WO2015052821A1 - Agent de revêtement pour l'impression et film à revêtement pour l'impression - Google Patents

Agent de revêtement pour l'impression et film à revêtement pour l'impression Download PDF

Info

Publication number
WO2015052821A1
WO2015052821A1 PCT/JP2013/077686 JP2013077686W WO2015052821A1 WO 2015052821 A1 WO2015052821 A1 WO 2015052821A1 JP 2013077686 W JP2013077686 W JP 2013077686W WO 2015052821 A1 WO2015052821 A1 WO 2015052821A1
Authority
WO
WIPO (PCT)
Prior art keywords
printing
coating agent
resin
film
coating
Prior art date
Application number
PCT/JP2013/077686
Other languages
English (en)
Japanese (ja)
Inventor
那須　健司
直希 神谷
Original Assignee
リンテック株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by リンテック株式会社 filed Critical リンテック株式会社
Priority to JP2015517532A priority Critical patent/JP5844010B2/ja
Priority to PCT/JP2013/077686 priority patent/WO2015052821A1/fr
Publication of WO2015052821A1 publication Critical patent/WO2015052821A1/fr

Links

Classifications

    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/06—Polyurethanes from polyesters
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/5263—Macromolecular coatings characterised by the use of polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • B41M5/5272—Polyesters; Polycarbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/5263—Macromolecular coatings characterised by the use of polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • B41M5/5281—Polyurethanes or polyureas
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic

