Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M1/00—Inking and printing with a printer's forme
  • B41M1/26—Printing on other surfaces than ordinary paper
  • B41M1/30—Printing on other surfaces than ordinary paper on organic plastics, horn or similar materials
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/02—Printing inks
  • C09D11/10—Printing inks based on artificial resins
  • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
• • 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
  • C09D191/00—Coating compositions based on oils, fats or waxes; Coating compositions based on derivatives thereof
  • C09D191/06—Waxes
• • 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
  • C09D201/00—Coating compositions based on unspecified macromolecular compounds
  • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
  • C09D201/06—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
• • 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
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
• • 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
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/20—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for coatings strippable as coherent films, e.g. temporary coatings strippable as coherent films
• • 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
  • C09D7/20—Diluents or solvents

Definitions

• the present invention relates to a composition used to form a coating that can be detached from a substrate.
• Patent Document 1 a method is disclosed in which a film containing a styrene-acrylic acid resin, a phenolic resin, and a styrene-maleic acid resin as a vehicle printed on a heat-shrinkable PET film is removed with alkaline water.
• Patent Document 2 a coating layer containing a styrene-maleic acid resin, a rosin-maleic acid resin, and an acrylic acid copolymer resin is placed between printed layers of a heat-shrinkable PET film, and the coating layer is removed with alkaline water.
• packaging materials suitable for plastic recycling have also been disclosed in which a release layer made of printing ink is placed between two types of substrates, and the release layer is peeled off by treatment with a basic aqueous solution, allowing each substrate to be released (Patent Document 7, Patent Document 8, and Patent Document 9).
• the colorant contained in the coating may dissolve in the alkaline solution, causing the alkaline solution after the removal treatment (also referred to as the alkaline solution after treatment) to become colored. If the alkaline solution after treatment is colored, it will cause environmental pollution problems and will increase the cost of waste liquid treatment, so it is necessary to prevent the alkaline solution after treatment from being colored. Therefore, it is desirable to provide a method for recycling plastic substrates that can remove the coating in a simple manner and easily remove the coating layer from the plastic substrate, and that does not discolor the alkaline solution used to remove the coating after the removal process.
• the coating can be easily detached from the substrate, but that the coating is firmly attached to the substrate before the detachment process. Therefore, the coating is required to have high adhesion to the substrate.
• the coating has excellent abrasion resistance.
• the coating formed on the substrate has good toughness, excellent adhesion to the substrate, and abrasion resistance. If the coating has excellent toughness, it can be applied not only to printed matter in the form of reverse printing (lamination) printing as in Patent Documents 7 to 9, which require two types of substrates and have a printed layer between the substrates, but also to printed matter in the form of front printing, in which a substrate is disposed on only one side of the printed layer.
• the present invention aims to provide a film-forming material (film-forming composition) that can be used to remove a film from a general-purpose plastic substrate by a simple method, can easily remove a film layer from the plastic substrate, and can form a film that has excellent adhesion to the substrate, excellent abrasion resistance, and good toughness, in order to simultaneously solve the above-mentioned marine plastic problem and the problems with worker health and the environment, and can be used suitably for printed matter in the form of surface printing.
• film-forming material film-forming composition
• a removable film-forming composition for forming a film that is removable by treatment with an alkaline solution on the surface of a substrate A directly or via another layer the film-forming composition comprising an acrylic resin having an acid value of 10 to 100 mg KOH/g, a hydroxyl value of 1 mg KOH/g or more, and a glass transition temperature of 30 to 130° C.
• the film-forming composition according to [1] which contains a wax.
• the present invention provides a film-forming composition that can be used to remove a film from a general-purpose plastic substrate in a simple manner, can easily remove the film layer from the plastic substrate, and can form a film that prevents discoloration of the alkaline solution after removal, has excellent adhesion to the substrate, is highly resistant to friction, and has good toughness.
• the film-forming composition of the present invention is used to form a film on the surface of the substrate A directly or via another layer.
• the other layer may be a single layer or a plurality of layers.
• the film formed by the film-forming composition of the present invention can be removed by treatment with an alkaline solution.
• the film-forming composition contains an acrylic resin.
• the acrylic resin has an acid value of 10 to 100 mgKOH/g, a hydroxyl value of 1 mgKOH/g or more, and a glass transition temperature of 30 to 130°C.
• the acrylic resin has a specific acid value, hydroxyl value, and glass transition point, which, in combination, allow the film to be removed by a simple method, the film layer to be easily removed from the plastic substrate, and coloring of the alkaline solution after removal can be prevented. Furthermore, a film having excellent adhesion to the substrate and excellent abrasion resistance and good toughness can also be formed.
• having an acid value means that when the acid value of the acrylic resin is measured by the neutralization titration method of JIS K 0070 (1992), titration with one drop does not reach the end point.
• having a hydroxyl value means that when the hydroxyl value of the acrylic resin is measured by the neutralization titration method of JIS K 0070 (1992), titration with one drop does not reach the end point.
• the film formed from the film-forming composition of the present invention is used to remove from the substrate A a printed layer that has been formed on the surface of the substrate A directly or via another layer.
• the printed layer refers to a layer formed by printing with printing ink.
• Methods for removing the printed layer from the substrate A include, for example, a method in which the printed layer itself has a detachment function and the printed layer is detached from the substrate A (hereinafter also referred to as the pattern A method), and a method in which a separate layer is provided between the printed layer and the substrate A, the separate layer has a detachment function, and the printed layer is also detached from the substrate A by detaching the separate layer (hereinafter also referred to as the pattern B method).
• the film formed from the film-forming composition of the present invention includes both the printed layer in the method of pattern A and another layer in the method of pattern B. More specifically, the film according to the present invention includes both the printed layer and the primer layer and varnish layer described below. That is, the film-forming composition of the present invention can be used in any of the forms of printing ink, primer, and varnish.
• the film-forming composition of the present invention may be used to form at least one of a printed layer, a primer layer, and a varnish layer, and one or more of these layers may be formed using the film-forming composition of the present invention.
• the film and the substrate A according to the present invention may be arranged, for example, as follows.
• ⁇ Base material A - Printed layer (white) - Printed layer (color) Substrate A - primer layer - printed layer (white) - printed layer (color) ⁇ Base material A - Printed layer (white) - Printed layer (color) - Varnish layer ⁇ Base material A - Primer layer - Printed layer (white) - Printed layer (color) - Varnish layer ⁇ Base material A - Printed layer (color) - Printed layer (white) Substrate A - primer layer - printed layer (color) - printed layer (white) ⁇ Substrate A - Printed layer (color) - Printed layer (white) - Varnish layer ⁇ Substrate A - Primer layer - Printed layer (color) - Printed layer (white) - Varnish layer ⁇ Substrate A - Primer layer - Printed
• substrate A refers to substrate A described later
• printed layer (white) refers to a printed layer formed by printing the film-forming composition of the present invention as a printing ink and using a colorant used in white ink as a colorant to be contained in the film-forming composition
• printed layer (color) refers to a printed layer formed by printing the film-forming composition of the present invention as a printing ink and using a colorant other than the colorant used in white ink as a colorant to be contained in the film-forming composition
• primer layer refers to a layer formed using the film-forming composition of the present invention as a primer described later
• varnish layer refers to a layer formed using the film-forming composition of the present invention as a varnish described later.
