WO2023002853A1 - Acrylic resin for ink - Google Patents

Acrylic resin for ink Download PDF

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Publication number
WO2023002853A1
WO2023002853A1 PCT/JP2022/026943 JP2022026943W WO2023002853A1 WO 2023002853 A1 WO2023002853 A1 WO 2023002853A1 JP 2022026943 W JP2022026943 W JP 2022026943W WO 2023002853 A1 WO2023002853 A1 WO 2023002853A1
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Prior art keywords
meth
parts
mass
acrylate
group
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PCT/JP2022/026943
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French (fr)
Japanese (ja)
Inventor
芳峰 坂元
秀明 安藤
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株式会社日本触媒
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Priority to JP2023536685A priority Critical patent/JPWO2023002853A1/ja
Publication of WO2023002853A1 publication Critical patent/WO2023002853A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • 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
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks

Definitions

  • the present invention relates to an acrylic resin for ink.
  • Ink compositions using the acrylic resin for ink of the present invention can be used as inks such as inkjet inks, flexographic printing inks, offset printing inks, lithographic printing inks, gravure printing inks, and screen printing inks. It can be used preferably.
  • the acrylic resin for ink of the present invention can be suitably used particularly as a water-based ink for inkjet and an ink for gravure printing.
  • Patent Document 1 describes a biopolyurethane resin obtained by reacting a biopolyol component (A) and an isocyanate component (B).
  • the biopolyol component (A) comprises, as raw materials, a diol component (a) containing a plant-derived component and a dicarboxylic acid component (b) containing a plant-derived component. It is a biopolyester polyol polymerized with an acid component.
  • the diol component (a) contains plant-derived 1,2-propanediol and/or 1,3-propanediol, and the dicarboxylic acid component (b) contains adipic acid or dimer acid and plant-derived succinate.
  • a printing ink obtained by applying this bio-polyurethane resin having a high degree of biomass as a binder exhibits excellent adhesion performance to various plastic substrates, especially biomass plastic substrates.
  • An object of the present invention is to provide an ink resin having good water resistance and weather resistance and a high degree of biomass.
  • the inventors of the present invention conducted studies in view of the above problems, and found that an ink acrylic resin having a biomass content of 10% or more has good water resistance and weather resistance, and completed the present invention. .
  • the configuration of the present invention is as follows. [1] Acrylic resin for ink having a biomass content of 10% or more. [2] The acrylic resin for ink according to [1], which has a (meth)acrylate-derived structural unit having a cycloaliphatic group. [3] The acrylic resin for ink according to [2], wherein the (meth)acrylate having a cycloaliphatic group is an ester of a cycloaliphatic hydrocarbon having one hydroxyl group and (meth)acrylic acid.
  • An ink composition comprising the acrylic resin according to any one of [1] to [6] or the aqueous dispersion according to [7].
  • the ink composition according to [8] further comprising polymeric wax.
  • a method for producing a laminate comprising the step of applying the ink composition according to [8] onto a printing substrate.
  • the acrylic resin for ink which has favorable water resistance and weather resistance, and has little environmental load can be provided. Furthermore, according to the present invention, an acrylic resin for ink is provided which has good adhesion to a substrate. In a preferred embodiment, an acrylic resin for ink is provided which has excellent adhesion to olefinic substrates such as biaxially oriented polypropylene (OPP) and has good scratch resistance.
  • OPP biaxially oriented polypropylene
  • the acrylic resin for ink of the present disclosure is an acrylic resin having a biomass degree of 10% or more.
  • the degree of biomass in the present disclosure is based on the formula shown below.
  • Biomass degree (%) (biomass-derived carbon mass/total carbon mass) x 100
  • This measurement can be performed by the accelerator mass spectrometry (AMS method) by applying the radiocarbon dating method. That is, it can be obtained by measuring the ratio of the radioactive isotope 14 C in all carbon elements and converting it.
  • AMS method accelerator mass spectrometry
  • the acrylic resin of the present disclosure has a biomass degree of 10% or more, preferably 20% or more, more preferably 30% or more, and even more preferably 40% or more, from the viewpoint of water resistance, weather resistance, and environmental load.
  • the upper limit of the biomass degree is not particularly limited, and may be 100%, but may be, for example, 90% or less, particularly 80% or less. That is, the biomass degree is preferably 20-100%, more preferably 30-90%, and even more preferably 40-80%.
  • the resin is a broader concept than “polymer”.
  • the resin may be composed of, for example, one or more polymers, and if necessary, materials other than polymers, such as UV absorbers, antioxidants, additives such as fillers, compatibilizers, stabilizers, etc. Additives such as agents (preferably solid agents) may be included.
  • the acrylic resin of the present disclosure belongs to resins having a structural unit derived from a monomer having an ethylenic double bond, and at least a structure derived from an acrylic monomer as a structural unit derived from the monomer having an ethylenic double bond It includes a polymer having one or more units (acrylic polymer).
  • the above acrylic monomer means an acryloyl group or a methacryloyl group, or a group in which a hydrogen atom in these groups is replaced with another atom or atomic group (the substituted group includes, for example, a malenoyl group, a fumaroyl group, a crotonoyl group , an itaconoyl group, a citraconyl group, etc.) or a derivative of such a monomer.
  • the acrylic monomers of the present disclosure are preferably monomers having an acroyl group or a methacryloyl group, in which the hydrogen atoms in these groups are not replaced by other atoms or atomic groups.
  • the acrylic resin of the present disclosure may contain one or more acrylic polymers.
  • the acrylic polymer content is preferably 50 parts by mass or more, more preferably 70 parts by mass or more, and even more preferably 90 parts by mass or more per 100 parts by mass of the acrylic resin of the present disclosure.
  • the acrylic polymer contained in the acrylic resin of the present disclosure may be a polymer having 50 parts by mass or more of structural units derived from an acrylic monomer in 100 parts by mass of the polymer. It is preferably at least 70 parts by mass, even more preferably at least 80 parts by mass.
  • “(meth)acrylate” means “acrylate” or “methacrylate”.
  • “(Meth)acrylic acid” means “acrylic acid” or “methacrylic acid”.
  • (Meth)acryl means "acryl” or "methacryl”.
  • (meth)acryloyl” means “acryloyl” or "methacryloyl.”
  • the acrylic polymer of the present disclosure has a structural unit derived from a monomer having an ethylenic double bond, and as long as the monomer having an ethylenic double bond has at least one or more acrylic monomers, the acrylic It may or may not contain monomers other than monomers.
  • Monofunctional monomers and polyfunctional monomers are included in the monomers having an ethylenic double bond of the present disclosure and the acrylic monomers that are one aspect thereof, and both of these can be used in the present invention. It preferably contains at least a monofunctional monomer. Monofunctional monomers and polyfunctional monomers may be used alone or in combination.
  • the ratio of the monofunctional monomer and the polyfunctional monomer is preferably 100/0 to 50/50, more preferably 100/0 to 90/10, more preferably 100/0 to 95/5. More preferably, it may be 100/0.
  • ⁇ Monofunctional monomer> Specific examples of monomers having an ethylenic double bond, which correspond to monofunctional monomers, are described below. Examples of monofunctional monomers among monomers having an ethylenic double bond of the present disclosure include acid group-containing monomers, alkyl or alkenyl (meth)acrylates, aromatic group-containing (meth)acrylates, and hydroxyl group-containing (meth)acrylates.
  • piperidine group-containing monomer oxo group-containing monomer, fluorine atom or chlorine atom-containing monomer, nitrogen atom-containing monomer, epoxy group-containing monomer, alkoxyalkyl (meth)acrylate, silane group-containing monomer, carbonyl group-containing monomer, aziridinyl group-containing monomer , styrene-based monomers, addition-polymerizable oxazolines, etc., but are not limited to these examples.
  • Each of these ethylenic double bond-containing monomers may be used alone, or two or more of them may be used in combination.
  • the alkyl or alkenyl (meth)acrylates, the aromatic group-containing (meth)acrylates, the hydroxyl group-containing (meth)acrylates, the alkoxyalkyl (meth)acrylates, and the aralkyl (meth)acrylates correspond to acrylic monomers.
  • the aziridinyl group-containing monomers and the like include those corresponding to acrylic monomers and monomers not corresponding to acrylic monomers but having an ethylenic double bond.
  • the styrene-based monomer, the addition-polymerizable oxazoline, and the like do not correspond to acrylic monomers, but correspond to monomers having an ethylenic double bond.
  • monomers corresponding to acrylic monomers include, for example, (meth)acrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, maleic anhydride, and other vinyl aliphatic mono- or dicarboxylic acids; vinyl aliphatic dicarboxylic acid monoesters such as monomethyl maleate, monobutyl maleate, monomethyl itaconate, and monobutyl itaconate, and carboxyl group-containing aliphatic monomers; , the invention is not limited to such examples only.
  • monomers that do not correspond to acrylic monomers include vinyl aromatic carboxylic acids such as vinyl benzoic acid, but the present invention is not limited only to such examples. .
  • These acid group-containing monomers may be used alone or in combination of two or more.
  • vinyl aliphatic mono- or dicarboxylic acids such as acrylic acid, methacrylic acid and itaconic acid are preferred, and vinyl monomers such as acrylic acid and methacrylic acid are preferred. Aliphatic monocarboxylic acids are more preferred.
  • the acid group-containing monomer of the present disclosure may have a biomass degree of 0%.
  • the biomass degree of the acid group-containing monomer is preferably 20% or more, more preferably 30% or more, and still more preferably 40% or more.
  • Alkyl or alkenyl (meth)acrylates of the present disclosure include (meth)acrylates with linear alkyl groups, (meth)acrylates with branched alkyl groups, (meth)acrylates with cycloaliphatic groups, and the like.