Definitions

  • the present invention relates to a printing coating agent and a printing coating film, and more particularly to a printing coating agent and a printing film using a metal-based crosslinking accelerator other than a tin-based compound having a butyl group.
  • organic coating agents are mainly used to improve the adhesion of ink to the film substrate.
  • a cross-linking agent is added to an organic coating agent in order to improve the durability of the coating film or impart performance, but a cross-linking accelerator should be added depending on the reactivity of the cross-linking agent.
  • tin-based compounds having a butyl group such as tributyltin laurylate and dibutyltin dilaurate have been used as reaction accelerators for urethanization reactions, but there are concerns that these compounds may adversely affect the human body. There is a movement to limit its use, which is not preferable in terms of environmental problems.
  • a coating agent that does not contain a metal compound as a reaction accelerator see Patent Document 1
  • the reaction may be insufficient depending on the type of the crosslinking agent. JP 2007-021862 A
  • the present invention has been made in view of the above-described prior art, the film base material and the coating agent layer have excellent adhesion, and the printing ink has excellent adhesion and blocking resistance. It aims at providing the coating agent for printing which can form a coating agent layer, and the coating film for printing manufactured using it.
  • the present inventors have developed a metal-based cross-linking accelerator as a cross-linking accelerator in a printing coating agent containing a polyester-based resin as a resin component and an isocyanate-based compound as a cross-linking agent.
  • the present invention contains a polyester resin, an isocyanate compound as a crosslinking agent, and a metal crosslinking accelerator (however, excluding a tin compound having a butyl group). Is to provide.
  • the present invention provides the printing coating agent, wherein the metal-based crosslinking accelerator is a tin-based crosslinking accelerator, a bismuth-based crosslinking accelerator, a titanium-based crosslinking accelerator, a vanadium-based crosslinking accelerator, or a zirconium-based crosslinking accelerator.
  • a coating agent for printing which is at least one selected from an aluminum-based crosslinking accelerator and a nickel-based crosslinking accelerator.
  • this invention provides the coating agent for printing whose said isocyanate type compound is hexamethylene diisocyanate in the said coating agent for printing.
  • this invention provides the coating agent for printing whose said polyester-type resin is urethane-modified polyester-type resin in the said coating agent for printing.
  • this invention provides the coating film for printing characterized by apply
  • this invention provides the coating film for printing whose said film base material is a film base material which consists of a polyethylene terephthalate resin, a polypropylene resin, or a polyethylene resin in the said coating film for printing.
  • this invention provides the coating film for printing in which the adhesive layer is provided in the back surface of the said film base material in the said coating film for printing.
  • the coating agent for printing of the present invention can form a coating agent layer in which the film base material and the coating agent layer have excellent adhesion, and the printing ink has excellent adhesion and blocking resistance. .
  • the coating film for printing of this invention has the adhesiveness which the film base material and the coating agent layer were excellent, and is excellent also in the adhesiveness of printing ink, and blocking resistance.
  • the printing coating agent of the present invention is a printing coating agent containing a polyester resin as a resin component.
  • polyester resins include polyester resins and urethane-modified polyester resins.
  • the polyester resin is preferably a polyester copolymer resin obtained by copolymerizing a dicarboxylic acid and a glycol compound.
  • the dicarboxylic acid include aromatic dicarboxylic acids such as terephthalic acid, phthalic acid, isophthalic acid, sulfoterephthalic acid, and 2,6-naphthalenedicarboxylic acid, and aliphatic dicarboxylic acids such as oxalic acid, sebacic acid, succinic acid, and adipic acid.
  • glycol compound examples include ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, 1,2-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, p-xylene glycol, triethylene glycol and the like are preferably used.
  • the urethane-modified polyester resin examples include those having a urethane bond in the polyester resin.
  • the urethane-modified polyester resin can be obtained, for example, by reacting a polyester resin having two or more functional groups such as a hydroxyl group in one molecule with a polyisocyanate compound.
  • the polyisocyanate compound used for urethane modification of the polyester resin can be used alone or in combination of two or more.
  • the polyester resin is preferably a urethane-modified polyester resin, and particularly preferably a urethane-modified polyester resin having a basic structure of an aromatic polyester.
  • the basic structure of the aromatic polyester is one having a repeating unit derived from an aromatic compound in the main-chain polyester structure. For example, one or both of a dicarboxylic acid and a glycol compound which are part or all of a copolymer raw material Is obtained when is an aromatic compound.
  • Polyester resin may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the number average molecular weight of the polyester-based resin is preferably from 5,000 to 100,000, more preferably from 10,000 to 60,000.
  • the hydroxyl value of the polyester-based resin is preferably 1 to 50 mgKOH / g, more preferably 1 to 25 mgKOH / g, and further preferably 1.5 to 20 mgKOH / g.
  • the acid value of the polyester resin is preferably 0 to 40 mgKOH / g, and more preferably 0 to 30 mgKOH / g.
  • the glass transition temperature of the polyester resin is preferably 40 to 105 ° C, more preferably 50 to 100 ° C, and further preferably 70 to 95 ° C.
  • the polyester-type resin which has a glass transition temperature lower by 20 degreeC or more than the glass transition temperature of the said polyester-type resin is used.
  • the glass transition temperature is preferably ⁇ 30 to 15 ° C., more preferably ⁇ 25 to 5 ° C. As the glass transition temperature falls within the above preferable range and the more preferable range, the effect of improving the adhesion of the coating agent layer and preventing blocking can be further exhibited.
  • polyester resin for improving the adhesion of the coating agent layer and preventing blocking examples include a polyester resin and a urethane-modified polyester resin as in the case of the polyester resin.