• the printing layer is formed by laminating two layers, one using white ink and the other using a color ink as a colorant other than white ink.
• the printing layer does not have to be formed of two or more layers in this manner, and may be formed of a single layer of either white or color.
• the organic solvent-based composition which is the film-forming composition of the present invention, is used to form a printed layer that is detached by treatment with an alkaline solution directly or via another layer on the surface of the substrate A.
• the organic solvent-based composition contains an acrylic resin.
• the organic solvent-based composition contains an organic solvent, and optionally contains a colorant and other components.
• the organic solvent-based composition may use a raw material derived from biomass. Due to problems such as the depletion of petroleum resources, it is preferable that petroleum-derived products are replaced by those produced using plants as alternative energy sources and/or those produced using microorganisms, etc. In that case, the organic solvent-based composition can contribute to reducing the environmental load by being carbon neutral.
• the acrylic resin has an acid value.
• the acid value of the acrylic resin is 10 to 100 mgKOH/g. If the acid value of the acrylic resin is 10 mgKOH/g or more, the coating can be easily detached from the substrate, and if the acid value is 100 mgKOH/g or less, coloring of the alkaline solution after detachment can be effectively prevented.
• the acid value of the acrylic resin is preferably from 10 to 100 mgKOH/g, and more preferably from 30 to 70 mgKOH/g.
• the acrylic resin has a hydroxyl value.
• the hydroxyl value of the acrylic resin is 1 mgKOH/g or more from the viewpoints of achieving a balance with the acid value, enabling easy detachment of the coating from the substrate, and effectively preventing coloration of the alkaline solution after detachment.
• the hydroxyl value of the acrylic resin is preferably from 1 to 300 mgKOH/g, and more preferably from 30 to 200 mgKOH/g.
• the glass transition temperature of the acrylic resin is 30 to 130°C.
• the coating can be given appropriate film surface strength and elasticity against breakage.
• the glass transition temperature is 30°C or higher, the coating film becomes too soft, and the problems of reduced adhesion and reduced friction resistance can be effectively prevented.
• the glass transition temperature is 130°C or lower, the coating film is not too hard, and the surface friction resistance can be kept good, and further, the strength against film breakage can be maintained, so that the adhesion can be kept good.
• a coating that is excellent not only in abrasion resistance but also in water abrasion resistance can be formed.
• the glass transition temperature of the acrylic resin is preferably from 40 to 110°C, and more preferably from 50 to 90°C.
• the weight average molecular weight of the acrylic resin is preferably 2,000 to 100,000 from the viewpoint of achieving both releasability and adhesion to the substrate.
• the weight average molecular weight of the acrylic resin can be determined by gel permeation chromatography (GPC).
• the acrylic resin is a resin obtained by polymerizing a (meth)acrylic monomer.
• the acrylic resin When the acrylic resin is used as the sole binder resin, the acrylic resin must have a carboxyl group, and is preferably an acrylic resin obtained by polymerizing a monomer containing a (meth)acrylic monomer having a carboxyl group, such as (meth)acrylic acid or maleic acid.
• a monomer containing a (meth)acrylic monomer having a functional group such as 2-hydroxyethyl (meth)acrylate or glycidyl (meth)acrylate, can be polymerized, and after polymerization, the functional group can be reacted with a compound having a carboxyl group and reactive with the functional group (such as maleic anhydride), thereby providing the acrylic resin with a carboxyl group.
• a monomer containing a (meth)acrylic monomer having a functional group such as 2-hydroxyethyl (meth)acrylate or glycidyl (meth)acrylate
• Examples of monomers other than the (meth)acrylic monomer having a carboxyl group include (meth)acrylic monomers such as methyl (meth)acrylate and butyl (meth)acrylate;
• Examples of the vinyl monomer include maleic acid, maleic anhydride, styrene, vinyl acetate, butadiene, and acrylonitrile.
• the acrylic resin may be used as an aqueous resin after neutralization reaction.
• the aqueous resin may be in the form of an emulsion or a solution.
• the content of the acrylic resin in the composition of the present invention in terms of solid content relative to the total mass of the composition, is preferably 1% by mass or more, more preferably 2% by mass or more, even more preferably 3% by mass or more, and particularly preferably 5% by mass or more, and is preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, and particularly preferably 25% by mass or less, with any combination of these upper and lower limits being used.
• the content of the acrylic resin in the composition is preferably 1 to 50 mass%, more preferably 2 to 40 mass%, further preferably 3 to 30 mass%, and particularly preferably 5 to 25 mass%, in terms of solid content relative to the total mass of the composition.
• the organic solvent is not particularly limited, and examples thereof include various organic solvents such as aromatic hydrocarbons such as toluene, xylene, Solvesso #100, Solvesso #150, etc.; aliphatic hydrocarbons such as hexane, methylcyclohexane, heptane, octane, decane, etc.; esters such as methyl acetate, ethyl acetate, isopropyl acetate, normal propyl acetate, butyl acetate, amyl acetate, ethyl formate, butyl propionate, etc.; and cyclic ester compounds such as ⁇ -butyrolactone having 4 carbon atoms, ⁇ -valerolactone having 5 carbon atoms, ⁇ -caprolactone having 6 carbon atoms, oxilican-2-one having 7 carbon atoms, ⁇ -caprylolactone having 8 carbon atoms,
• water-miscible organic solvents include various organic solvents such as alcohols, such as methanol, ethanol, propanol, butanol, and isopropyl alcohol, ketones, such as acetone, methyl ethyl ketone, and cyclohexanone, and glycol ethers, such as ethylene glycol (mono, di) methyl ether, ethylene glycol (mono, di) ethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, monobutyl ether, diethylene glycol (mono, di) methyl ether, diethylene glycol (mono, di) ethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, triethylene glycol (mono, di) methyl ether, propylene glycol (mono, di) methyl ether, propylene glycol monopropyl ether, propylene glycol,
• the ester-based organic solvent preferably contains an ester-based organic solvent having 4 or more carbon atoms in order to prevent the organic solvent-based composition of the present invention from drying out due to its high volatility.
• the ester-based organic solvent having 4 or more carbon atoms is not limited, but ethyl acetate, isopropyl acetate, n-propyl acetate, and butyl acetate are more preferred, and n-propyl acetate is particularly preferred.