  • As the alkyl or alkenyl (meth)acrylate a (meth)acrylate having a cycloaliphatic group is used from the viewpoint of adhesion to substrates, particularly adhesion to olefinic substrates such as biaxially oriented polypropylene (OPP). is preferred.
  • the alkyl or alkenyl (meth)acrylate of the present disclosure may have a biomass degree of 0%, but from the viewpoint of environmental load
  • the degree of biomass is preferably 20% or higher, more preferably 30% or higher, even more preferably 40% or higher.
  • the (meth)acrylate having a linear alkyl group of the present disclosure preferably has, for example, a linear alkyl group having 1 to 30 carbon atoms, and may have a linear alkyl group having 1 to 25 carbon atoms. More preferably, it has a linear alkyl group having 1 to 20 carbon atoms.
  • methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) Acrylates are preferred.
  • the (meth)acrylate having a linear alkyl group of the present disclosure may have a biomass degree of 0%, From the viewpoint of environmental load, the biomass degree is preferably 20% or more, more preferably 30% or more, and even more preferably 40% or more.
  • the (meth)acrylate having a branched alkyl group of the present disclosure preferably has, for example, a branched alkyl group having 4 to 40 carbon atoms, and more preferably has a branched alkyl group having 4 to 30 carbon atoms. It is more preferable to have a branched alkyl group having 4 to 20 carbon atoms.
  • the (meth)acrylate having a branched alkyl group of the present disclosure may have a biomass degree of 0%. From the viewpoint of environmental load, the biomass degree is preferably 20% or more, more preferably 30% or more, and even more preferably 40% or more.
  • the (meth)acrylate having a cyclic aliphatic group of the present disclosure preferably has, for example, a cyclic aliphatic group having 5 to 20 carbon atoms, and more preferably has a cyclic aliphatic group having 5 to 15 carbon atoms, It is more preferable to have a cycloaliphatic group with 5 to 12 carbon atoms.
  • the (meth)acrylate having a cyclic aliphatic group is preferably an ester of a cyclic aliphatic hydrocarbon having one hydroxyl group and (meth)acrylic acid, specifically cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate.
  • t-butyl cyclohexyl (meth) acrylate bornyl (meth) acrylate, isobornyl (meth) acrylate, thuyanyl (meth) acrylate, 1-isopropyl-4-methylcyclohexyl (meth) acrylate (hydrogenated terpinen-4-ol and ( meth)ester with acrylic acid), 1-methyl-4-isopropylcyclohexyl (meth)acrylate (ester of hydrogenated terpeneol and (meth)acrylic acid), 2-isopropyl-5-methylcyclohexyl (meth)acrylate (water ester of added menthol and (meth)acrylic acid), dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and the like.
  • (Meth)acrylates having a cyclic saturated aliphatic group particularly cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, bornyl (meth)acrylate, isobornyl (meth)acrylate, etc. are preferred, and cyclohexyl (meth)acrylate, bornyl (meth)acrylate, etc. Acrylates and isobornyl (meth)acrylates are more preferred.
  • These (meth)acrylates having a cycloaliphatic group can be used alone or in combination.
  • the (meth)acrylate having a cycloaliphatic group of the present disclosure may have a biomass degree of 0%. From the viewpoint of environmental load, the biomass degree is preferably 20% or more, more preferably 30% or more, and even more preferably 40% or more.
  • Cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, and isobornyl (meth)acrylate having the above biomass degree are preferable from the viewpoint of water resistance, weather resistance, adhesion to substrates, and environmental load, and cyclohexyl (meth)acrylate and isobornyl (Meth)acrylates are more preferred.
  • (Meth)acrylates having an aromatic group of the present disclosure include, for example, aralkyl (meth)acrylates such as benzyl (meth)acrylate, phenylethyl (meth)acrylate, methylbenzyl (meth)acrylate, and naphthylmethyl (meth)acrylate. ; phenoxyethyl (meth)acrylate; and the like, but are not limited to these examples.
  • aromatic group-containing (meth)acrylates may be used alone or in combination of two or more.
  • the (meth)acrylate having an aromatic group is preferably an aralkyl (meth)acrylate, more preferably an aralkyl (meth)acrylate having an aralkyl group having 7 to 18 carbon atoms. If the monomer other than the (meth)acrylate having an aromatic group has a predetermined biomass degree, the (meth)acrylate having an aromatic group of the present disclosure may have a biomass degree of 0%, but environmental From the viewpoint of load, the biomass degree is preferably 1% or more, more preferably 5% or more, and even more preferably 10% or more.
  • hydroxyl group-containing (meth)acrylates of the present disclosure include 2-hydroxyethyl (meth)acrylate (also referred to as ethylene glycol (meth)acrylate), 2-hydroxypropyl (meth)acrylate, and 3-hydroxypropyl (meth)acrylate. , 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and other hydroxyl group-containing (meth) acrylates having 1 to 18 carbon atoms in the ester group, but are limited only to these examples. is not. These hydroxyl group-containing (meth)acrylates may be used alone or in combination of two or more.
  • the number of carbon atoms in the ester group means the number of carbon atoms in the portion derived from alcohol in the ester composed of carboxylic acid and alcohol. If the monomer other than the hydroxyl group-containing (meth)acrylate has a predetermined biomass degree, the hydroxyl group-containing (meth)acrylate of the present disclosure may have a biomass degree of 0%, but from the viewpoint of environmental load, the biomass degree is preferably 20% or more, more preferably 30% or more, even more preferably 40% or more.
  • monomers corresponding to acrylic monomers include, for example, 4-(meth)acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-(meth)acryloylamino-2 , 2,6,6-tetramethylpiperidine, 4-(meth)acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4-(meth)acryloyl-1-methoxy-2,2,6, 6-tetramethylpiperidine, 4-cyano-4-(meth)acryloyloxy-2,2,6,6-tetramethylpiperidine, 1-(meth)acryloyl-4-(meth)acryloylamino-2,2,6 ,6-tetramethylpiperidine, 4-crotonoylamino-2,2,6,6-tetramethylpiperidine, 4-(meth)acryloylamino-1,2,2,6,6-pentamethylpiperidine, 4-cyano -4-(meth)acryl
  • piperidine group-containing (meth)acrylates having two methyl groups but are not limited to such examples.
  • monomers that do not correspond to acrylic monomers include piperidines having four methyl groups at the 2- and 6-positions, such as 2,2,6,6-tetramethyl-4-vinyloxypiperidine. Examples include group-containing monomers, but are not limited to these examples. These piperidine group-containing monomers may be used alone or in combination of two or more. When the acrylic polymer of the present disclosure uses a piperidine group-containing monomer, the piperidine group-containing monomer is not included in the nitrogen atom-containing monomer.
  • the piperidine group-containing monomer of the present disclosure may have a biomass degree of 0%.
  • the biomass degree is preferably 1% or more, more preferably 5% or more, and even more preferably 10% or more.
  • monomers corresponding to acrylic monomers include, for example, ethylene glycol methoxy (meth) acrylate, diethylene glycol (meth) acrylate, diethylene glycol methoxy (meth) acrylate, diethylene glycol ethoxy (meth) acrylate (ethyl Carbitol (meth)acrylate), polyethylene glycol ethoxy (meth)acrylate (also referred to as ethoxypolyethylene glycol (meth)acrylate) (di- or poly)ethylene glycol (methoxy or ethoxy) (meth)acrylate, etc.
  • ethylene glycol methoxy (meth) acrylate diethylene glycol (meth) acrylate
  • diethylene glycol methoxy (meth) acrylate diethylene glycol ethoxy (meth) acrylate
  • ethyl Carbitol (meth)acrylate ethyl Carbitol (meth)acrylate
  • oxo group-containing monomers of the present disclosure monomers that do not correspond to acrylic monomers include (2-methoxyethyl) vinyl ether and the like, but are not limited to such examples. These oxo group-containing monomers may be used alone or in combination of two or more.
  • the oxo group-containing monomers of the present disclosure do not include the hydroxyl group-containing monomers described above and alkoxyalkyl (meth)acrylates described later.
  • the oxo group-containing monomer of the present disclosure may have a biomass degree of 0%. From the viewpoint of environmental load, the biomass degree is preferably 20% or more, more preferably 30% or more, and even more preferably 40% or more.
  • monomers corresponding to acrylic monomers include, for example, trifluoroethyl (meth)acrylate, tetrafluoropropyl (meth)acrylate, octafluoropentyl (meth)acrylate, heptadeca
  • Examples of monomers containing fluorine atoms or chlorine atoms that do not correspond to acrylic monomers include pentafluoroethyltrifluorovinyl ether, but are not limited to these examples. These fluorine atom- or chlorine atom-containing monomers may be used alone, respectively, or two or more of them may be used in combination.
  • the biomass degree of the fluorine atom- or chlorine atom-containing monomer of the present disclosure may be 0%, but from the viewpoint of environmental load, the biomass degree is preferably 1% or more, more preferably 5% or more, and even more preferably 10% or more.
  • monomers corresponding to acrylic monomers include, for example, (meth)acrylamide; N-monomethyl(meth)acrylamide, N-monoethyl(meth)acrylamide, N,N-dimethyl(meth) N-mono C 1-6 alkyl (meth)acrylamide or N,N-di C 1-6 alkyl (meth)acrylamide such as acrylamide, Nn-propyl (meth)acrylamide, N-isopropyl (meth)acrylamide; C 1-4 alkylene bis(meth)acrylamides such as (meth)acrylamide; N-methylol (meth)acrylamide, N-butoxymethyl (meth)acrylamide, dimethylaminoethyl (meth)acrylamide, N,N-dimethylaminopropyl ( N-mono C 1-6 alkyl (meth)acrylamide such as meth)acrylamide, diacetone (meth)acrylamide, which is
  • nitrogen atom-containing monomers of the present disclosure monomers that do not correspond to acrylic monomers include N-vinylpyrrolidone, (meth)acrylonitrile, and the like, but are not limited to these examples. Each of these nitrogen atom-containing monomers may be used alone, or two or more of them may be used in combination.