  • the polyester resin for improving the adhesion of the coating agent layer and preventing blocking is preferably a polyester copolymer resin obtained by copolymerizing a dicarboxylic acid and a glycol compound.
  • Specific examples of the dicarboxylic acid and the glycol compound include the same ones as described above.
  • examples of the urethane-modified polyester resin include those having a urethane bond in the polyester resin.
  • the urethane-modified polyester resin can be obtained, for example, by reacting a polyester resin having two or more functional groups such as a hydroxyl group in one molecule with a polyisocyanate compound.
  • a polyisocyanate compound the same compounds as described above can be used.
  • the polyisocyanate compound used for urethane modification of the polyester resin can be used alone or in combination of two or more.
  • the polyester resin for improving the adhesion of the coating agent layer and preventing blocking may be used singly or in combination of two or more.
  • the former polyester-based resin is a urethane-modified polyester resin
  • the latter is also preferably a urethane-modified polyester resin for improving adhesion and blocking of the coating agent layer used in combination with the latter
  • the former polyester-based resin is a urethane-modified polyester resin having a basic structure of an aromatic polyester
  • the latter polyester resin for improving adhesion and preventing blocking of the coating agent layer used in combination is also the basic structure of an aromatic polyester. It is preferable that it is a urethane-modified polyester resin having.
  • the number average molecular weight, the hydroxyl value, and the acid value of the polyester resin for preventing and blocking the coating agent layer become the following preferable range, more preferable range, and further preferable range, the adhesion improvement of the coating agent layer and The effect of preventing blocking can be further exhibited.
  • the number average molecular weight is preferably from 5,000 to 100,000, more preferably from 10,000 to 60,000.
  • the hydroxyl value is preferably 1 to 50 mgKOH / g, more preferably 1 to 15 mgKOH / g, and still more preferably 1.5 to 10 mgKOH / g.
  • the acid value is preferably 0 to 20 mgKOH / g, more preferably 0 to 8 mgKOH / g, and further preferably 0 to 3 mgKOH / g.
  • the mixing ratio of the polyester resin for improving the adhesion of the coating agent layer and preventing blocking is preferably 1 to 50% by mass, more preferably 10 to 45% by mass, and more preferably 15 to 15% by mass with respect to the total mass of all polyester resins. 40% by mass is particularly preferred.
  • the printing coating agent of the present invention contains an isocyanate compound as a crosslinking agent together with the polyester resin.
  • the isocyanate compound as a crosslinking agent, various isocyanate compounds can be used as long as they react with a functional group such as a hydroxyl group of the polyester resin to form a crosslinked structure.
  • the isocyanate compound is preferably a polyisocyanate compound having two or more isocyanate groups per molecule.
  • the polyisocyanate compound include diisocyanate compounds, triisocyanate compounds, tetraisocyanate compounds, pentaisocyanate compounds, and hexaisocyanate compounds.
  • aromatic compounds such as tolylene diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate.
  • Polyisocyanate cycloaliphatic isocyanate compounds such as dicyclohexylmethane-4,4-diisocyanate, bicycloheptane triisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, hydrogenated xylylene diisocyanate; pentamethylene diisocyanate, hexamethylene Diisocyanate, heptamethylene diisocyanate Chromatography, tri-methyl-hexamethylene diisocyanate, and aliphatic isocyanate compounds such as lysine diisocyanate.
  • cycloaliphatic isocyanate compounds such as dicyclohexylmethane-4,4-diisocyanate, bicycloheptane triisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, methylcyclohe
  • modified products such as biurets and isocyanurates of these compounds, and adducts that are the reaction products of these compounds with non-aromatic low-molecular active hydrogen-containing compounds such as ethylene glycol, trimethylolpropane, and castor oil.
  • non-aromatic low-molecular active hydrogen-containing compounds such as ethylene glycol, trimethylolpropane, and castor oil.
  • isocyanate compounds aliphatic isocyanate compounds are preferred, aliphatic diisocyanate compounds are more preferred, and pentamethylene diisocyanate, hexamethylene diisocyanate, and heptamethylene diisocyanate are particularly preferred.
  • An isocyanate type compound may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the coating agent for printing of the present invention contains a metal-based crosslinking accelerator (excluding a tin-based compound having a butyl group) together with the isocyanate compound as the crosslinking agent.
  • a metal-based crosslinking accelerator include a tin crosslinking accelerator, a bismuth crosslinking accelerator, a titanium crosslinking accelerator, a vanadium crosslinking accelerator, a zirconium crosslinking accelerator, an aluminum crosslinking accelerator, and a nickel crosslinking.
  • the metal crosslinking accelerator include accelerators. Of these, tin-based crosslinking accelerators and bismuth-based crosslinking accelerators are preferably used.
  • the tin-based crosslinking accelerator is an organometallic compound of tin, which is a compound having a structure such as an alkoxide, a carboxylate, or a chelate, and is preferably an acetylacetone complex, an acetylacetonate, an octylate compound, or a naphthene of these metals. An acid compound etc. are mentioned.
  • bismuth-based crosslinking accelerator, titanium-based crosslinking accelerator, vanadium-based crosslinking accelerator, zirconium-based crosslinking accelerator, aluminum-based crosslinking accelerator, and nickel-based crosslinking accelerator are bismuth, titanium, and vanadium, respectively.
  • An organometallic compound of zirconium, aluminum, or nickel which has a structure such as alkoxide, carboxylate, chelate, etc., preferably acetylacetone complex, acetylacetonate, octylic acid compound or naphthenic acid of these metals Compound etc. are mentioned.
  • Specific examples of the metal acetylacetone complex include acetylacetone tin, acetylacetone titanium, acetylacetone vanadium, acetylacetone zirconium, acetylacetone aluminum, and acetylacetone nickel.
  • acetylacetonate examples include tin acetylacetonate, bismuth acetylacetonate, titanium acetylacetonate, vanadium acetylacetonate, zirconium acetylacetonate, aluminum acetylacetonate, nickel acetylacetonate and the like.