• the organic solvent preferably contains at least one of n-propyl acetate, isopropyl alcohol, and a cyclic ester compound having 4 to 10 carbon atoms.
• the organic solvent-based composition contains a cyclic ester compound having 4 to 10 carbon atoms, a coating that exhibits excellent adhesion to shrinkable substrates can be formed.
• the content of the ester-based organic solvent in the organic solvent-based composition of the present invention is preferably 1 to 60% by mass, preferably 3 to 55% by mass, preferably 5 to 50% by mass, preferably 7 to 45% by mass, preferably 10 to 40% by mass, preferably 12 to 35% by mass, preferably 15 to 30% by mass, preferably 18 to 28% by mass, preferably 20 to 25% by mass, and preferably 20 to 23% by mass.
• the organic solvent-based composition of the present invention When the organic solvent-based composition of the present invention is used for gravure ink applications, it is preferable that it does not contain an aromatic hydrocarbon organic solvent, and contains an alcohol having a specific evaporation rate of 100 or less, where the evaporation rate of butyl acetate is taken as 100.
• an alcohol having a specific evaporation rate of 100 or less By containing an alcohol having a specific evaporation rate of 100 or less, it is possible to maintain highlight transferability with a dot area of 10% or less, and to maintain highlight improvement.
• the mechanism for this is as follows: 1) After the organic solvent-based composition of the present invention is transferred to the substrate, half of the organic solvent-based composition of the present invention remains in the cells of the gravure plate.
• alcohols with a specific evaporation rate of 100 or less when the evaporation rate of butyl acetate is taken as 100, have a low ratio of hydroxyl groups (alcohol groups) per alcohol molecule, and therefore tend to increase the solubility of acrylic resins.
• ethyl acetate, normal propyl acetate, isopropanol, normal propanol, etc. and not to use aromatic solvents such as toluene or ketone-based solvents such as methyl ethyl ketone.
• glycol ethers can be added in an amount of less than 10% by mass of the total composition.
• the organic solvent-based composition of the present invention may further contain a colorant.
• Colorants that can be used in the organic solvent-based composition of the present invention include inorganic pigments, organic pigments, and dyes that are commonly used in inks, paints, and recording materials.
• organic pigments include soluble azo pigments, insoluble azo pigments, azo pigments, phthalocyanine pigments, halogenated phthalocyanine pigments, anthraquinone pigments, anthanthrone pigments, dianthraquinonyl pigments, anthrapyrimidine pigments, perylene pigments, perinone pigments, quinacridone pigments, thioindigo pigments, dioxazine pigments, isoindolinone pigments, quinophthalone pigments, azomethine azo pigments, flavanthrone pigments, diketopyrrolopyrrole pigments, isoindoline pigments, indanthrone pigments, and carbon black pigments.
• examples of the pigments include carmine 6B, lake red C, permanent red 2B, disazo yellow, pyrazolone orange, carmine FB, chromophthalic yellow, chromophthalic red, phthalocyanine blue, phthalocyanine green, dioxazine violet, quinacridone magenta, quinacridone red, indanthrone blue, pyrimidine yellow, thioindigo bordeaux, thioindigo magenta, perylene red, perinone orange, isoindolinone yellow, aniline black, diketopyrrolopyrrole red, and daylight fluorescent pigments.
• non-acid-treated pigments and acid-treated pigments can be used. Specific examples of preferred organic pigments are given below.
• black pigments examples include C.I. Pigment Black 1, C.I. Pigment Black 6, C.I. Pigment Black 7, C.I. Pigment Black 9, and C.I. Pigment Black 20.
• indigo pigments examples include C.I. Pigment Blue 15, C.I. Pigment Blue 15:1, C.I. Pigment Blue 15:2, C.I. Pigment Blue 15:3, C.I. Pigment Blue 15:4, C.I. Pigment Blue 15:5, C.I. Pigment Blue 15:6, C.I. Pigment Blue 16, C.I. Pigment Blue 17:1, C.I. Pigment Blue 22, C.I. Pigment Blue 24:1, C.I. Pigment Blue 25, C.I. Pigment Blue 26, C.I. Pigment Blue 60, C.I. Pigment Blue 61, C.I. Pigment Blue 62, C.I. Pigment Blue 63, C.I. Examples include C.I. Pigment Blue 64, C.I. Pigment Blue 75, C.I. Pigment Blue 79, and C.I. Pigment Blue 80.
• green pigments examples include C.I. Pigment Green 1, C.I. Pigment Green 4, C.I. Pigment Green 7, C.I. Pigment Green 8, C.I. Pigment Green 10, and C.I. Pigment Green 36.
• red pigments examples include C.I. Pigment Red 1, C.I. Pigment Red 2, C.I. Pigment Red 3, C.I. Pigment Red 4, C.I. Pigment Red 5, C.I. Pigment Red 6, C.I. Pigment Red 7, C.I. Pigment Red 8, C.I. Pigment Red 9, C.I. Pigment Red 10, C.I. Pigment Red 11, C.I. Pigment Red 12, C.I. Pigment Red 15, C.I. Pigment Red 16, C.I. Pigment Red 17, C.I. Pigment Red 18, C.I. Pigment Red 19, C.I. Pigment Red 20, C.I. Pigment Red 21, C.I. Pigment Red 22, C.I. Pigment Red 23, C.I. Pigment Red 31, C.I.
• Examples of the pigment red include C.I. Pigment Red 266, C.I. Pigment Red 268, C.I. Pigment Red 269, C.I. Pigment Red 270, C.I. Pigment Red 271, C.I. Pigment Red 272, C.I. Pigment Red 279, and the like.
• purple pigments examples include C.I. Pigment Violet 1, C.I. Pigment Violet 2, C.I. Pigment Violet 3, C.I. Pigment Violet 3:1, C.I. Pigment Violet 3:3, C.I. Pigment Violet 5:1, C.I. Pigment Violet 13, C.I. Pigment Violet 19 ( ⁇ type, ⁇ type), C.I. Pigment Violet 23, C.I. Pigment Violet 25, C.I. Pigment Violet 27, C.I. Pigment Violet 29, C.I. Pigment Violet 31, C.I. Pigment Violet 32, C.I. Pigment Violet 36, C.I. Pigment Violet 37, C.I. Pigment Violet 38, C.I. Pigment Violet 42, C.I. Pigment Violet 50, etc.
• yellow pigments examples include C.I. Pigment Yellow 1, C.I. Pigment Yellow 3, C.I. Pigment Yellow 12, C.I. Pigment Yellow 13, C.I. Pigment Yellow 14, Pigment Yellow 17, C.I. Pigment Yellow 24, C.I. Pigment Yellow 42, C.I. Pigment Yellow 55, C.I. Pigment Yellow 62, C.I. Pigment Yellow 65, C.I. Pigment Yellow 74, C.I. Pigment Yellow 83, C.I. Pigment Yellow 86, C.I. Pigment Yellow 93, C.I. Pigment Yellow 94, C.I. Pigment Yellow 95, C.I. Pigment Yellow 109, C.I. Pigment Yellow 110, C. C.I. Pigment Yellow 117, C.I.