  • the nitrogen atom-containing monomers of the present disclosure do not include the piperidine group-containing monomers.
  • the nitrogen atom-containing monomer of the present disclosure may have a biomass degree of 0%. From the viewpoint of environmental load, the biomass degree is preferably 1% or more, more preferably 5% or more, and even more preferably 10% or more.
  • epoxy group-containing monomers of the present disclosure monomers corresponding to acrylic monomers include, for example, epoxy group-containing (meth)acrylates such as glycidyl (meth)acrylate and ⁇ -methylglycidyl (meth)acrylate. It is not limited only to such examples.
  • epoxy group-containing monomers of the present disclosure monomers that do not correspond to acrylic monomers include glycidyl allyl ether, but are not limited to such examples. These epoxy group-containing monomers may be used alone, respectively, or two or more of them may be used in combination.
  • the epoxy group-containing monomer of the present disclosure may have a biomass degree of 0%.
  • the biomass degree is preferably 1% or more, more preferably 5% or more, and even more preferably 10% or more.
  • Alkoxyalkyl (meth)acrylates of the present disclosure include, for example, C 1 Examples include -4 alkyl (meth)acrylates in which C 1-4 alkoxy is bonded to the C 1-4 alkyl group, but are not limited to these examples. These alkoxyalkyl (meth)acrylates may be used alone or in combination of two or more. If the monomer other than the alkoxyalkyl (meth)acrylate has a predetermined biomass degree, the alkoxyalkyl (meth)acrylate of the present disclosure may have a biomass degree of 0%. is preferably 20% or more, more preferably 30% or more, even more preferably 40% or more.
  • monomers corresponding to acrylic monomers include, for example, ⁇ -(meth)acryloyloxypropyltrimethoxysilane, ⁇ -(meth)acryloyloxypropylhydroxysilane, ⁇ -(meth)acryloyl (Meth)acryloyloxy C 2-6 alkylsilane compounds such as oxypropylmethylhydroxysilane, but are not limited to such examples.
  • silane group-containing monomers of the present disclosure monomers that do not correspond to acrylic monomers include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri(methoxyethoxy)silane, 2-styrylethyltrimethoxysilane, vinyltrichlorosilane, and the like. However, it is not limited only to such examples. These silane group-containing monomers may be used alone or in combination of two or more. If the monomer other than the silane group-containing monomer has a predetermined biomass degree, the silane group-containing monomer of the present disclosure (especially the silane group-containing monomer as an acrylic monomer) may have a biomass degree of 0%. From the viewpoint of environmental load, the biomass degree is preferably 1% or more, more preferably 5% or more, and even more preferably 10% or more.
  • Examples of monomers corresponding to acrylic monomers among the carbonyl group-containing monomers of the present disclosure include (meth)acryloxyalkylpropenal, acetonyl (meth)acrylate, diacetone (meth)acrylate, and 2-hydroxypropyl (meth)acrylate.
  • carbonyl group-containing monomers of the present disclosure monomers that do not correspond to acrylic monomers include acrolein, bormylstyrene, vinyl ethyl ketone, and the like, but are not limited to these examples. These carbonyl group-containing monomers may be used alone or in combination of two or more. If the monomer other than the carbonyl group-containing monomer has a predetermined biomass degree, the carbonyl group-containing monomer of the present disclosure (especially the carbonyl group-containing monomer as an acrylic monomer) may have a biomass degree of 0%. From the viewpoint of environmental load, the biomass degree is preferably 20% or more, more preferably 30% or more, and even more preferably 40% or more.
  • Examples of monomers corresponding to acrylic monomers among the aziridinyl group-containing monomers of the present disclosure include (meth)acryloylaziridine, (meth)acrylic acid 2-aziridinylethyl, etc., but are limited only to such examples. not something. These aziridinyl group-containing monomers may be used alone or in combination of two or more. If the monomer other than the aziridinyl group-containing monomer has a predetermined biomass degree, the biomass degree of the aziridinyl group-containing monomer of the present disclosure (especially the aziridinyl group-containing monomer as an acrylic monomer) may be 0%. From the viewpoint of environmental load, the biomass degree is preferably 1% or more, more preferably 5% or more, and even more preferably 10% or more.
  • Styrenic monomers of the present disclosure include, for example, styrene, ⁇ -methylstyrene, p-methylstyrene, tert-methylstyrene, chlorostyrene, vinyltoluene, and the like, but are not limited to these examples. These styrenic monomers may be used alone, respectively, or two or more of them may be used in combination. Styrene-based monomers may have functional groups such as alkyl groups such as methyl groups and tert-butyl groups, nitro groups, nitrile groups, alkoxyl groups, acyl groups, sulfone groups, hydroxyl groups, and halogen atoms on the benzene ring. good.
  • the biomass degree of the styrene-based monomer of the present disclosure may be 0% as long as the monomer other than the styrene-based monomer has a predetermined biomass degree.
  • addition polymerizable oxazolines of the present disclosure include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2 -oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline, etc., but only such examples is not limited to Each of these addition-polymerizable oxazolines may be used alone, or two or more of them may be used in combination.
  • the biomass degree of the addition polymerizable oxazoline of the present disclosure may be 0% as long as the monomer other than the addition polymerizable oxazoline has a predetermined biomass degree.
  • At least one of the monofunctional monomers preferably has a biomass degree of more than 0% (for example, 10% or more, preferably 30% or more, more preferably 50% or more).
  • Monofunctional monomers having a biomass degree of more than 0% include acid group-containing monomers, alkyl or alkenyl (meth)acrylates, aromatic group-containing (meth)acrylates, hydroxyl group-containing (meth)acrylates, piperidine group-containing monomers, oxo groups at least one selected from containing monomers, fluorine atom- or chlorine atom-containing monomers, nitrogen atom-containing monomers, epoxy group-containing monomers, alkoxyalkyl (meth)acrylates, silane group-containing monomers, carbonyl group-containing monomers, aziridinyl group-containing monomers, etc.
  • alkyl or alkenyl (meth)acrylates is preferably at least one selected from acid group-containing monomers, alkyl or alkenyl (meth)acrylates, hydroxyl group-containing (meth)acrylates, oxo group-containing monomers, alkoxyalkyl (meth)acrylates, and carbonyl group-containing monomers are more preferred, acid group-containing monomers and alkyl (meth)acrylates are even more preferred, and alkyl (meth)acrylates are particularly preferred.
  • Monofunctional monomers having a biomass degree of more than 0% include monomers having a plant-derived (meth)acryloyl group (hereinafter referred to as a bio (meth)acryloyl group) among the above monofunctional monomers, plant-derived alcohols (hereinafter , bioalcohol) is also a preferred embodiment.
  • a bio(meth)acryloyl group is a group that can be introduced from plant-derived glycerin.
  • Bioalcohols include bioalkanols such as bioethanol, biopropanol, biobutanol, terpene-derived alcohols, etc., all of which are commercially available.
  • Examples of the monomer having a bio(meth)acryloyl group include those classified as acrylic monomers among the above monofunctional monomers.
  • Examples of the monomer having a bioalcohol-derived group include esters of bioalcohol and (meth)acrylic acid, specifically a (meth)acrylate having a linear alkyl group or a branched alkyl group.
  • the (meth)acrylic acid that forms an ester with bioalcohol may be bio(meth)acrylic acid or petroleum-derived (meth)acrylic acid.
  • Examples of monofunctional monomers having a biomass degree of more than 0% include monomers having a bio (meth)acryloyl group, (meth)acrylates having a terpene-derived branched alkyl group, and (meth) having a terpene-derived cycloaliphatic group. Acrylate is preferred. Using a plant-derived acryloyl group can increase the biomass content of many types of monomer components when forming an acrylic polymer with a copolymer composed of multiple acrylic monomers, resulting in biomass production. It is easy to improve the degree.
  • a (meth)acrylate having a terpene-derived branched alkyl group As the monofunctional monomer having a biomass degree of more than 0%, a (meth)acrylate having a terpene-derived branched alkyl group, a (meth)acrylate having a terpene-derived cycloaliphatic group, and the like are more preferable, and a terpene-derived cyclic (Meth)acrylates with aliphatic groups are particularly preferred.
  • a (meth)acrylate having a terpene-derived branched alkyl group or a cycloaliphatic group is used, adhesion, adhesive tape peelability, and weather resistance are improved compared to the case of using a non-terpene-derived alkyl (meth)acrylate. one or more of the properties are improved, and in particular adhesion is improved.
  • (Meth)acrylates having a terpene-derived branched alkyl group include 1-methyl-1-ethyl-5-methylhexyl (meth)acrylate (ester of hydrogenated linalool and (meth)acrylic acid), 2-isopropyl -5-methylhexyl (meth)acrylate (ester of hydrogenated lavandulol and (meth)acrylic acid), 3,7-dimethyloctyl (meth)acrylate (hydrogenated geraniol, hydrogenated nerol, or hydrogenated citronellol) (meth)ester with acrylic acid) and the like.
  • (Meth)acrylates having a terpene-derived cycloaliphatic group include bornyl (meth)acrylate, isobornyl (meth)acrylate, thuyanyl (meth)acrylate, 1-isopropyl-4-methylcyclohexyl (meth)acrylate (hydrogenated terpinene -4-ol and (meth)acrylic acid ester), 1-methyl-4-isopropylcyclohexyl (meth)acrylate (hydrogenated terpeneol and (meth)acrylic acid ester), 2-isopropyl-5-methylcyclohexyl (Meth)acrylates (esters of hydrogenated menthol and (meth)acrylic acid) and the like, preferably bornyl (meth)acrylate, isobornyl (meth)acrylate and the like.