  • octylic acid compound examples include bismuth 2-ethylhexylate, nickel 2-ethylhexylate, zirconium 2-ethylhexylate, tin 2-ethylhexylate, and the like.
  • the naphthenic acid compound examples include bismuth naphthenate, nickel naphthenate, zirconium naphthenate, tin naphthenate, and the like.
  • the tin-based crosslinking accelerator the general formula R x Sn (L) (4-X) (wherein R is an alkyl group having 1 to 3 or 5 to 25 carbon atoms, or an aryl group, and L is an alkyl group) And an organic group other than an aryl group, or an inorganic group, and x is 1, 2 or 4.
  • the alkyl group of R is preferably an alkyl group having 5 to 25 carbon atoms, more preferably an alkyl group having 5 to 20 carbon atoms, and the aryl group of R is not particularly limited, 6-20 aryl groups are preferred.
  • each R may be the same or different.
  • L is preferably an aliphatic carboxylic acid, aromatic carboxylic acid or aromatic sulfonic acid having 2 to 20 carbon atoms, more preferably an aliphatic carboxylic acid having 2 to 20 carbon atoms.
  • Examples of the aliphatic carboxylic acid having 2 to 20 carbon atoms include an aliphatic monocarboxylic acid having 2 to 20 carbon atoms and an aliphatic dicarboxylic acid having 2 to 20 carbon atoms.
  • each L may be the same or different.
  • a metal type crosslinking accelerator may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the content ratio of the polyester resin and the isocyanate compound as the crosslinking agent is 1 to 30 parts by mass of the isocyanate compound as the crosslinking agent with respect to 100 parts by mass of the polyester resin in solid ratio.
  • the content ratio of the isocyanate compound as a crosslinking agent and the metal crosslinking accelerator is 100 parts by mass of the polyester resin.
  • the metal-based crosslinking accelerator is preferably 0.001 to 5 parts by mass, more preferably 0.005 to 2 parts by mass in terms of metal amount, and 0.01 ⁇ 1 part by mass is particularly preferred.
  • the printing coating agent of the present invention contains a diluent medium in addition to the polyester resin, the isocyanate compound as a crosslinking agent, and a metal crosslinking accelerator (except for a tin compound having a butyl group).
  • a diluent medium in addition to the polyester resin, the isocyanate compound as a crosslinking agent, and a metal crosslinking accelerator (except for a tin compound having a butyl group).
  • the dilution medium include an organic dilution medium and an aqueous dilution medium, and an organic dilution medium is preferable.
  • the organic dilution medium include aromatic solvents such as toluene and xylene, aliphatic ketones such as methyl ethyl ketone and diethyl ketone, and organic solvents such as alicyclic ketones such as cyclohexanone. Can be used in combination.
  • the content of resin solids such as an isocyanate compound as a polyester resin and a crosslinking agent is preferably 0.5 to 10% by mass, and preferably 1 to 7% by mass. More preferred.
  • various fillers such as organic fillers and inorganic fillers can be blended in the coating agent for printing of the present invention in order to improve slipperiness and obtain a matte feeling.
  • the organic filler examples include resin powder such as polystyrene resin, acrylonitrile-butadiene-styrene copolymer resin (ABS resin), polycarbonate resin, acrylic resin such as methyl methacrylate, or a mixture thereof.
  • the inorganic filler examples include inorganic oxides such as silica and alumina, and metal powders such as gold powder and silver powder.
  • the blending amount of the filler is preferably 0.1 to 20 parts by mass, and more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the total amount of the resin component and the crosslinking agent of the printing coating agent.
  • the coating agent for printing of the present invention preferably has a gel fraction of 50% or more, particularly preferably 60% or more after 14 days of coating. Below this range, the cohesive force of the coating agent for printing becomes insufficient, which may cause cohesive failure of the coating agent layer. Further, the ratio of the gel fraction after 14 days of coating to the gel fraction after 3 days of coating (gel fraction after 14 days of coating / gel fraction after 3 days of coating) is preferably within 4.5. Is more preferably within 2.5, and particularly preferably within 1.5. Below this range, the blocking resistance at the time of production may be insufficient.
  • the coating film for printing of the present invention is obtained by applying the above-mentioned printing coating agent to the surface of a film substrate and providing a coating agent layer for printing.
  • the amount of the coating agent for printing applied to the film substrate is usually such that the thickness of the coating layer for printing after drying is in the range of 10 to 600 nm, preferably in the range of 20 to 400 nm, particularly preferably in the range of 30 to 200 nm. Such an amount is preferred.
  • Various plastic films can be used as the film substrate.
  • the film substrate include, for example, polyolefin resins such as polyethylene resin and polypropylene resin, polyester resins such as polyethylene terephthalate resin, polyethylene naphthalate resin and polybutylene terephthalate resin, polyvinyl chloride resin, polystyrene resin, acrylonitrile-butadiene- Styrene copolymer resin (ABS resin), polyurethane resin, polycarbonate resin, polyamide resin, polyimide resin, poly (meth) acrylate, polybutene resin, polybutadiene resin, polymethylpentene resin, acrylic urethane resin, ethylene-vinyl acetate resin , Ethylene- (meth) acrylic ester resin, ionomer resin, thermoplastic elastomer resin, fluororesin, and mixtures of two or more of these Film or synthetic resin, two or more layers of laminated film of these same or different, and synthetic paper.
  • polyolefin resins such as polyethylene resin and polyprop
  • the film which consists of a polyester resin or polyolefin resin is preferable, and the film base material which consists of a polyethylene terephthalate resin, a polypropylene resin, or a polyethylene resin is mentioned more preferably.
  • the thickness of the film substrate is not particularly limited, but is usually preferably 5 to 350 ⁇ m, more preferably 10 to 300 ⁇ m, and particularly preferably 15 to 250 ⁇ m.
  • Examples of the method for applying the printing coating agent to the film substrate include conventionally known methods such as bar coating, knife coating, roll coating, blade coating, and die coating.
  • an anchor coat layer is provided on the surface of the film substrate as necessary, and the printing coat layer is provided on the surface of the anchor coating layer.
  • the anchor coat agent used for providing the anchor coat layer include a polyurethane anchor coat agent and a polyester anchor coat agent.