• orange pigments examples include C.I. Pigment Orange 5, C.I. Pigment Orange 13, C.I. Pigment Orange 16, C.I. Pigment Orange 34, C.I. Pigment Orange 36, C.I. Pigment Orange 37, C.I. Pigment Orange 38, C.I. Pigment Orange 43, C.I. Pigment Orange 51, C.I. Pigment Range 55, C.I. Pigment Orange 59, C.I. Pigment Orange 61, C.I. Pigment Orange 64, C.I. Pigment Orange 71, and C.I. Pigment Orange 74.
• brown pigments examples include C.I. Pigment Brown 23, C.I. Pigment Brown 25, and C.I. Pigment Brown 26.
• preferred pigments include C.I. Pigment Black 7 as a black pigment, C.I. Pigment Blue 15, C.I. Pigment Blue 15:1, C.I. Pigment Blue 15:2, C.I. Pigment Blue 15:3, C.I. Pigment Blue 15:4, C.I. Pigment Blue 15:6 as an indigo pigment, C.I. Pigment Green 7 as a green pigment, and C.I. Pigment Red 57:1, C.I. Pigment Red 48:1, C.I. Pigment Red 48:2, C.I. Pigment Red 48:3, C.I. Pigment Red 146, C.I.
• the pigments include C.I. Pigment Red 178, C.I. Pigment Red 149, C.I. Pigment Red 144, C.I. Pigment Red 166, purple pigments include C.I. Pigment Violet 23 and C.I. Pigment Violet 37, yellow pigments include C.I. Pigment Yellow 83, C.I. Pigment Yellow 14, C.I. Pigment Yellow 180, and C.I. Pigment Yellow 139, and orange pigments include C.I. Pigment Orange 38, C.I. Pigment Orange 13, C.I. Pigment Orange 34, and C.I. Pigment Orange 64. It is preferable to use at least one or more pigments selected from these groups.
• Inorganic pigments include carbon black, titanium oxide, red ocher, aluminum, mica, zinc oxide, barium sulfate, calcium carbonate, and silica. Also usable are glittering pigments (Metashine; Nippon Sheet Glass Co., Ltd.) made of glass flakes or clumped flakes as a base material coated with a metal or metal oxide. From the standpoint of cost and coloring power, it is preferable to use carbon black for black ink, titanium oxide for white ink, aluminum for gold and silver ink, and mica for pearl ink.
• the total pigment content is preferably 1% by mass or more and preferably 60% by mass or less in the total amount of the organic solvent-based composition of the present invention, from the viewpoint of ensuring the concentration and coloring power of the organic solvent-based composition of the present invention.
• the organic solvent-based composition of the present invention may further contain other components such as a binder resin and an auxiliary.
• the binder resin include cellulose-based resins, urethane resins, polyamide resins, vinyl chloride-vinyl acetate copolymer resins, ketone resins, polyester resins, (meth)acrylic resins, rosin-modified maleic acid resins and rosin-modified fumaric acid resins, chlorinated polypropylene resins, ethylene-vinyl acetate copolymer resins, vinyl acetate resins, alkyd resins, polyvinyl chloride resins, cyclized rubbers, chlorinated rubbers, butyral resins, and petroleum resins.
• Polymerizable monomers having a carboxyl group such as itaconic acid, maleic acid, fumaric acid, cinnamic acid, or acid anhydrides thereof, polymerizable monomers having a sulfonic acid group such as sulfonated styrene, and polymerizable monomers having a sulfonamide group such as vinylbenzenesulfonamide are copolymerized with polymerizable monomers, such as (meth)acrylic resins, styrene-(meth)acrylic resins, styrene-(anhydride)maleic acid resins, and terpene-(anhydride)maleic acid resins, and acid-modified polyolefin resins.
• the organic solvent-based composition contains a (meth)acrylic resin and/or a styrene-(meth)acrylic resin as a binder resin
• the content of the above ⁇ acrylic resin>> includes the content of the (meth)acrylic resin and/or the styrene-(meth)acrylic resin in this item.
• waxes such as paraffin wax, polyethylene wax, polypropylene wax, carnauba wax, candelilla wax, montan wax, microcrystalline wax, amide wax, and modified montan wax, which are used to impart abrasion resistance and slipperiness, etc.; fatty acid amide compounds such as oleic acid amide, stearic acid amide, and erucic acid amide; silicone and non-silicone defoamers to suppress foaming during printing; dispersants, etc., can be used as appropriate. As dispersants, nonionic dispersants are preferred.
• the wax content is calculated as the solid content in the total amount of the organic solvent-based composition, and the lower limit is preferably 0.1 mass% or more, and the upper limit is preferably 5.0 mass% or less, more preferably 4.0 mass% or less, and even more preferably 3.0 mass% or less. Any combination of these upper and lower limits can be used.
• the acid value of the dispersant is preferably 30 mgKOH/g or less, more preferably 25 mgKOH/g or less, and even more preferably 20 mgKOH/g or less. It may also be, for example, 1 mgKOH/g or more, or even 3 mgKOH/g or more.
• the content of the dispersant is preferably 1 part by mass or more, more preferably 2 parts by mass or more, more preferably 5 parts by mass or more, more preferably 10 parts by mass or more, more preferably 15 parts by mass or more, and even more preferably 20 parts by mass or more, and is preferably 100 parts by mass or less, more preferably 80 parts by mass or less, more preferably 75 parts by mass or less, more preferably 70 parts by mass or less, more preferably 65 parts by mass or less, and even more preferably 60 parts by mass or less.
• the viscosity of the organic solvent-based composition of the present invention is preferably 6 seconds or more, more preferably 10 seconds or more, and even more preferably 13 seconds or more. It is also preferably 25 seconds or less, more preferably 20 seconds or less, and even more preferably 18 seconds or less.
• the surface tension of the organic solvent-based composition of the present invention is preferably 25 mN/m or more, more preferably 33 mN/m or more. Also, it is preferably 50 mN/m or less, more preferably 43 mN/m or less.
• the organic solvent-based composition of the present invention when used for gravure printing or flexographic printing, it can be produced using an Eiger mill, sand mill, bead mill, gamma mill, attritor, or the like that is commonly used in the production of gravure or flexographic inks.
• a preliminary composition (kneaded base ink) may be prepared by previously mixing at least a portion of the acrylic resin, the colorant, and at least a portion of the organic solvent.
• resist ink is an example of a composition that is removed from a substrate in the same way as in the present invention.
