E-type viscometer and appropriately selecting a rotation speed of 1 to 100 rpm from the optimum torque number in each viscosity range with an appropriate cone plate.
• the UV-curable composition for printing of the present invention is used for printing. If a pressure-sensitive adhesive layer is formed by applying a desired pattern on an adherend (substrate) by printing, there is an advantage that the cutting process can be omitted compared to the case where a sheet-shaped composition is cut just before lamination to obtain a composition of a desired shape. As a result, it is possible to suppress the generation of waste and reduce the environmental load.
• the ultraviolet ray curable composition for printing of the present invention is preferably used for screen printing or flexographic printing.
• the present invention also provides a method for producing a laminate, in which the printing ultraviolet-curable composition of the present invention is applied onto a first adherend, the composition is exposed to light to form an adhesive layer, and a second adherend is attached onto the adhesive layer to produce a laminate.
• the method for applying the ultraviolet-curable composition for printing is preferably screen printing or flexographic printing.
• the ultraviolet-curable composition for printing is preferably applied partially onto the first adherend.
• the present invention can provide an ultraviolet-curable composition for printing that has excellent printability and removability.
• the present invention can also provide a method for producing a laminate using the ultraviolet-curable composition for printing.
• the obtained UV-curable composition for printing was applied onto a release PET film (manufactured by Nippa Corporation, "1-E", thickness 50 ⁇ m) using an applicator.
• a batch-type UV LED curing device was used to simultaneously irradiate UV light with a wavelength of 365 nm and an illuminance of 20 mW/ cm2 and light with a wavelength of 405 nm and an illuminance of 40 mW/ cm2 so that the total irradiation amount was 900 mJ/ cm2 , thereby curing the UV-curable composition for printing and obtaining a cured product with a thickness of 100 ⁇ m.
• M UVBA manufactured by ITEC Co., Ltd.
• the cured product was subjected to dynamic viscoelasticity measurement using a dynamic viscoelasticity measuring device (manufactured by IT Measurement & Control Co., Ltd., "DVA-200") under the conditions of a shear method, a measurement temperature of -100°C to 200°C, a heating rate of 5°C/min, a strain of 1.0%, and a frequency of 1 Hz to determine the shear storage modulus at 150°C, and the tan ⁇ peak temperature was determined as the glass transition temperature.
• a dynamic viscoelasticity measuring device manufactured by IT Measurement & Control Co., Ltd., "DVA-200
• a shear method a measurement temperature of -100°C to 200°C
• a heating rate of 5°C/min a strain of 1.0%
• a frequency of 1 Hz to determine the shear storage modulus at 150°C
• the release PET film on the opposite side to the transfer surface was peeled off, and the exposed surface was attached to a SUS substrate and pressed by moving it back and forth with a 2 kg roller to obtain a test piece.
• the obtained test piece was adjusted to 25°C and stored for 24 hours.
• the adhesive strength of the test piece after storage was measured by performing a 90° peel test at 25°C and a peel speed of 300 mm/min using an angle variable peel force measuring device (manufactured by Kyowa Interface Science Co., Ltd., "VPA-2").
• the adhesive strength of the test piece after storage for 7 days was also measured in the same manner.
• the SUS substrate after the 90° peel test on the test piece stored at 25° C.
• CBA Ethyl carbitol acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., "Viscoat #190")
• #192 Phenoxyethyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., "Viscoat #192")
• #216 2-butylcarbamoyloxyethyl acrylate (manufactured by Osaka Organic Chemical Industry Ltd., "Viscoat #216")
• M140 N-acryloyloxyethylhexahydrophthalimide (manufactured by Toagosei Co., Ltd.) (Nitrogen Compounds Containing Polymerizable Carbon-Carbon Double Bonds)
• NVC N-vinyl- ⁇ -caprolactam (Tokyo Chemical Industry Co., Ltd.)
• NPMI N-phenylmaleimide (manufactured by Nippon Shokubai Co.
• the obtained UV-curable composition for printing was applied onto a release PET film (manufactured by Nippa Corporation, "1-E", thickness 50 ⁇ m) using an applicator. Thereafter, without sealing the upper surface of the coating, in an atmospheric environment, a batch-type UV LED curing device was used to simultaneously irradiate UV light with a wavelength of 365 nm and an illuminance of 20 mW/ cm2 and light with a wavelength of 405 nm and an illuminance of 40 mW/ cm2 so that the total irradiation amount was 900 mJ/ cm2 , thereby curing the UV-curable composition for printing and obtaining a cured product with a thickness of 100 ⁇ m.
• the release PET film on the opposite side to the transfer surface was peeled off, and the exposed surface was attached to a SUS substrate and pressed by moving it back and forth with a 2 kg roller to obtain a test piece.
• the obtained test piece was adjusted to 25 ° C. and stored for 24 hours.
• a 90 ° peel test was performed at 25 ° C. and a peel speed of 300 mm / min using an angle variable peel force measuring device (manufactured by Kyowa Interface Science Co., Ltd., "VPA-2”) to measure the adhesive strength.
• the adhesive strength of the test piece after adjustment to 40 ° C. and storage for 7 days was also measured in the same manner.
• the SUS substrate after the 90° peel test on the test piece stored at 25° C. for 24 hours was observed to check for the presence or absence of peeling residue, and removability was evaluated according to the following criteria. ⁇ : No peeling residue, and adhesive strength after storage at 25° C. for 24 hours is less than 8.0 N/inch. ⁇ : Peeling residue is present, or no peeling residue is present, but adhesive strength after storage at 25° C. for 24 hours is 8.0 N/inch or more.
• the present invention can provide an ultraviolet-curable composition for printing that has excellent printability and removability.
• the present invention can also provide a method for producing a laminate using the ultraviolet-curable composition for printing.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Laminated Bodies (AREA)
• Polymerisation Methods In General (AREA)
• Inks, Pencil-Leads, Or Crayons (AREA)

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• 2023
  • 2023-11-30 JP JP2024540630A patent/JPWO2024117222A1/ja active Pending
  • 2023-11-30 WO PCT/JP2023/042937 patent/WO2024117222A1/ja not_active Ceased
  • 2023-12-01 TW TW112146811A patent/TW202440817A/zh unknown

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