  • the drying is usually preferably performed at 60 to 130 ° C, more preferably 80 to 120 ° C.
  • the drying time is not particularly limited, but usually 10 seconds to 5 minutes is sufficient.
  • the coated film for printing of the present invention can be used as an adhesive label by providing an adhesive layer on the back surface of the film substrate.
  • the back surface of the film substrate may be subjected to an easy adhesion treatment in order to further increase the adhesion with the pressure-sensitive adhesive layer.
  • an easy adhesion treatment in order to further increase the adhesion with the pressure-sensitive adhesive layer.
  • a corona discharge process etc. are mentioned.
  • Various pressure-sensitive adhesives can be used as the pressure-sensitive adhesive used in the pressure-sensitive adhesive layer.
  • Specific examples of the adhesive include, for example, natural rubber-based adhesives, synthetic rubber-based adhesives, acrylic resin-based adhesives, polyvinyl ether resin-based adhesives, urethane resin-based adhesives, silicone resin-based adhesives, and the like.
  • an acrylic resin-based adhesive, a rubber-based adhesive, a silicone resin-based adhesive, etc. are used.
  • the pressure-sensitive adhesive may be a solvent-type pressure-sensitive adhesive, a water-type pressure-sensitive adhesive, or a strong pressure-sensitive adhesive or a re-peelable pressure-sensitive adhesive.
  • you may provide a peeling sheet in the surface on the opposite side to the base film side of an adhesive layer.
  • the release sheet is not particularly limited. Examples of the base material of the release sheet include paper, synthetic paper, and synthetic resin film.
  • a paper base such as fine paper, glassine paper, coated paper, a paper base such as a laminated paper obtained by laminating a thermoplastic resin such as polyethylene or polypropylene to these paper bases, and high-quality paper
  • a paper base or the like that is subjected to a sealing treatment with glassine paper, coated paper, etc. with cellulose, starch, polyvinyl alcohol, acrylic-styrene resin, or the like.
  • plastic synthetic resin films include films made of polyolefin resins such as polyethylene resins and polypropylene resins, films made of polyester resins such as polybutylene terephthalate resins and polyethylene terephthalate resins, and films obtained by subjecting these synthetic resin films to easy adhesion treatment. It is desirable that these are coated with a release agent.
  • the release agent include fluorine resins, silicone resins, olefin resins, and long-chain alkyl group-containing carbamates.
  • various inks such as ultraviolet curable ink are used.
  • the ultraviolet curable ink various ultraviolet curable inks are used, and polyacrylate ultraviolet curable inks are preferable.
  • Example 1 Preparation of coating agent for printing Urethane-modified polyester resin having a basic structure of aromatic polyester (manufactured by Toyobo Co., Ltd., trade name “Byron UR1700”, number average molecular weight 16000, hydroxyl value 19 mgKOH / g, acid value 26 mgKOH / G, 70 parts by mass of glass transition temperature 92 ° C., urethane-modified polyester resin having a basic structure of aromatic polyester (manufactured by Toyobo Co., Ltd., trade name “Byron UR8700”, number average molecular weight 32000, hydroxyl value 2-4 mg KOH) / G, acid value of less than 1 mg KOH / g, glass transition temperature -22 ° C.
  • Byron UR1700 number average molecular weight 16000, hydroxyl value 19 mgKOH / g, acid value 26 mgKOH / G, 70 parts by mass of glass transition temperature 92 ° C.
  • hexamethylene diisocyanate (trade name “Coronate HL”, manufactured by Nippon Polyurethane Co., Ltd.) as a crosslinking agent, bismuth-based crosslinking accelerator ( Product name “Pucat 25” manufactured by Nippon Chemical Industry Co., Ltd. 25 parts by mass) 0.05 part by mass, and 900 parts by mass of toluene, 900 parts by mass of methyl ethyl ketone, and 90 parts by mass of cyclohexanenone were mixed to obtain a coating agent for printing.
  • hexamethylene diisocyanate (trade name “Coronate HL”, manufactured by Nippon Polyurethane Co., Ltd.) as a crosslinking agent
  • bismuth-based crosslinking accelerator Product name “Pucat 25” manufactured by Nippon Chemical Industry Co., Ltd. 25 parts by mass) 0.05 part by mass
  • 900 parts by mass of toluene 900 parts by mass of methyl ethyl ketone,
  • Example 2 In Example 1 (1), the compounding amount of the bismuth-based crosslinking accelerator (trade name “Pucat 25” manufactured by Nippon Chemical Industry Co., Ltd.) was changed to 0.30 parts by mass instead of 0.05 parts by mass. Produced a coated film for printing and a pressure-sensitive adhesive sheet for printing in the same manner as in Example 1.
  • Example 3 In Example 1 (1), the blending amount of the bismuth-based cross-linking accelerator (manufactured by Nippon Chemical Industry Co., Ltd., trade name “Pucat 25”) was changed to 1.00 parts by mass instead of 0.05 parts by mass. Produced a coated film for printing and a pressure-sensitive adhesive sheet for printing in the same manner as in Example 1.
  • Example 4 In Example 2 (1), Example 2 was used except that the amount of hexamethylene diisocyanate (trade name “Coronate HL” manufactured by Nippon Polyurethane Co., Ltd.) was changed to 5 parts by mass instead of 3 parts by mass. A coating film for printing and a pressure-sensitive adhesive sheet for printing were prepared in the same manner. (Example 5) In Example 1 (1), printing was carried out in the same manner as in Example 1 except that 1.5 parts by mass of silica filler (trade name “Aerosil 200”, average particle diameter of 12 nm, manufactured by Nippon Aerosil Co., Ltd.) was blended. Coating film and printing pressure-sensitive adhesive sheet were prepared.
  • silica filler trade name “Aerosil 200”, average particle diameter of 12 nm, manufactured by Nippon Aerosil Co., Ltd.
  • Example 6 In Example 1 (1), instead of 0.05 parts by mass of a bismuth-based crosslinking accelerator (trade name “Pucat 25”, manufactured by Nippon Chemical Industry Co., Ltd.), a vanadium-based crosslinking accelerator (acetylacetone vanadium, Nippon Chemical Industry Co., Ltd.) Coated film for printing in the same manner as in Example 1 except that the product name is “Narsemvanadil”, 19% by mass in terms of metal), 0.40 part by mass, and 3 parts by mass of silica filler is blended. A pressure-sensitive adhesive sheet for printing was prepared.
  • a bismuth-based crosslinking accelerator trade name “Pucat 25”, manufactured by Nippon Chemical Industry Co., Ltd.
  • a vanadium-based crosslinking accelerator acetylacetone vanadium, Nippon Chemical Industry Co., Ltd.