• the resist ink is intended to remove the coating from the substrate in advance, leaving only a portion of it, and then process the substrate. It has a fundamentally different use and purpose from the coating-forming composition of the present invention, which is intended to remove the entire coating and recycle the substrate, and therefore does not fall under the well-known technology of the present invention.
• the film-forming composition of the present invention can also be used as a primer composition to form a primer layer.
• the film-forming composition of the present invention contains the above-mentioned ⁇ acrylic resin>>.
• the primer composition may contain, in addition to the acrylic resin, a commercially available binder resin, a solvent such as an organic solvent or an aqueous solvent, additives, and the like, without any particular limitation.
• binder resins examples include cellulose-based resins, urethane resins, polyamide resins, vinyl chloride-vinyl acetate copolymer resins, ketone resins, polyester resins, (meth)acrylic resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, chlorinated polypropylene resins, ethylene-vinyl acetate copolymer resins, vinyl acetate resins, alkyd resins, polyvinyl chloride resins, cyclized rubber, chlorinated rubber, butyral resins, and petroleum resins; radical copolymers of polymerizable monomers such as (meth)acrylic resins, styrene-(meth)acrylic resins, styrene-maleic acid (anhydride) resins, and terpene-maleic acid (anhydride) resins, which are copolymerized with polymerizable monomers such as polymerizable monomers having a
• the content of the above ⁇ acrylic resin>> includes the content of the (meth)acrylic resin and/or styrene-(meth)acrylic resin in this item.
• the solvent may be an organic solvent, for example, the same organic solvents as those described in the "Organic Solvent” section of "Organic Solvent-Based Composition” above can be used.
• Additives include extender pigments, pigment dispersants, leveling agents, defoamers, waxes, plasticizers, anti-blocking agents, infrared absorbers, ultraviolet absorbers, fragrances, flame retardants, etc.
• the amount of acrylic resin added may be determined as appropriate within a range that does not impair the properties of the primer layer, but it is preferable that the amount is within the range of 5 to 30% by weight, for example, relative to the total weight of the primer layer composition.
• primers to which resins with acidic groups or low molecular weight compounds have been added can also be preferably used.
• resins with acidic groups or low molecular weight compounds that can be used as long as they can be easily mixed with the above-mentioned acrylic resin, which is the main component of the primer, or with organic solvents, etc.
• resins having acidic groups include cellulose resins, urethane resins, polyamide resins, vinyl chloride-vinyl acetate copolymer resins, ketone resins, polyester resins, (meth)acrylic resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, chlorinated polypropylene resins, ethylene-vinyl acetate copolymer resins, vinyl acetate resins, alkyd resins, polyvinyl chloride resins, cyclized rubber, chlorinated rubber, butyral resins, and petroleum resins to which an acid value has been imparted; resins which are radical copolymers of polymerizable monomers having acidic groups, such as itaconic acid, maleic acid, fumaric acid, cinnamic acid, or acid anhydrides thereof, polymerizable monomers having sulfonic acid groups, such as sulfonated styrene, and polymerizable mono
• the content of the above ⁇ acrylic resin>> includes the content of the (meth)acrylic resin and/or styrene-(meth)acrylic resin in this item.
• low molecular weight compounds having an acidic group include organic acids such as saturated fatty acids, unsaturated fatty acids, hydroxy acids, aromatic carboxylic acids, dicarboxylic acids, tricarboxylic acids, oxocarboxylic acids, and carboxylic acid derivatives, and these can be used singly or in combination.
• saturated fatty acids include lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, decanoic acid, undecanoic acid, and dodecanoic acid.
• Examples of unsaturated fatty acids include oleic acid, linoleic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid, docosahexaenoic acid, and sorbic acid.
• Examples of hydroxy acids include lactic acid, malic acid, and citric acid.
• Examples of aromatic carboxylic acids include benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, gallic acid, mellitic acid, and ketone.
• Examples of the dicarboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, undecane diacid, dodecane diacid, dimer acid, fumaric acid, maleic acid, azelaic acid, etc.
• Examples of the tricarboxylic acid include aconitic acid and trimer acid, etc.
• Examples of the oxocarboxylic acid include pyruvic acid and oxaloacetic acid, etc.
• Examples of the carboxylic acid derivative include amino acid and nitrocarboxylic acid, and these can be used singly or in combination.
• citric acid, butyric acid, caproic acid, enanthic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, linoleic acid, eleostearic acid, arachidic acid, sebacic acid, etc. can comply with the so-called Swiss Ordinance, and it is preferable to use substances that comply with various regulations.
• the film-forming composition of the present invention can also be used as a varnish composition to form a varnish layer.
• the film-forming composition of the present invention contains the above-mentioned ⁇ acrylic resin>>.
• the varnish composition may contain, without particular limitation, commercially available binder resins, solvents such as organic solvents and aqueous solvents, additives, etc.
• binder resins examples include cellulose-based resins, urethane resins, polyamide resins, vinyl chloride-vinyl acetate copolymer resins, ketone resins, polyester resins, (meth)acrylic resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, chlorinated polypropylene resins, ethylene-vinyl acetate copolymer resins, vinyl acetate resins, alkyd resins, polyvinyl chloride resins, cyclized rubber, chlorinated rubber, butyral resins, and petroleum resins; radical copolymers of polymerizable monomers such as (meth)acrylic resins, styrene-(meth)acrylic resins, styrene-maleic acid (anhydride) resins, and terpene-maleic acid (anhydride) resins, which are copolymerized with polymerizable monomers such as polymerizable monomers having a
• the content of the above ⁇ acrylic resin>> includes the content of the (meth)acrylic resin and/or styrene-(meth)acrylic resin in this item.
• the solvent may be an organic solvent, for example, the same organic solvents as those described in the "Organic Solvent” section of the “Organic Solvent-Based Composition” above can be used.
• Additives include extender pigments, pigment dispersants, leveling agents, defoamers, waxes, plasticizers, anti-blocking agents, infrared absorbers, ultraviolet absorbers, fragrances, flame retardants, etc.
• the amount of acrylic resin added may be determined appropriately within a range that does not impair the properties of the varnish layer, but it is preferable that the amount is within the range of 5 to 30% by mass of the varnish layer composition, for example.
• Varnishes to which resins with acidic groups or low molecular weight compounds have been added can also be preferably used.
• the resins with acidic groups or low molecular weight compounds that can be used as long as they can be easily mixed with the acrylic resins and organic solvents that are the main components of the varnish.