  • Suitable monofunctional monomers of the present disclosure include, for example, alkyl or alkenyl (meth)acrylates ((meth)acrylates with linear alkyl groups, (meth)acrylates with branched alkyl groups, or cycloaliphatic groups).
  • monomers and the like may be mentioned, and (meth)acrylates having a linear alkyl group, (meth)acrylates having a branched alkyl group, (meth)acrylates having a cycloaliphatic group, hydroxyl group-containing (meth) ) It preferably contains one or more selected from acrylates, piperidine group-containing monomers, and acid group-containing monomers, and one or more selected from (meth)acrylates having a cycloaliphatic group and hydroxyl group-containing (meth)acrylates.
  • These monomers may be used alone, respectively, or two or more of them may be used in combination. From the viewpoint of further improving adhesion to corona-treated PET, OPP, etc., preferred monofunctional monomers can be selected, and piperidine group-containing monomers, nitrogen atom-containing monomers, addition-polymerizable oxazolines, etc. are preferred.
  • piperidine group-containing monomers, addition polymerizable oxazolines are more preferable, 4-(meth)acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-(meth)acryloyloxy-1,2,2,6, More preferred are 6-pentamethylpiperidine and 2-isopropenyl-2-oxazoline.
  • a hydroxyl group-containing (meth)acrylate is contained as a monofunctional monomer, it is easy to obtain emulsion particles free of coarse particles, and from the viewpoint of excellent ejection stability of the ink containing the emulsion particles, the hydroxyl group-containing (meth)acrylate It preferably contains an acrylate.
  • the content of structural units derived from acrylic monomers (especially acrylic monomers as monofunctional monomers) in 100 parts by mass of the acrylic polymer of the present disclosure may be 50 parts by mass or more, and should be 60 parts by mass or more. is preferred, 70 parts by mass or more is more preferred, and 80 parts by mass or more is even more preferred.
  • the biomass degree of the acrylic polymer of the present disclosure is 10% or more, preferably 20% or more, more preferably 30% or more, and even more preferably 40% or more.
  • the content of structural units derived from an acid group-containing monomer (preferably an acid group-containing monomer as an acrylic monomer) in 100 parts by mass of the acrylic polymer of the present disclosure may be 0 parts by mass, but polymerization stability and storage stability , from the viewpoint of improving ejection stability and adhesion, 0.1 parts by mass or more is preferable, 0.5 parts by mass or more is more preferable, 1 part by mass or more is even more preferable, and from the viewpoint of ejection stability and low viscosity, 10 parts by mass Parts or less is preferable, 8 parts by mass or less is more preferable, and 6 parts by mass or less is more preferable (that is, 0 to 10 parts by mass is preferable, 0.1 to 10 parts by mass is more preferable, and 0.5 to 8 parts by mass is more preferable. More preferably, 1 to 6 parts by mass is particularly preferable).
  • the content of structural units derived from alkyl or alkenyl (meth)acrylate in 100 parts by mass of the acrylic polymer of the present disclosure is preferably 10 parts by mass or more, and 15 parts by mass from the viewpoint of improving scratch resistance, adhesion, and blocking resistance.
  • the content of structural units derived from (meth)acrylate having a linear alkyl group in 100 parts by mass of the acrylic polymer of the present disclosure may be 0 parts by mass, but is preferably 10 parts by mass or more from the viewpoint of improving scratch resistance. , more preferably 15 parts by mass or more, more preferably 20 parts by mass or more, preferably 70 parts by mass or less from the viewpoint of improving adhesion and blocking resistance, more preferably 65 parts by mass or less, and further preferably 60 parts by mass or less; 30 parts by mass or less is particularly preferable (that is, 0 to 70 parts by mass is preferable, 10 to 65 parts by mass is more preferable, 15 to 60 parts by mass is even more preferable, and 20 to 30 parts by mass is particularly preferable).
  • the content ratio of the (meth)acrylate-derived structural unit having a branched alkyl group in 100 parts by mass of the acrylic polymer of the present disclosure may be 0 parts by mass, but from the viewpoint of low viscosity and ejection stability, it is 10 parts by mass or more. is preferably 15 parts by mass or more, more preferably 20 parts by mass or more, and from the viewpoint of improving adhesion and blocking resistance, it is preferably 70 parts by mass or less, more preferably 65 parts by mass or less, and further 60 parts by mass or less. 30 parts by weight or less is particularly preferred (that is, 0 to 70 parts by weight is preferred, 10 to 65 parts by weight is more preferred, 15 to 60 parts by weight is even more preferred, and 20 to 30 parts by weight is particularly preferred).
  • the content ratio of the (meth)acrylate-derived structural unit having a cycloaliphatic group in 100 parts by mass of the acrylic polymer of the present disclosure may be 30 parts by mass or more, preferably 35 parts by mass or more, from the viewpoint of improving adhesion. , More preferably 40 parts by mass or more, more preferably 45 parts by mass or more, may be 95 parts by mass or less, preferably 90 parts by mass or less, more preferably 85 parts by mass or less (that is, preferably 30 to 95 parts by mass, 35 to 95 parts by mass is more preferable, 40 to 90 parts by mass is more preferable, and 45 to 85 parts by mass is particularly preferable).
  • the content of structural units derived from (meth)acrylate having a cycloaliphatic group in 100 parts by mass of structural units derived from alkyl or alkenyl (meth)acrylate is 30 mass from the viewpoint of improving adhesion.
  • parts or more, preferably 35 parts by mass or more, more preferably 40 parts by mass or more, even more preferably 45 parts by mass or more may be 95 parts by mass or less, preferably 90 parts by mass or less, and 85 parts by mass or less is more preferred (that is, 30 to 95 parts by weight is preferred, 35 to 95 parts by weight is more preferred, 40 to 90 parts by weight is even more preferred, and 45 to 85 parts by weight is particularly preferred).
  • the content ratio derived from hydroxyl group-containing (meth)acrylate in 100 parts by mass of the acrylic polymer of the present disclosure is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, from the viewpoint of improving adhesion and ejection stability. , More preferably 1 part by mass or more, preferably 30 parts by mass or less from the viewpoint of low viscosity and stability over time, more preferably 25 parts by mass or less, further preferably 20 parts by mass or less (that is, 0.1 to 30 parts by mass is preferred, 0.5 to 25 parts by weight is more preferred, and 1 to 20 parts by weight is even more preferred).
  • the content ratio derived from the piperidine group-containing monomer (preferably the piperidine group-containing monomer as the acrylic monomer) in 100 parts by mass of the acrylic polymer of the present disclosure may be 0 parts by mass, but from the viewpoint of further improving weather resistance and adhesion 0.1 parts by mass or more is preferable, 0.2 parts by mass or more is more preferable, 0.5 parts by mass or more is more preferable, and 3 parts by mass or more or 5 parts by mass or more is particularly preferable, from the viewpoint of improving water resistance 30 parts by mass or less is preferable, 20 parts by mass or less is more preferable, 15 parts by mass or less is even more preferable, and 10 parts by mass or less is even more preferable (that is, 0 to 30 parts by mass is preferable, and 0.1 to 30 parts by mass is more preferably 0.2 to 20 parts by mass, even more preferably 0.5 to 15 parts by mass, particularly preferably 3 to 10 parts by mass, and most preferably 5 to 10 parts by mass).
  • the content of the styrene-based monomer in 100 parts by mass of the acrylic polymer of the present disclosure may be 0 parts by mass, but is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, from the viewpoint of improving gloss and water resistance. It is more preferably 60 parts by mass or less from the viewpoint of light resistance and yellowing resistance, more preferably 55 parts by mass or less, and even more preferably 50 parts by mass or less (that is, 0 to 60 parts by mass is preferable, and 10 to 60 parts by mass is preferable. 60 parts by mass is more preferable, 15 to 55 parts by mass is even more preferable, and 20 to 50 parts by mass is particularly preferable).
  • Monomers other than the above that is, (meth)acrylates having aromatic groups, oxo group-containing monomers (preferably oxo group-containing monomers as acrylic monomers), fluorine atom- or chlorine atom-containing monomers (preferably fluorine as acrylic monomers) atom or chlorine atom-containing monomer), nitrogen atom-containing monomer (preferably nitrogen atom-containing monomer as acrylic monomer), epoxy group-containing monomer (preferably epoxy group-containing monomer as acrylic monomer), alkoxyalkyl (meth)acrylate , a silane group-containing monomer (preferably a silane group-containing monomer as an acrylic monomer), a carbonyl group-containing monomer (preferably a carbonyl group-containing monomer as an acrylic monomer), an aziridinyl group-containing monomer (preferably aziridinyl as an acrylic monomer group-containing monomer), the proportion of structural units derived from monomers such as addition-polymerizable oxazoline is, for example, 0 parts by mass or more, or
  • Monomers with ethylenic double bonds also include polyfunctional monomers.
  • the polyfunctional monomer may or may not be an acrylic monomer, but is preferably an acrylic monomer.
  • Examples of polyfunctional monomers to be acrylic monomers of the present disclosure include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, (Meth)acrylate, 1,6-hexanediol di(meth)acrylate, ethylene oxide-modified 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, propylene oxide-modified neopentyl glycol di(meth)acrylate (Meth) acrylate, tripropylene glycol di (meth) acrylate, di (meth) acrylate of polyhydric
  • the polyfunctional monomer of the present disclosure may have a biomass degree of 0%, but environmental load From the viewpoint of , the biomass degree is preferably 1% or more, more preferably 5% or more.