  • Example 7 In Example 1 (1), instead of 0.05 parts by mass of a bismuth-based crosslinking accelerator (manufactured by Nippon Chemical Industry Co., Ltd., trade name “Pucat 25”), a tin-based crosslinking accelerator (dioctyltin bis (2- A coating film for printing and a pressure-sensitive adhesive sheet for printing were prepared in the same manner as in Example 1 except that the amount was changed to 0.50 parts by mass (ethylhexyl malate) and 15% by mass in terms of metal).
  • a bismuth-based crosslinking accelerator manufactured by Nippon Chemical Industry Co., Ltd., trade name “Pucat 25”
  • a tin-based crosslinking accelerator dioctyltin bis (2- A coating film for printing and a pressure-sensitive adhesive sheet for printing were prepared in the same manner as in Example 1 except that the amount was changed to 0.50 parts by mass (ethylhexyl malate) and 15% by mass in terms of metal).
  • Example 8 In Example 1 (1), instead of 0.05 parts by mass of a bismuth-based crosslinking accelerator (trade name “Pucat 25” manufactured by Nippon Chemical Industry Co., Ltd.), an aluminum-based crosslinking accelerator (acetylacetone aluminum, Nippon Chemical Industry Co., Ltd.) A coated film for printing and a pressure-sensitive adhesive sheet for printing were prepared in the same manner as in Example 1 except that the product name was “Nursem Aluminum” (8% by mass in terms of metal amount) and 1.00 parts by mass. Created.
  • Example 9 A coating film for printing and a pressure-sensitive adhesive sheet for printing were prepared in the same manner as in Example 6 except that the silica filler was not blended in (1) of Example 6.
  • Example 10 In Example 1 (1), instead of 0.05 parts by mass of a bismuth-based crosslinking accelerator (trade name “Pucat 25” manufactured by Nippon Chemical Industry Co., Ltd.), a nickel-based crosslinking accelerator (nickel octylate metal soap) Manufactured by Nippon Kagaku Sangyo Co., Ltd., trade name “Nikka Octix Nickel, 11% by mass in terms of metal amount) 0.80 parts by mass, in the same manner as in Example 1, except that the coating film for printing, printing An adhesive sheet was prepared.
  • a bismuth-based crosslinking accelerator trade name “Pucat 25” manufactured by Nippon Chemical Industry Co., Ltd.
  • a nickel-based crosslinking accelerator nickel octylate metal soap
  • Example 11 In Example 2 (2), an oriented polypropylene resin film (OPP, manufactured by Toray Industries, Inc., trade name “Toray Co., Ltd., trade name“ Lumirror PET50 T-60 ”, thickness 50 ⁇ m) was used instead of polyester resin film (trade name“ A coating film for printing and a pressure-sensitive adhesive sheet for printing were prepared in the same manner as in Example 2 except that Olefan BO # 50 ", thickness 50 ⁇ m) was used.
  • OPP oriented polypropylene resin film
  • polyester resin film trade name“
  • a coating film for printing and a pressure-sensitive adhesive sheet for printing were prepared in the same manner as in Example 2 except that Olefan BO # 50 ", thickness 50 ⁇ m
  • Example 12 In Example 3 (2), an oriented polypropylene resin film (OPP, manufactured by Toray Industries, Inc., trade name “Toray, Inc., trade name“ Lumirror PET50 T-60 ”, thickness 50 ⁇ m)” was used instead of the polyester resin film (trade name “Lumirror PET50 T-60”, thickness 50 ⁇ m).
  • OPP oriented polypropylene resin film
  • Lumirror PET50 T-60 thickness 50 ⁇ m
  • a coating film for printing and a pressure-sensitive adhesive sheet for printing were prepared in the same manner as in Example 3 except that Olefan BO # 50 ", thickness 50 ⁇ m) was used.
  • Example 13 In Example 7 (2), instead of a polyester resin film (manufactured by Toray Industries, Inc., trade name “Lumirror PET50 T-60”, thickness 50 ⁇ m), an oriented polypropylene resin film (OPP, manufactured by Toray Industries, Inc., trade name “ A coating film for printing and a pressure-sensitive adhesive sheet for printing were prepared in the same manner as in Example 7 except that Olefan BO # 50 ”and a thickness of 50 ⁇ m were used. (Comparative Example 1) In Example 1 (1), a printing film was prepared in the same manner as in Example 1 except that no crosslinking accelerator was added.
  • OPP oriented polypropylene resin film
  • Example 2 In Example 1 (1), a printing film was produced in the same manner as in Example 1 except that the crosslinking agent and the crosslinking accelerator were not blended. The gel fraction of the coating agent layer, the adhesion between the film substrate and the coating agent layer, the printing adhesion, the blocking resistance and the thermal transfer printing property were evaluated and evaluated by the methods shown below. The results are shown in Tables 1 to 3.
  • the coating agent for printing obtained in Examples and Comparative Examples was applied to the surface of the release sheet so that the film thickness after drying was 2 ⁇ m, and 23 ° C., 50
  • the coating agent layer after 3 days and 14 days was peeled off from the release sheet for 3 days and 14 days at% RH, and a coating agent layer for gel fraction measurement was prepared.
  • the obtained coating agent layer was immersed in toluene at 23 ° C. for 72 hours, undissolved components were dried at 120 ° C. for 3 hours, and left to stand at 23 ° C. and 50% relative humidity for 3 hours to adjust the humidity. Then, the mass was measured, and the gel fraction was calculated by the following formula.
  • Adhesive tape (made by Nichiban Co., Ltd., trade name “Cellotape”) is pasted on the surface of the coating agent layer, and a cellotape peel test is performed in accordance with the cross-cut tape method of JIS K5600-5-6 (cross-cut method). The adhesion between the film substrate and the coating agent layer was evaluated based on the above criteria.
  • A The number of cells in which the coating agent layer remains after the cellophane peeling test is 95 or more per 100 cells.
  • (Circle) The number of squares in which a coating agent layer remains after a cellophane peeling test is 90 or more and 94 or less per 100 squares.
  • X The number of squares in which the coating agent layer remains after the cellophane peeling test is less than 90 per 100 squares.
  • a cross cut with a 1 mm width is applied to the surface of the printed layer, and an adhesive tape (product name “Cello Tape”, manufactured by Nichiban Co., Ltd.) is pasted on the surface of the printed layer that has been cross-cut into the grid pattern.
  • JIS K5600- A cello tape peeling test was conducted in accordance with the grid tape method of 5-6 (cross cut method), and the printing adhesion of the coating agent layer was evaluated according to the following criteria. (Double-circle): The number of the squares in which a printing layer remains after a cellophane peeling test is 95 or more per 100 squares.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Laminated Bodies (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Paints Or Removers (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