• resins having acidic groups include cellulose resins, urethane resins, polyamide resins, vinyl chloride-vinyl acetate copolymer resins, ketone resins, polyester resins, (meth)acrylic resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, chlorinated polypropylene resins, ethylene-vinyl acetate copolymer resins, vinyl acetate resins, alkyd resins, polyvinyl chloride resins, cyclized rubber, chlorinated rubber, butyral resins, and petroleum resins to which an acid value has been imparted; resins which are radical copolymers of polymerizable monomers having acidic groups, such as itaconic acid, maleic acid, fumaric acid, cinnamic acid, or acid anhydrides thereof, polymerizable monomers having sulfonic acid groups, such as sulfonated styrene, and polymerizable mono
• the content of the above ⁇ acrylic resin>> includes the content of the (meth)acrylic resin and/or styrene-(meth)acrylic resin in this item.
• low molecular weight compounds having an acidic group include organic acids such as saturated fatty acids, unsaturated fatty acids, hydroxy acids, aromatic carboxylic acids, dicarboxylic acids, tricarboxylic acids, oxocarboxylic acids, and carboxylic acid derivatives, and these can be used singly or in combination.
• Saturated fatty acids include lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, decanoic acid, undecanoic acid, and dodecanoic acid.
• Unsaturated fatty acids include oleic acid, linoleic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid, docosahexaenoic acid, and sorbic acid.
• Hydroxy acids include lactic acid, malic acid, and citric acid.
• Aromatic carboxylic acids include benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, gallic acid, mellitic acid
• dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, dimer acid, fumaric acid, maleic acid, azelaic acid, etc.
• examples of tricarboxylic acids include aconitic acid and trimer acid
• examples of oxocarboxylic acids include pyruvic acid and oxaloacetic acid, etc.
• carboxylic acid derivatives include amino acids and nitrocarboxylic acids, and these can be used singly or in combination.
• citric acid, butyric acid, caproic acid, enanthic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, linoleic acid, eleostearic acid, arachidic acid, sebacic acid, etc. are compatible with the so-called Swiss Ordinance, and it is preferable to use substances that comply with various regulations.
• the film-forming composition of the present invention has excellent adhesion to various substrates and can be used for printing on paper, synthetic paper, cloth, thermoplastic resin films, plastic products, steel plates, etc., and is useful as an ink for gravure printing using a gravure printing plate by electronic engraving intaglio, etc., or for flexographic printing using a flexographic printing plate by a resin plate, etc., but can also be used for an inkjet method in which ink is discharged from an inkjet nozzle without using a plate, but this is not preferred.
• ink droplets discharged from a nozzle directly adhere to a substrate to form a printed matter
• the printing ink is once adhered to and transferred to a printing plate or a printing pattern, and then only the ink is again adhered to a substrate and dried as necessary to form a printed matter.
• the thickness of the printing ink formed by the gravure printing method or flexographic printing method using the film-forming composition of the present invention is, for example, preferably 10 ⁇ m or less, and more preferably 5 ⁇ m or less.
• a printed matter having a film can be obtained by printing the film-forming composition of the present invention on the surface of the substrate A directly or via another layer.
• the coating according to the present invention has excellent adhesion to the substrate, excellent abrasion resistance, and good toughness. Therefore, the film according to the present invention can be preferably applied to a printed matter in the form of surface printing in which a substrate is arranged only on one side of the printed layer (i.e., no substrate is arranged on the side opposite to the side on which the substrate A is arranged with respect to the film).
• the film according to the present invention can also be applied to a printed matter in the form of back printing (lamination) printing in which the substrate B is arranged on the film side of the printed matter, that is, two types of substrates are essential and a printed layer is arranged between the substrates, but more preferably, it is applied to a printed matter in the form of surface printing as described above.
• a printed matter in the form of surface printing does not require multiple substrates compared to a printed matter in the form of back printing (lamination) printing, and is therefore convenient because it has a simple configuration, but the film is required to have toughness.
• the film according to the present invention has excellent toughness and can be applied to a printed matter in the form of surface printing.
• the embodiment of the printed matter printed using the film-forming composition of the present invention and the laminate constructed using the printed matter are not limited, but preferred examples include the following surface printing embodiments.
• the mode in which a coating is formed on the surface of the substrate A directly or via another layer is as follows.
• ⁇ Surface printing> ⁇ Base material A - Printed layer (white) - Printed layer (color)
• Substrate A - primer layer - printed layer (white) - printed layer (color) ⁇ Base material A - Printed layer (white) - Printed layer (color) - Varnish layer ⁇ Base material A - Primer layer - Printed layer (white) - Printed layer (color) - Varnish layer ⁇ Base material A - Printed layer (color) - Printed layer (white)
• the printing layer (white), the printing layer (color), the primer layer, and the varnish layer are as described above.
• the substrate A will now be described.
• the substrate A is preferably a plastic substrate, and examples thereof include polyamide resins such as nylon 6, nylon 66, and nylon 46; polyester resins such as polyethylene terephthalate (PET), polyethylene naphthalate, polytrimethylene terephthalate, polytrimethylene naphthalate, polybutylene terephthalate, and polybutylene naphthalate; biodegradable resins such as polyhydroxycarboxylic acids such as polylactic acid, aliphatic polyester resins such as poly(ethylene succinate) and poly(butylene succinate); polyolefin resins such as polypropylene and polyethylene, polyimide resins, polyarylate resins, and mixtures thereof; and thermoplastic resins such as films and laminates thereof.
• polyamide resins such as nylon 6, nylon 66, and nylon 46
• polyester resins such as polyethylene terephthalate (PET), polyethylene naphthalate, polytrimethylene terephthalate, polytrimethylene naphthalate, polybuty
• films and laminates made of polyester, polyamide, polyethylene, and polypropylene can be preferably used, and polypropylene or polyethylene is more preferable when the release property of the film-forming composition of the present invention is emphasized.
• These substrate films may be unstretched or stretched films, and the manufacturing method thereof is not limited.
• the thickness of the substrate film is also not particularly limited, but it is usually sufficient to be in the range of 1 to 500 ⁇ m.
• the printing surface of substrate A is preferably subjected to corona discharge treatment, and silica, alumina, etc. may be vapor-deposited.
• the substrate A, the printed layer (white), the printed layer (color), the primer layer, or the varnish layer in the laminate may each have a barrier layer interposed therebetween.
• the barrier layer include an inorganic vapor deposition layer and a barrier coat layer, and these may be used alone or in combination.
• the inorganic vapor deposition layer is a layer that has gas barrier properties that prevent the permeation of oxygen gas and water vapor gas, and is a vapor deposition layer made of an inorganic substance or an inorganic oxide.
• inorganic substances or inorganic oxides include aluminum, alumina, silica, etc., and these can be used alone or in combination of two or more.
• Two or more inorganic vapor deposition layers may be provided. When two or more inorganic vapor deposition layers are provided, they may have the same composition or different compositions.
• the barrier coat layer protects the inorganic vapor deposition layer and can improve the gas barrier properties against oxygen, water vapor, etc.