  • the content ratio derived from a polyfunctional monomer (especially a polyfunctional monomer as an acrylic monomer) in 100 parts by mass of the acrylic polymer of the present disclosure is, for example, 0 parts by mass or more or 1 part by mass or more, and 10 parts by mass or less or 5 It may be less than or equal to parts by mass (that is, preferably 0 to 10 parts by mass, more preferably 1 to 5 parts by mass).
  • the acrylic polymer of the present disclosure may contain an ultraviolet absorbing monomer as a monomer component.
  • ultraviolet absorbing monomers include benzotriazole-based ultraviolet absorbing monomers and benzophenone-based ultraviolet absorbing monomers, but are not limited to these examples. These UV-absorbing monomers may be used alone or in combination of two or more.
  • Benzotriazole-based UV-absorbing monomers include, for example, 2-[2′-hydroxy-5′-(meth)acryloyloxymethylphenyl]-2H-benzotriazole, 2-[2′-hydroxy-5′- (Meth)acryloyloxyethylphenyl]-2H-benzotriazole, 2-[2′-hydroxy-5′-(meth)acryloyloxymethylphenyl]-5-tert-butyl-2H-benzotriazole, 2-[2′ -hydroxy-5′-(meth)acryloylaminomethyl-5′-tert-octylphenyl]-2H-benzotriazole, 2-[2′-hydroxy-5′-(meth)acryloyloxypropylphenyl]-2H-benzo triazole, 2-[2′-hydroxy-5′-(meth)acryloyloxyhexylphenyl]-2H-benzotriazole, 2-[2′-hydroxy-3′-tert-butyl
  • Benzophenone-based UV-absorbing monomers include, for example, 2-hydroxy-4-(meth)acryloyloxybenzophenone, 2-hydroxy-4-[2-hydroxy-3-(meth)acryloyloxy]propoxybenzophenone, 2- Hydroxy-4-[2-(meth)acryloyloxy]ethoxybenzophenone, 2-hydroxy-4-[3-(meth)acryloyloxy-2-hydroxypropoxy]benzophenone, 2-hydroxy-3-tert-butyl-4- Examples include [2-(meth)acryloyloxy]butoxybenzophenone and the like, but are not limited to these examples. These benzophenone-based UV-absorbing monomers may be used alone or in combination of two or more.
  • the acrylic resin of the present disclosure is preferably emulsion particles, and more preferably an aqueous dispersion containing acrylic resin particles (also referred to as resin particles) from the viewpoint of safety.
  • an aqueous dispersion containing acrylic resin particles also referred to as resin particles
  • the resin particles of the present disclosure may have a single layer, or may be formed with multiple layers.
  • the resin particles of the present disclosure may have the composition described above for the acrylic polymer.
  • one or more selected from piperidine group-containing monomers, addition polymerizable oxazolines, and hydroxyl group-containing (meth)acrylates are monomer components constituting any layer. may be contained in, but from the viewpoint of further improving adhesion, it is preferably contained in at least the monomer component constituting the outermost layer.
  • the monomer component constituting the resin particles of the present disclosure preferably contains at least one selected from piperidine group-containing monomers, addition polymerizable oxazolines, and hydroxyl group-containing (meth)acrylates.
  • the monomer component constituting at least the outermost layer contains at least one selected from piperidine group-containing monomers, addition polymerizable oxazolines, and hydroxyl group-containing (meth)acrylates.
  • the content of the piperidine group-containing monomer, the addition polymerizable oxazoline, and the hydroxyl group-containing (meth)acrylate in the monomer component is more preferably 0.1 to 30% by mass, more preferably 0.2 to 20% by mass.
  • the total content of the piperidine group-containing monomer, addition polymerizable oxazoline, and hydroxyl group-containing (meth)acrylate in the monomer component is preferably 0.2 to 30% by mass, and is 0.2 to 20% by mass. is even more preferable.
  • the resin particles of the present disclosure are formed of multiple layers, it preferably has 2 to 4 layers, more preferably 2 or 3 layers.
  • the inner layer means the innermost layer (core) of the emulsion particle
  • the outer layer means the other layers excluding the innermost layer (that is, the layers other than the innermost layer, and the outermost layer and the outermost layer means the layer formed on the outermost side.
  • the content of structural units derived from (meth)acrylate having a cycloaliphatic group in 100 parts by mass of the monomer component forming the inner layer may be 30 parts by mass or more, preferably 35 parts by mass or more, more preferably 40 parts by mass or more, further preferably 45 parts by mass or more, may be 95 parts by mass or less, preferably 90 parts by mass or less, It is more preferably 85 parts by mass or less (that is, preferably 30 to 95 parts by mass, more preferably 35 to 95 parts by mass, even more preferably 40 to 90 parts by mass, and particularly preferably 45 to 85 parts by mass).
  • a monomer other than (meth)acrylate having a cycloaliphatic group in 100 parts by mass of the monomer component forming the inner layer (innermost layer), a monomer other than (meth)acrylate having a cycloaliphatic group (
  • the content of the structural unit derived from other monomer A) may be 20 parts by mass or more, preferably 25 parts by mass or more, more preferably 30 parts by mass or more, further preferably 35 parts by mass or more, and 70 parts by mass or more. It may be at most parts by mass, preferably at most 65 parts by mass, more preferably at most 60 parts by mass, and even more preferably at most 55 parts by mass.
  • the resin particles of the present disclosure are formed of a plurality of layers, in 100 parts by mass of the monomer component forming the inner layer (innermost layer), as a structural unit derived from other monomer A, an acid group-containing monomer (especially (meth)acrylic acid, etc.), (meth)acrylates having linear or branched alkyl groups (especially methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate) acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isostearyl (meth)acrylate, etc.), hydroxyl group-containing (meth)acrylate (especially 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-
  • styrenic monomers especially styrene
  • piperidine group-containing monomers especially 4-(meth)acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-(meth)acryloyloxy-1,2,2 , 6,6-pentamethylpiperidine
  • the resin particles of the present disclosure are formed of multiple layers, in 100 parts by mass of the monomer component forming the outer layer (layer other than the innermost layer), a (meth)acrylate-derived structure having a cycloaliphatic group
  • the content of the unit may be 30 parts by mass or more, preferably 35 parts by mass or more, more preferably 40 parts by mass or more, even more preferably 45 parts by mass or more, and may be 95 parts by mass or less and 90 parts by mass or less. is preferred, and 85 parts by weight or less is more preferred (that is, 30 to 95 parts by weight is preferred, 35 to 90 parts by weight is more preferred, 40 to 90 parts by weight is even more preferred, and 45 to 85 parts by weight is particularly preferred).
  • a monomer other than (meth)acrylate having a cycloaliphatic group is included in 100 parts by mass of the monomer component forming the outer layer (layer other than the innermost layer).
  • the content of the structural unit derived from the monomer (hereinafter referred to as other monomer B) may be 20 parts by mass or more, preferably 25 parts by mass or more, more preferably 30 parts by mass or more, and further 35 parts by mass or more.
  • it may be 70 parts by mass or less, preferably 65 parts by mass or less, more preferably 60 parts by mass or less, and further preferably 55 parts by mass or less (that is, preferably 20 to 70 parts by mass, and 25 to 65 parts by mass more preferably 30 to 60 parts by mass, and particularly preferably 35 to 55 parts by mass).
  • the resin particles of the present disclosure are formed of multiple layers, in 100 parts by mass of the monomer component forming the outer layer (layer other than the innermost layer), as a structural unit derived from other monomer B, acid Group-containing monomers (especially (meth)acrylic acid, etc.), (especially meth)acrylates having linear or branched alkyl groups (especially methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, Butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isostearyl (meth) acrylate, etc.), hydroxyl group-containing (meth) acrylate (especially 2-hydroxyethyl ( meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth)
  • the content of structural units derived from (meth)acrylate having a cycloaliphatic group is 30 in 100 parts by mass of the monomer component forming the outermost layer. It may be at least 35 parts by mass, preferably at least 40 parts by mass, even more preferably at least 45 parts by mass, may be at most 95 parts by mass, preferably at most 90 parts by mass, and 85 parts by mass. The following are more preferred (that is, 30 to 95 parts by weight are preferred, 35 to 95 parts by weight are more preferred, 40 to 90 parts by weight are even more preferred, and 45 to 85 parts by weight are particularly preferred).
  • a monomer other than (meth)acrylate having a cycloaliphatic hydrocarbon group (hereinafter , Other monomer C) derived structural unit content may be 20 parts by mass or more, preferably 25 parts by mass or more, more preferably 30 parts by mass or more, further preferably 35 parts by mass or more, and 70 parts by mass parts or less, preferably 65 parts by mass or less, more preferably 60 parts by mass or less, and even more preferably 55 parts by mass or less (that is, preferably 20 to 70 parts by mass, more preferably 25 to 65 parts by mass, 30 to 60 parts by mass is more preferable, and 35 to 55 parts by mass is particularly preferable).
  • the resin particles of the present disclosure are formed of multiple layers, in 100 parts by mass of the monomer component forming the outermost layer, as structural units derived from other monomer C, an acid group-containing monomer ((meta ) acrylic acid, etc.), (meth)acrylates with linear or branched alkyl groups (especially methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, isobutyl ( meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isostearyl (meth) acrylate, etc.), hydroxyl group-containing (meth) acrylate (especially 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (me
  • the polymer layer constituting the inner layer (innermost layer) of the present disclosure and the polymer layer constituting the outer layer (layer other than the innermost layer) is preferably 10 from the viewpoint of improving flexibility, blocking resistance, adhesion to the substrate and scratch resistance. /90 to 90/10, more preferably 20/80 to 80/20, still more preferably 30/70 to 70/30, even more preferably 40/60 to 60/40.