La présente invention concerne : un agent de revêtement pour l'impression, qui est caractérisé en ce qu'il contient une résine de polyester, un composé isocyanate servant d'agent de réticulation, et un accélérateur de réticulation à base de métal (excepté un composé à base d'étain avec un groupe butyle); et un film à revêtement pour l'impression, qui est produit en utilisant cet agent de revêtement pour l'impression. Un agent de revêtement pour l'impression de la présente invention et un film à revêtement pour l'impression, qui est produit en utilisant cet agent de revêtement pour l'impression, sont capables de former une couche d'agent de revêtement qui présente une excellente adhésion à une base de film, tout en présentant une excellente adhésion à une encre d'impression et une excellente résistance au blocage.
PCT/JP2013/077686 2013-10-07 2013-10-07 Agent de revêtement pour l'impression et film à revêtement pour l'impression WO2015052821A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2015517532A JP5844010B2 (ja) 2013-10-07 2013-10-07 印刷用コート剤及び印刷用コートフィルムの製造方法
PCT/JP2013/077686 WO2015052821A1 (fr) 2013-10-07 2013-10-07 Agent de revêtement pour l'impression et film à revêtement pour l'impression

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2013/077686 WO2015052821A1 (fr) 2013-10-07 2013-10-07 Agent de revêtement pour l'impression et film à revêtement pour l'impression