• a gas barrier coat layer is formed from a resin composition such as a hydrolyzate of a metal alkoxide obtained by polycondensing a mixture of a metal alkoxide and a water-soluble polymer by the sol-gel method in the presence of a sol-gel catalyst and a solvent such as water or an organic solvent, or a hydrolysis polycondensate of a metal alkoxide.
• the coating film is removed from the substrate A by treating the printed matter with an alkaline solution, thereby producing a recycled substrate A.
• the removal process includes a step of immersing the printed matter or laminate in an alkaline solution while heating and stirring at 20 to 90°C or ultrasonically vibrating it. Heating and stirring and ultrasonic vibration may be performed simultaneously.
• the heating temperature is preferably 30°C or higher, more preferably 40°C or higher, more preferably 50°C or higher, and more preferably 60°C or higher, and it is more preferable to perform heating and stirring and ultrasonic vibration simultaneously.
• the alkaline solution used in the desorption step is not limited, but preferably has a pH of 9 or higher, and is preferably an aqueous solution of sodium hydroxide, potassium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium dihydrogen carbonate, potassium dihydrogen carbonate, etc.
• the aqueous solutions of sodium hydroxide, potassium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium dihydrogen carbonate, potassium dihydrogen carbonate, etc. are preferably aqueous solutions with a concentration of 0.5% to 10% by mass, more preferably 1% to 5% by mass.
• the alkaline solution may also contain a water-soluble organic solvent.
• the water-soluble organic solvent include methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, ethylene glycol monomethyl ether (methyl cellosolve), ethylene glycol monoethyl ether (cellosolve), ethylene glycol monobutyl ether (butyl cellosolve), ethylene glycol dibutyl ether, diethylene glycol monomethyl ether (methyl carbitol), diethylene glycol dimethyl ether, diethylene glycol monoethyl ether (carbitol), diethylene glycol diethyl ether (diethyl carbitol), diethylene glycol monobutyl ether (butyl carbitol), diethylene glycol dibutyl ether, and triethylene glycol.
• Examples include cholesteryl monomethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, methylene dimethyl ether (methylal), propylene glycol monobutyl ether, tetrahydrofuran, acetone, diacetone alcohol, acetonylacetone, acetylacetone, ethylene glycol monomethyl ether acetate (methyl cellosolve acetate), diethylene glycol monomethyl ether acetate (methyl carbitol acetate), diethylene glycol monoethyl ether acetate (carbitol acetate), ethyl hydroxyisobutyrate, and ethyl lactate, which may be used alone or in combination of two or more.
• the content of the water-soluble organic solvent in the alkaline solution is preferably 0.1% by mass to 20% by mass, and more preferably 1% by mass to 10% by mass.
• the alkaline solution may also contain a water-insoluble organic solvent.
• the water-insoluble organic solvent include alcohol-based solvents such as n-butanol, 2-butanol, isobutanol, and octanol; aliphatic hydrocarbon-based solvents such as hexane, heptane, and normal paraffin; aromatic hydrocarbon-based solvents such as benzene, toluene, xylene, and alkylbenzene; halogenated hydrocarbon-based solvents such as methylene chloride, 1-chlorobutane, 2-chlorobutane, 3-chlorobutane, and carbon tetrachloride; ester-based solvents such as methyl acetate, ethyl acetate, and butyl acetate; ketone
• the alkaline solution may also contain a surfactant.
• the surfactant include various anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants, and among these, anionic surfactants, nonionic surfactants, and amphoteric surfactants are preferred.
• anionic surfactants include alkylbenzenesulfonates, alkylphenylsulfonates, alkylnaphthalenesulfonates, higher fatty acid salts, sulfates of higher fatty acid esters, sulfonates of higher fatty acid esters, sulfates and sulfonates of higher alcohol ethers, higher alkyl sulfosuccinates, polyoxyethylene alkyl ether carboxylates, polyoxyethylene alkyl ether sulfates, alkyl phosphates, and polyoxyethylene alkyl ether phosphates.
• dodecylbenzenesulfonates include dodecylbenzenesulfonates, isopropylnaphthalenesulfonates, monobutylphenylphenol monosulfonates, monobutylbiphenylsulfonates, and dibutylphenylphenol disulfonates.
• nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene glycerin fatty acid esters, polyglycerin fatty acid esters, sucrose fatty acid esters, polyoxyethylene alkylamines, polyoxyethylene fatty acid amides, fatty acid alkylol amides, alkyl alkanol amides, acetylene glycol, oxyethylene adducts of acetylene glycol, polyethylene glycol polypropylene glycol block copolymers, and the like.
• polyoxyethylene nonylphenyl ether polyoxyethylene octylphenyl ether, polyoxyethylene dodecylphenyl ether, polyoxyethylene alkyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, fatty acid alkylol amides, acetylene glycol, oxyethylene adducts of acetylene glycol, and polyethylene glycol polypropylene glycol block copolymers are preferred.
• surfactants that can be used include silicone surfactants such as polysiloxane oxyethylene adducts; fluorine-based surfactants such as perfluoroalkyl carboxylates, perfluoroalkyl sulfonates, and oxyethylene perfluoroalkyl ethers; and biosurfactants such as spiculisporic acid, rhamnolipids, and lysolecithin.
• silicone surfactants such as polysiloxane oxyethylene adducts
• fluorine-based surfactants such as perfluoroalkyl carboxylates, perfluoroalkyl sulfonates, and oxyethylene perfluoroalkyl ethers
• biosurfactants such as spiculisporic acid, rhamnolipids, and lysolecithin.
• surfactants can be used alone or in combination of two or more.
• the amount added is preferably in the range of 0.001 to 2 mass % of the total amount of the alkaline solution, more preferably 0.001 to 1.5 mass %, and even more preferably 0.01 to 1 mass %.
• the target printed matter or laminate is immersed in the alkaline solution, for example in a treatment tank, while the alkaline solution is heated to 20-90°C or ultrasonically vibrated.
• the heating method There are no particular limitations on the heating method, and known heating methods using heat rays, infrared rays, microwaves, etc. can be used.
• Ultrasonic vibration can be achieved, for example, by attaching an ultrasonic vibrator to the treatment tank and applying ultrasonic vibration to the warm water or alkaline solution.
• the alkaline solution is stirred during immersion.
• Stirring methods include, for example, mechanical stirring of the dispersion of the printed matter or laminate contained in the treatment tank using a stirring blade, water flow stirring using a water flow pump, and bubbling with an inert gas such as nitrogen gas. These methods may be used in combination to achieve efficient peeling.
• the time for which the printed matter or laminate is immersed in the alkaline solution varies depending on the composition of the printed matter, but is generally in the range of 2 minutes to 48 hours. In the present invention, it is not necessary for 100% of the coating on the printed matter to be completely detached from the substrate, but it is preferable for 60% or more of the 100% by weight of the coating to be detached, more preferably 70% or more, even more preferably 80% or more, and particularly preferably 90% or more.