  • the mass ratio (polymer layer constituting the inner layer/polymer layer constituting the outermost layer) of the polymer layer constituting the inner layer (innermost layer) and the polymer layer constituting the outermost layer of the present disclosure is , From the viewpoint of improving flexibility, blocking resistance, adhesion to substrates and scratch resistance, preferably 10/90 to 90/10, more preferably 20/80 to 80/20, still more preferably 30 /70 to 70/30, even more preferably 40/60 to 60/40.
  • the glass transition temperature of the acrylic resin of the present disclosure may be ⁇ 30° C. or higher or ⁇ 10° C. or higher from the viewpoint of improving blocking resistance, scratch resistance, adhesion, and adhesive tape peeling resistance, and 0° C. or higher is preferably 5° C. or higher, more preferably 10° C. or higher, may be 90° C. or lower, preferably 80° C. or lower, more preferably 70° C. or lower, further preferably 60° C. or lower (that is, ⁇ 30 to 90 °C, preferably -10 to 90°C, more preferably 0 to 80°C, even more preferably 5 to 70°C, and particularly preferably 10 to 60°C).
  • the glass transition temperature of the acrylic polymer constituting the acrylic resin is preferably within the above range.
  • the glass transition temperature of the acrylic polymer can be adjusted by adjusting the type and amount of monomers forming the acrylic polymer.
  • the glass transition temperature of the polymer constituting the inner layer (innermost layer) is -10 from the viewpoint of adhesion and scratch resistance. ° C. or higher, preferably 0 ° C. or higher, and the upper limit of the glass transition temperature is preferably 120 ° C. or lower, more preferably 100 ° C. or lower from the viewpoint of adhesion and scratch resistance (that is, -10 to 120 °C is preferred, and 0 to 100°C is more preferred).
  • the glass transition temperature of the polymer forming the inner layer (innermost layer) can be adjusted by adjusting the type and amount of the monomer forming the inner layer (innermost layer).
  • the glass transition temperature of the polymer that constitutes the outer layer has adhesion, scratch resistance, and film-forming properties.
  • the upper limit of the glass transition temperature is preferably 100 ° C. or lower, more preferably 90 ° C. or lower from the viewpoint of adhesion and scratch resistance ( That is, 0 to 100°C is preferable, and 10 to 90°C is more preferable).
  • the glass transition temperature of the polymer forming the outer layer (layer other than the innermost layer) can be adjusted by adjusting the type and amount of the monomer forming the outer layer (layer other than the innermost layer).
  • the glass transition temperature of the polymer constituting the outermost layer is 0° C. from the viewpoint of adhesion, scratch resistance, and film-forming properties. Above, it is preferably 10° C. or higher, and the upper limit of the glass transition temperature is preferably 100° C. or lower, more preferably 90° C. or lower from the viewpoint of adhesion and scratch resistance (that is, 0 to 100° C. preferably 10 to 90° C.).
  • the glass transition temperature of the polymer forming the outermost layer can be adjusted by adjusting the type and amount of the monomer forming the outermost layer.
  • the acrylic resin of the present disclosure may not have an acid value, but if it has an acid value, the value may be 50 mgKOH / g or less, preferably 40 mgKOH / g or less, and 35 mgKOH / g It is more preferably 30 mgKOH/g or less, particularly preferably 10 mgKOH/g or less.
  • the polymer constituting the inner layer may not have an acid value, but if it has an acid value, The value may be 50 mgKOH/g or less, preferably 40 mgKOH/g or less, more preferably 35 mgKOH/g or less, further preferably 30 mgKOH/g or less, and 10 mgKOH/g or less. is particularly preferred.
  • the acid value of the polymer constituting the inner layer of the resin particles (the innermost layer) is within the above range, it is possible to obtain a water-based ink with a viscosity that is preferable as an inkjet ink, and has adhesion, scratch resistance, blocking resistance, and adhesion resistance. Effects of improving tape releasability and ejection stability can be expected.
  • the polymer constituting the outer layer may not have an acid value of 50 mg KOH/ g or less, preferably 40 mgKOH/g or less, more preferably 35 mgKOH/g or less, even more preferably 30 mgKOH/g or less, and particularly preferably 10 mgKOH/g or less.
  • the acid value of the outer layer (layer other than the innermost layer) of the resin particles within the above range, it is possible to obtain a viscosity water-based ink that is preferable as an inkjet ink, and has adhesion, scratch resistance, blocking resistance, and adhesive tape resistance. The effect of improving releasability and ejection stability can be expected.
  • the polymer constituting the outermost layer may not have an acid value, but if it has an acid value, the value may be 50 mgKOH/g or less, preferably 40 mgKOH/g or less, more preferably 35 mgKOH/g or less, even more preferably 30 mgKOH/g or less, and 10 mgKOH/g or less. is particularly preferred.
  • the acid value of the outermost layer of the resin particles within the above range, it is possible to obtain a water-based ink with a viscosity that is preferable as an inkjet ink, and it has excellent adhesion, scratch resistance, blocking resistance, adhesive tape releasability, and ejection stability. An improvement effect can be expected.
  • the polymerization average molecular weight of the acrylic resin of the present disclosure is preferably 100,000 or more, more preferably 300,000 or more, still more preferably 400,000 or more, and even more preferably 50,000 from the viewpoint of improving adhesion, film-forming properties, and leveling properties. more than 10,000.
  • the upper limit of the weight average molecular weight of the resin is not particularly limited because it is difficult to measure the weight average molecular weight when it has a crosslinked structure. It is preferably 4,000,000 or less from the viewpoint of obtaining a water-based ink that is comprehensively excellent in adhesion to liquid, blocking resistance, viscosity change stability, and continuous ejection stability.
  • the weight average molecular weight of the acrylic resin is determined by gel permeation chromatography equipped with an RI detector [manufactured by Tosoh Corporation, product number: HLC-8120GPC, column: TSKgel G-5000HXL and TSKgelGMHXL-L are connected in series. used, developing solvent: tetrahydrofuran (THF)] and standard polystyrene F-450, A-5000, A-1000 and A-300 manufactured by Tosoh Corporation. Means the weight average molecular weight (polystyrene conversion) obtained from the calibration curve created using.
  • THF tetrahydrofuran
  • ⁇ Method for producing acrylic resin Existing methods such as bulk polymerization, suspension polymerization, solution polymerization, precipitation polymerization, and emulsion polymerization can be applied as the method for producing the acrylic resin of the present disclosure.
  • emulsion polymerization is preferable from the viewpoint of reducing environmental load, and it is more preferable to use an aqueous medium such as water as a solvent from the viewpoint of safety.
  • the method of emulsion polymerization of the monomer component includes, for example, an aqueous medium containing a water-soluble organic solvent such as a lower alcohol such as methanol and water, or an emulsifier in a medium such as water.
  • a water-soluble organic solvent such as a lower alcohol such as methanol and water
  • an emulsifier in a medium such as water.
  • examples include a method of dissolving and dropping the monomer component and the polymerization initiator under stirring, and a method of dropping the monomer component previously emulsified using an emulsifier and water into water or an aqueous medium, but only such a method. is not limited to
  • the amount of the medium may be appropriately set in consideration of the amount of non-volatile matter contained in the obtained emulsion.
  • the medium may be charged into the reaction vessel in advance, or may be used as a pre-emulsion.
  • the medium may be used, if necessary, during emulsion polymerization
  • the emulsion polymerization may be performed after mixing the monomer component, the emulsifier and the medium.
  • emulsion polymerization may be carried out by mixing at least one of the monomer components, emulsifier and medium with the rest of the pre-emulsion.
  • the monomer component, emulsifier and medium may be added all at once, added in portions, or added dropwise continuously.
  • the monomer component is emulsion-polymerized in the emulsion in the same manner as described above to obtain the above
  • An outer layer can be formed on the emulsion particles.
  • the monomer component is emulsion-polymerized in the emulsion in the same manner as described above to form an additional layer on the emulsion particles.
  • An outer layer comprising other outer layer polymer components can be formed.
  • emulsion particles having a multilayer structure core-shell emulsion particles
  • one-stage or multiple-stage emulsion polymerization may be carried out prior to the emulsion polymerization for forming the inner layer composed of the polymer component for the inner layer.
  • One or more stages of emulsion polymerization may be carried out between the emulsion polymerization for forming the intermediate layer.
  • one or more stages of emulsion polymerization may be performed between the emulsion polymerization for forming the intermediate layer and the emulsion polymerization for forming the outer layer.
  • one or more stages of emulsion polymerization may be performed between the emulsion polymerization for forming the outer layer.
  • emulsifiers examples include anionic emulsifiers, nonionic emulsifiers, cationic emulsifiers, amphoteric emulsifiers, polymer emulsifiers, etc. These emulsifiers may be used alone or in combination of two or more.
  • the biomass degree of the emulsifier of the present disclosure is preferably 10% or more, more preferably 20% or more, even more preferably 30% or more, and particularly preferably 40% or more, from the viewpoint of environmental load.
  • anionic emulsifiers include alkylsulfate salts such as ammonium dodecylsulfate and sodium dodecylsulfate; alkylsulfonate salts such as ammonium dodecylsulfonate, sodium dodecylsulfonate and sodium alkyldiphenylether disulfonate; ammonium dodecylbenzenesulfonate, sodium dodecylnaphthalenesulfonate and the like.