Publications (1)

Publication Number Publication Date
WO2015052821A1 true WO2015052821A1 (fr) 2015-04-16

Family

ID=52812668

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2013/077686 WO2015052821A1 (fr) 2013-10-07 2013-10-07 Agent de revêtement pour l'impression et film à revêtement pour l'impression

Country Status (2)

Country Link
JP (1) JP5844010B2 (fr)
WO (1) WO2015052821A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111087571A (zh) * 2019-12-27 2020-05-01 黄山中泽新材料有限公司 一种耐溶剂稀释型聚氨酯油墨连接料及其制备方法与应用

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1990001419A1 (fr) * 1988-08-13 1990-02-22 Dai Nippon Insatsu Kabushiki Kaisha Support d'enregistrement sensible a la chaleur
JPH05155164A (ja) * 1991-12-09 1993-06-22 Oji Paper Co Ltd 染料熱転写画像受容シート
JP2003005651A (ja) * 2001-06-18 2003-01-08 Sony Corp 染料熱転写受容シート
JP2004322319A (ja) * 2003-04-21 2004-11-18 Dainippon Printing Co Ltd 熱転写受像シート
JP2007154009A (ja) * 2005-12-02 2007-06-21 Kaneka Corp 硬化性組成物

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4779266B2 (ja) * 2001-09-07 2011-09-28 東ソー株式会社 ポリウレタン樹脂製造用触媒組成物及びポリウレタン樹脂の製造方法
DE102004060284A1 (de) * 2004-12-15 2006-06-29 Bayer Materialscience Ag Reaktive Polyurethan-Prepolymere mit einem geringen Gehalt an monomeren Diisocyanaten
JP5386771B2 (ja) * 2006-03-17 2014-01-15 横浜ゴム株式会社 有機金属触媒およびこれを含有する２液型ポリウレタン組成物

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1990001419A1 (fr) * 1988-08-13 1990-02-22 Dai Nippon Insatsu Kabushiki Kaisha Support d'enregistrement sensible a la chaleur
JPH05155164A (ja) * 1991-12-09 1993-06-22 Oji Paper Co Ltd 染料熱転写画像受容シート
JP2003005651A (ja) * 2001-06-18 2003-01-08 Sony Corp 染料熱転写受容シート
JP2004322319A (ja) * 2003-04-21 2004-11-18 Dainippon Printing Co Ltd 熱転写受像シート
JP2007154009A (ja) * 2005-12-02 2007-06-21 Kaneka Corp 硬化性組成物

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111087571A (zh) * 2019-12-27 2020-05-01 黄山中泽新材料有限公司 一种耐溶剂稀释型聚氨酯油墨连接料及其制备方法与应用

Also Published As

Publication number Publication date
JP5844010B2 (ja) 2016-01-13
JPWO2015052821A1 (ja) 2017-03-09

Similar Documents

Publication Publication Date Title
JP5509079B2 (ja) 粘着シート
JP6594637B2 (ja) 粘着シート、及び、光学部材
JP5746188B2 (ja) フィルム状基材の接着法
JP6030843B2 (ja) フレキソ印刷用シートおよびその製造方法
JP3886225B2 (ja) 両面粘着シ―ト類
JP5818561B2 (ja) 黒色箔状粘着剤および黒色粘着シート
JP2011026425A (ja) 粘着シート
JP6310711B2 (ja) 剥離シートおよび転写シート
JP2008222953A (ja) 粘着シート
WO2013108845A1 (fr) Feuille adhésive, sac de sang avec feuille adhésive, et son procédé de production
TWI499639B (zh) A release agent composition, a release film, and a subsequent film using the same
JP3819547B2 (ja) 両面粘着シ―ト類
JP5844010B2 (ja) 印刷用コート剤及び印刷用コートフィルムの製造方法
JP2012216619A (ja) 表面保護用シート
JP6594636B2 (ja) 粘着シート、及び、光学部材
JP4109710B2 (ja) シ―ル材
JP4523777B2 (ja) 剥離シート
JP6306394B2 (ja) 印刷用シート、塗工液および印刷用シートの製造方法
JP7203624B2 (ja) 光学透明粘着シート、積層シート及び貼り合わせ構造物
JP6062265B2 (ja) 印刷用シート、その印刷用シートを形成するための塗工液、およびその塗工液を用いる印刷用シートの製造方法
JP7036636B2 (ja) 印刷用シート
WO2018181108A1 (fr) Feuille adhésive sensible à la pression pour impression et son procédé de production
JP4044627B2 (ja) 粘着シート類
JP7478009B2 (ja) 粘着シート、及び粘着シートの製造方法
WO2018101335A1 (fr) Feuille adhésive double face et procédé de production de feuille adhésive double face

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2015517532

Country of ref document: JP

Kind code of ref document: A

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13895136

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 13895136

Country of ref document: EP

Kind code of ref document: A1