• the film may be immersed in the alkaline solution once or several times. That is, the film may be immersed once and then the separated film substrate may be recovered, or the film may be immersed several times and then the film substrate may be recovered.
• the concentration of the alkaline solution may be changed.
• known processes such as washing with water and drying may be added as appropriate.
• the film-forming composition of the present invention keeps the content of solvents that are harmful to health and the environment below a certain level, while maintaining the same properties for general-purpose plastic substrates as conventional film-forming materials. Furthermore, by containing a specific acrylic resin, it can be easily removed by alkaline solution treatment, and the film layer can be easily removed from the plastic substrate. In addition, it prevents discoloration of the alkaline solution after removal, and can form a film that has excellent adhesion to the substrate, excellent abrasion resistance, and good toughness.
• binder resin acrylic resin and other binder resins other than acrylic resin
• colorant pigment
• organic solvent organic solvent
• auxiliary wax
• Resin 1 Acrylic resin (acid value in solid content: 15 mg KOH/g, hydroxyl value 200 mg KOH/g, glass transition temperature 30° C., solid content 50 parts by mass)
• Resin 2 Acrylic resin (acid value in solid content: 30 mg KOH/g, hydroxyl value 150 mg KOH/g, glass transition temperature 50° C., solid content 50 parts by mass)
• Resin 3 Acrylic resin (acid value in solid content: 45 mg KOH/g, hydroxyl value 100 mg KOH/g, glass transition temperature 70° C., solid content 50 parts by mass)
• Resin 4 Acrylic resin (acid value in solid content: 60 mg KOH/g, hydroxyl value: 50 mg KOH/g, glass transition temperature: 90° C., solid content: 50 parts by mass)
• Resin 5 Acrylic resin (acid value in solid content: 90 mg KOH/g, hydroxyl value 10 mg KOH/g, glass transition temperature 110° C., solid content 50 parts by mass)
• Resin 6 Acrylic resin (acid value in solid
• composition of each component in the film-forming composition of Example 1 is shown in Table 1 below.
• the physical properties of the acrylic resin in the film-forming composition of Example 1 are also shown in Table 1.
• the prepared film-forming compositions were subjected to the following evaluations.
• the evaluation results are shown in Table 2 below.
• ⁇ Evaluation item 1 Adhesion to substrate>
• the prepared film-forming composition was used to print a solid pattern of 240 mm length x 80 mm width on substrate A using bar coater #4, and then dried with a dryer to form printed layer 1, obtaining a printed matter of configuration 1 below.
• Substrate A Printing layer 1
• Substrate A Corona-treated polyethylene terephthalate film (Toyobo Co., Ltd., Ester E5100, thickness 12 ⁇ m) (PET)
• Substrate B Biaxial polypropylene film (Toyobo Co., Ltd., Pylen P2161, thickness 20 ⁇ m) (OPP)
• Substrate C Polystyrene film (DXL-270-41S, manufactured by Mitsubishi Chemical Corporation, thickness 40 ⁇ m) (OPS)
• the resulting print was either immediately or left for 24 hours, after which 5 cm of cellophane tape (12 mm width, made by Nichiban) was applied to the printed surface, and one end of the cellophane tape was quickly pulled off perpendicular to the printed surface. The remaining percentage of the printed film was visually evaluated based on the area ratio.
• [Evaluation criteria] 5 The printing film does not peel off at all. 4: 80% or more of the printed film remained on the film. 3: 50% or more but less than 80% of the printed film remained on the film. 2: Less than 50% of the printed coating remained on the film. 1: When applying cellophane tape, the printed film peels off from the film onto the cellophane tape.
• ⁇ Evaluation item 2 Abrasion resistance>
• the prepared film-forming composition was used to print a solid pattern of 240 mm length x 80 mm width on substrate A using bar coater #4, and then dried with a dryer to form printed layer 1, obtaining a printed matter of configuration 1 below.
• ⁇ Configuration 1 Substrate A-Printed layer 1
• Substrate A Corona-treated polyethylene terephthalate film (Toyobo Co., Ltd., Ester E5100, thickness 12 ⁇ m) (PET)
• Substrate B Biaxial polypropylene film (Toyobo Co., Ltd., Pylen P2161, thickness 20 ⁇ m) (OPP)
• Substrate C Polystyrene film (DXL-270-41S, manufactured by Mitsubishi Chemical Corporation, thickness 40 ⁇ m) (OPS)
• the resulting prints were rubbed on the printed surface with high-quality paper and evaluated using a commercially available Gakushin-type rub fastness tester, with 100 strokes back and forth at a load of 500g. A rating of 4 or higher is within the practical range.
• the printed matter was cut into a test piece of 20 mm x 20 mm, which was then immersed in the solution and stirred with a stirrer. After checking the state of peeling after stirring, the printed matter was rubbed with a finger to see if the coating film would peel off due to rubbing.
• the peelability of the ink coating film under the above conditions was evaluated according to the following evaluation criteria.
• ⁇ Evaluation item 4 Contamination with cleaning fluid>
• the color difference between the cleaning liquid after the peeling tests performed under each of the test conditions 1 and 2 in the above ⁇ Evaluation item 3: peelability> and a 1.5 mass% aqueous solution of sodium hydroxide was measured using a spectrophotometric color/haze meter COH7700 (manufactured by Nippon Denshoku Industries Co., Ltd.) and evaluated according to the following evaluation criteria.
• the prepared film-forming composition was evaluated in the same manner as in Example 1.
• the composition of the film-forming composition and the evaluation results are shown in Tables 1 and 2 below.
• Example 3 A film-forming composition was prepared in the same manner as in Example 1, except that the composition for forming the film was changed to the composition shown in Table 1 below.
• the prepared film-forming composition was evaluated in the same manner as in Example 1.
• the composition of the film-forming composition and the evaluation results are shown in Tables 1 and 2 below.
• the prepared film-forming composition was evaluated in the same manner as in Example 1.
• the composition of the film-forming composition and the evaluation results are shown in Tables 1 and 2 below.
• Examples 5 to 11 A film-forming composition was prepared in the same manner as in Examples 1 and 4, except that the composition of the film-forming composition in Example 1 was changed to the composition shown in Table 1 below. The prepared film-forming composition was evaluated in the same manner as in Example 1. The composition of the film-forming composition and the evaluation results are shown in Tables 1 and 2 below.
• the film-forming composition of the present invention it is possible to form a film that can be easily removed by treatment with an alkaline solution and from which the film layer can be easily removed from the plastic substrate, and it is also possible to form a film that prevents discoloration of the alkaline solution after removal, has excellent adhesion to the substrate, is excellent in abrasion resistance, and has good toughness.

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• 2023
  • 2023-10-31 WO PCT/JP2023/039228 patent/WO2024106199A1/ja not_active Ceased
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