  • polyoxyethylene alkylsulfonate salts polyoxyethylene alkylsulfonate salts; polyoxyethylene alkylsulfate salts; polyoxyethylene alkylarylsulfate salts; dialkylsulfosuccinates; arylsulfonic acid-formalin condensates; Fatty acid salt; bis(polyoxyethylene polycyclic phenyl ether) methacrylate sulfonate salt, propenyl-alkyl sulfosuccinate ester salt, (meth)acrylic acid polyoxyethylene sulfonate salt, (meth)acrylic acid polyoxyethylene phosphonate salt, allyl allyl group-containing sulfate esters such as oxymethylalkyloxypolyoxyethylene sulfonate salts or salts thereof; allyloxymethylalkoxyethylpolyoxyethylene sulfate ester salts; is not limited to only
  • nonionic emulsifiers include polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, condensates of polyethylene glycol and polypropylene glycol, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, fatty acid monoglycerides, ethylene oxide and aliphatic Condensation products with amines, allyloxymethylalkoxyethylhydroxypolyoxyethylenes, polyoxyalkylene alkenyl ethers, etc., but not limited to these examples.
  • Cationic emulsifiers include, for example, alkylammonium salts such as dodecylammonium chloride, but are not limited to these examples.
  • amphoteric emulsifiers include betaine ester emulsifiers, but are not limited to these examples.
  • Polymeric emulsifiers include, for example, poly(meth)acrylates such as sodium polyacrylate; polyvinyl alcohol; polyvinylpyrrolidone; polyhydroxyalkyl(meth)acrylates such as polyhydroxyethyl acrylate; Examples thereof include copolymers containing one or more of the monomers as a copolymer component, but are not limited to these examples.
  • an emulsifier having a polymerizable group that is, a so-called reactive emulsifier is preferable from the viewpoint of further improving water resistance and image uniformity, and a non-nonylphenyl emulsifier is preferable from the viewpoint of environmental protection.
  • reactive emulsifiers include propenyl-alkylsulfosuccinate ester salts, (meth)acrylic acid polyoxyethylene sulfonate salts, (meth)acrylic acid polyoxyethylene phosphonate salts [for example, manufactured by Sanyo Chemical Industries, Ltd., Product name: Eleminol RS-30, etc.], polyoxyethylene alkylpropenyl phenyl ether sulfonate salt [for example, Daiichi Kogyo Seiyaku Co., Ltd., product name: Aqualon HS-10, etc.], allyloxymethylalkyloxypolyoxyethylene Sulfonate salts [for example, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon KH-10, etc.], sulfonate salts of allyloxymethyl nonylphenoxyethyl hydroxypolyoxyethylene [for example, manufactured by ADEKA Co., Ltd., trade name
  • the amount of the emulsifier per 100 parts by mass of the monomer component is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, still more preferably 2 parts by mass or more, and particularly preferably, from the viewpoint of improving polymerization stability. is 3 parts by mass or more, preferably 10 parts by mass or less, more preferably 6 parts by mass or less from the viewpoint of improving water resistance.
  • polymerization initiators examples include azobisisobutyronitrile, 2,2-azobis(2-methylbutyronitrile), 2,2-azobis(2,4-dimethylvaleronitrile), 2,2-azobis ( 2-diaminopropane) hydrochloride, 4,4-azobis (4-cyanovaleric acid), azo compounds such as 2,2-azobis (2-methylpropionamidine); persulfates such as ammonium persulfate and potassium persulfate; Hydrogen peroxide, benzoyl peroxide, parachlorobenzoyl peroxide, lauroyl peroxide, and peroxides such as ammonium peroxide are included, but are not limited to these examples. These polymerization initiators may be used alone or in combination of two or more.
  • the amount of the polymerization initiator per 100 parts by mass of the monomer component is preferably 0.05 parts by mass or more, more preferably 0, from the viewpoint of increasing the polymerization rate and reducing the residual amount of unreacted monomer components. .1 parts by mass or more, preferably 1 part by mass or less, more preferably 0.5 parts by mass or less from the viewpoint of improving water resistance (that is, 0.05 to 1 part by mass is preferable, 0.1 to 0.5 parts by mass is more preferable).
  • the method of adding the polymerization initiator is not particularly limited. Examples of the method of addition include batch charging, divided charging, and continuous dropwise addition. Moreover, from the viewpoint of advancing the completion time of the polymerization reaction, part of the polymerization initiator may be added before or after the completion of adding the monomer components to the reaction system.
  • a reducing agent such as sodium bisulfite and a decomposing agent for the polymerization initiator such as a transition metal salt such as ferrous sulfate are added to the reaction system in an appropriate amount.
  • a chain transfer agent can also be used to adjust the weight average molecular weight of the emulsion particles.
  • chain transfer agents examples include 2-ethylhexyl thioglycolate, tert-dodecylmercaptan, n-octylmercaptan, n-dodecylmercaptan, mercaptoacetic acid, mercaptopropionic acid, 2-mercaptoethanol, ⁇ -methylstyrene, ⁇ -methyl Examples include styrene dimer and the like, but are not limited to these examples. These chain transfer agents may be used alone or in combination of two or more.
  • the amount of the chain transfer agent per 100 parts by weight of the monomer component is preferably 0.01 to 10 parts by weight from the viewpoint of appropriately adjusting the weight average molecular weight of the emulsion particles.
  • Additives such as a pH buffer, a chelating agent, and a film-forming aid may be added to the reaction system, if necessary.
  • the amount of the additive varies depending on its type and cannot be determined unconditionally. Generally, the amount of the additive per 100 parts by weight of the monomer component is preferably about 0.01 to 5 parts by weight, more preferably about 0.1 to 3 parts by weight.
  • the atmosphere in which the monomer components are emulsion-polymerized is not particularly limited, but from the viewpoint of increasing the efficiency of the polymerization initiator, an inert gas such as nitrogen gas is preferable.
  • the polymerization temperature for emulsion polymerization of the monomer components is not particularly limited, but is generally preferably 50 to 100°C, more preferably 60 to 95°C. The polymerization temperature may be constant or may be changed during the polymerization reaction.
  • the polymerization time for emulsion polymerization of the monomer components is not particularly limited, and may be appropriately set according to the progress of the polymerization reaction, but is usually about 2 to 9 hours.
  • part or all of the acidic groups possessed by the obtained polymer component may be neutralized with a neutralizing agent.
  • the neutralizing agent may be used after adding the monomer component in the final stage, for example, may be used between the first-stage polymerization reaction and the second-stage polymerization reaction, and may be used during the initial emulsification. It may be used at the end of the polymerization reaction.
  • Neutralizing agents include, for example, hydroxides of alkali metals and alkaline earth metals such as sodium hydroxide; carbonates of alkali metals and alkaline earth metals such as sodium hydrogen carbonate and calcium carbonate; ammonia, monomethylamine, dimethyl Examples include, but are not limited to, alkaline substances such as organic amines such as aminoethanol. Among these neutralizing agents, a volatile alkaline substance such as ammonia is preferable from the viewpoint of improving water resistance, and sodium hydrogen carbonate is preferable from the viewpoint of improving the storage stability of emulsion particles. Neutralizing agents can be used, for example, as aqueous solutions.
  • Silane coupling agents include, for example, (meth)acryloyl groups, vinyl groups, allyl groups, silane coupling agents having polymerizable unsaturated bonds such as propenyl groups, etc., but are limited only to such examples. is not.
  • An emulsion containing emulsion particles is obtained by subjecting the monomer component to emulsion polymerization as described above.
  • the monomer component constituting the outer layer after the polymerization reaction rate in producing the emulsion particles reaches 90% or more, preferably 95% or more. is preferably emulsion-polymerized from the viewpoint of forming a layer-separated structure in the emulsion particles.
  • a layer made of other polymer components may be formed, if necessary, as long as the object of the present invention is not hindered. Therefore, when producing the emulsion particles contained in the emulsion for water-based ink of the present disclosure, after forming the inner layer of the emulsion particles and before forming the outer layer, the required may form a layer composed of other polymer components.
  • the monomer component used for forming the outer layer may be the same as the monomer component used as the starting material for the inner layer of the emulsion particles.
  • the emulsion polymerization method and polymerization conditions for forming the outer layer can be the same as the method and polymerization conditions for producing the inner layer of the emulsion particles.
  • Emulsion particles having an inner layer and an outer layer can be obtained as described above. If necessary, a surface layer made of other polymer components may be further formed on the surface of the outer layer as long as the object of the present invention is not hindered.
  • an outer layer is formed on the inner layer to obtain an emulsion particle having an inner layer and an outer layer.
  • Crosslinkability can be imparted to the above emulsion by further containing a crosslinking agent.
  • the cross-linking agent may be one that initiates the cross-linking reaction at room temperature, or one that initiates the cross-linking reaction by heat.
  • blocking resistance and adhesion can be further improved by incorporating a cross-linking agent into the emulsion particles.
  • Suitable cross-linking agents include, for example, oxazoline group-containing compounds, isocyanate group-containing compounds, aminoplast resins, and the like. These cross-linking agents may be used alone or in combination of two or more. Among these cross-linking agents, oxazoline group-containing compounds are preferable from the viewpoint of improving the storage stability of the aqueous ink emulsion of the present disclosure.
  • the content of the acrylic polymer in 100 parts by mass of the aqueous dispersion of the present disclosure may be 20 parts by mass or more, preferably 25 parts by mass or more, and more preferably 30 parts by mass or more from the viewpoint of low viscosity and ejection stability. It is preferably 35 parts by mass or more, more preferably 70 parts by mass or less, preferably 65 parts by mass or less, more preferably 60 parts by mass or less, and further preferably 55 parts by mass or less (that is, preferably 20 to 70 parts by mass , more preferably 25 to 65 parts by mass, still more preferably 30 to 60 parts by mass, and particularly preferably 35 to 55 parts by mass).
  • the content of the acrylic polymer in 100 parts by mass of the non-volatile content of the aqueous dispersion of the present disclosure may be 80 parts by mass or more, preferably 82 parts by mass or more, and 85 parts by mass from the viewpoint of low viscosity and ejection stability. More preferably, it may be 100 parts by mass or less, preferably 98 parts by mass or less, more preferably 95 parts by mass or less (that is, preferably 80 to 100 parts by mass, more preferably 82 to 98 parts by mass, 85 to 95 parts by mass Parts by weight are more preferred).
  • the aqueous dispersion of the present disclosure contains, for example, surfactants, film-forming aids, UV absorbers, UV inhibitors, fillers, leveling agents, dispersants, Additives such as thickeners, wetting agents, plasticizers, stabilizers, antioxidants, polymeric waxes and the like may be included in appropriate amounts.
  • Polymeric waxes of the present disclosure may include natural waxes and synthetic waxes.
  • Examples of natural waxes include petroleum-based waxes, plant-based waxes, and animal and plant-based waxes.
  • Examples of petroleum wax include paraffin wax, microcrystalline wax, petrolatum, and the like.
  • Plant-based waxes include carnauba wax, candelilla wax, rice wax, Japan wax, and the like.
  • Examples of animal and plant waxes include lanolin and beeswax.
  • Synthetic waxes include synthetic hydrocarbon waxes and modified waxes.
  • Synthetic hydrocarbon waxes include polyolefin waxes, (meth)acrylic waxes, Fischer-Tropsch waxes, and the like.
  • Modified waxes include paraffin wax derivatives, montan wax derivatives, microcrystalline wax derivatives and the like. Polyolefin waxes and (meth)acrylic waxes are preferred from the viewpoint of improving adhesion and scratch resistance.
  • the (meth)acrylic wax is not particularly limited.
  • acrylic monomers polymers produced from lauryl (meth)acrylate, tridecyl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, behenyl (meth)acrylate, or derivatives thereof, etc. mentioned.
  • a commercially available product can also be used as the (meth)acrylic wax.
  • Preferred commercially available products include ST100 and ST200 manufactured by Nippon Shokubai Co., Ltd.
  • the polyolefin wax is not particularly limited, and examples thereof include waxes produced from olefins such as ethylene, propylene and butylene or derivatives thereof, and copolymers thereof, specifically polyethylene waxes, polypropylene waxes and polybutylene. wax, a copolymer wax composed of ethylene and a monomer having a carboxylic acid group such as methacrylic acid or acrylic acid, and an oxidized polyethylene wax.
  • polyethylene waxes polypropylene waxes, copolymer waxes composed of ethylene and a monomer having a carboxylic acid group such as methacrylic acid or acrylic acid, and oxidized polyethylene waxes are preferred from the viewpoint of improving adhesion and scratch resistance.
  • the oxidized polyethylene wax of the present disclosure is obtained by oxidizing polyethylene wax, and has a skeleton derived from polyethylene (polyethylene skeleton).
  • the polyethylene skeleton mainly has structural units derived from ethylene.
  • the polyethylene skeleton may be a homopolyethylene (ethylene homopolymer) skeleton, a block polyethylene (a block copolymer of ethylene and another olefin) skeleton, or a random polyethylene (ethylene and another olefin random copolymer) skeleton.
  • Other olefins include alkenes such as propylene, isobutylene, 1-butene, 1-pentene and 1-hexene. These components may be linear or branched. Other olefin components have, for example, 2 to 6 carbon atoms.
  • the content of the ethylene component in the polyethylene skeleton is, for example, 60 mol% or more, and may be 70 mol% or more.
  • the content of the ethylene component in the polyethylene skeleton is, for example, 95 mol% or less, and 90 mol% or less. (that is, the content is preferably 60 to 95 mol %, more preferably 70 to 90 mol %).
  • the oxidized polyethylene wax preferably contains high-density oxidized polyethylene wax from the viewpoint of obtaining better adhesion and scratch resistance.
  • a commercially available product can also be used as the oxidized polyethylene wax.
  • Preferred commercially available products include BYK AQUACER497, AQUACER515, AQUACER4531, AQUACER1547, and the like.
  • the polymer wax can be used singly or in combination of two or more.
  • the polymer wax of the present disclosure is preferably in a state in which solid wax particles are dissolved or dispersed in a solvent, and more preferably in an emulsion state in which solid wax particles are dispersed in a solvent.
  • the solvent is preferably an aqueous medium, more preferably the same aqueous medium as the aqueous medium used for the solvent of the aqueous ink composition.
  • the content (based on solid content) of the polymer wax of the present disclosure is 0.1 per 100 parts by mass of the acrylic resin from the viewpoint of improving adhesion, scratch resistance, blocking resistance, and adhesive tape peeling resistance. It is preferably from 1 to 100 parts by mass, more preferably from 1 to 50 parts by mass, and even more preferably from 3 to 20 parts by mass.
  • the biomass degree of various additives used in the aqueous dispersion of the present disclosure is preferably 10% or more, more preferably 20% or more, even more preferably 30% or more, and particularly preferably 40% or more, from the viewpoint of environmental load. .
  • the minimum film-forming temperature of the aqueous dispersion of the present disclosure is preferably 100° C. or lower, more preferably 90° C. or lower, and even more preferably 70° C., from the viewpoint of improving scratch resistance, adhesion, and adhesive tape peeling resistance. It is below.
  • the lower limit of the lowest film-forming temperature of the aqueous dispersion of the present disclosure is preferably 0° C. from the viewpoint of further improving water resistance, weather resistance, scratch resistance, adhesion, adhesive tape peeling resistance and blocking resistance.
  • more preferably 10° C. or higher, still more preferably 30° C. or higher that is, the minimum film-forming temperature is preferably 0 to 100° C., more preferably 10 to 90° C., and still more preferably 30 to 70° C.).
  • the minimum film-forming temperature of the aqueous dispersion means the minimum temperature at which a crack-free uniform film is formed when the aqueous dispersion is dried, and is defined in JIS K6828-2: 2003. Measured in compliance.
  • the acrylic resin in the aqueous dispersion preferably exists as emulsion particles.
  • the average particle size of the acrylic resin particles is preferably 50 nm or more, more preferably 100 nm or more.
  • the upper limit of the average particle size is preferably 300 nm or less, more preferably 200 nm or less, from the viewpoint of improving scratch resistance, adhesion, etc., and improving water resistance, weather resistance, etc. (i.e., average particle size is preferably 50 to 300 nm, more preferably 100 to 200 nm).
  • the average particle size of the acrylic resin particles in the aqueous dispersion is a multi-sample nanoparticle size measurement system [manufactured by Otsuka Electronics Co., Ltd., product name: nanoSAQLA], the autocorrelation function is obtained by the photon correlation method, and the value (hydrodynamic diameter) is obtained by cumulant analysis.
  • the acrylic resin or the aqueous dispersion containing the acrylic resin of the present disclosure can be suitably used for ink, and is particularly preferably used as an aqueous ink containing an aqueous solvent.
  • the content of the acrylic resin in 100 parts by mass of the water-based ink of the present disclosure may be 1 part by mass or more from the viewpoint of ejection stability, storage stability, and dispersion stability when used for white ink, and may be 3 parts by mass or more.
  • the amount may be 1 part by mass or more, preferably 3 parts by mass or more, more preferably 5 parts by mass or more, and 40 parts by mass.
  • Aqueous inks of the present disclosure contain a colorant.
  • Colorant hues include, for example, achromatic colors such as white, black, and gray, and chromatic colors such as yellow, magenta, cyan, blue, red, orange, and green. is not limited to only
  • Colorants of the present disclosure include pigments and dyes. Among these, pigments are preferred because of their excellent weather resistance. When a pigment is used, the pigment may be used in the form of a pigment dispersion such as a paste. Examples of pigments include organic pigments and inorganic pigments, and these may be used alone or in combination.
  • the colorant used in the water-based ink of the present disclosure is preferably any one colorant selected from white pigments, yellow, magenta, cyan, black, red, blue and green.
  • the white pigment is not particularly limited, and any known inorganic white pigment can be used. Examples thereof include alkaline earth metal sulfates or carbonates; silicas such as fine powder silicic acid and synthetic silicate; calcium silicate, alumina, alumina hydrate, titanium oxide, zinc oxide, talc, clay and the like. .
  • the inorganic white pigment may be surface-treated by various surface treatment methods. Among them, surface-treated titanium oxide is preferable because it exhibits relatively good dispersibility in an aqueous medium. For example, in order to avoid photocatalytic effects, titanium oxide surface-treated with an inorganic substance is preferred, and titanium oxide surface-treated with silica and alumina is preferred.
  • titanium oxide which has been surface-treated with the silica and alumina and then further surface-treated with a silane coupling agent.
  • rutile-type or anatase-type titanium dioxide can be used as titanium oxide, and rutile-type titanium dioxide is more preferable.
  • the average particle size of the titanium oxide is preferably 100-500 nm, more preferably 150-400 nm.
  • the average particle size is 100 nm or less, non-settling property and dispersion stability in an aqueous medium are more likely to be achieved, but the whiteness and opacity are inferior, and there is a possibility that the practicality as an original white ink is reduced.
  • the average particle diameter is 500 nm or more, there is no problem in terms of whiteness and hiding power, but ejection stability tends to be insufficient. Practically, the particle size is more preferably 200 to 300 nm.
  • the average particle diameter of titanium oxide used as a raw material is obtained by measuring the particle diameters of 20 particles using an electron micrograph and taking the average.
  • the average particle size of the titanium oxide contained in the aqueous dispersion or the aqueous ink using the aqueous dispersion is not particularly limited, but the dynamic light scattering method, laser diffraction/scattering method, coulter counter, microscopic method, etc. can be measured by More specifically, the average particle size is measured by a photon correlation method using a multi-sample nanoparticle size measuring system [manufactured by Otsuka Electronics Co., Ltd., trade name: nanoSAQLA], which is a particle size measuring device using a dynamic light scattering method. It is preferable that the average particle diameter (hydrodynamic diameter) is obtained by obtaining the autocorrelation function in and by cumulant analysis.
  • Organic pigments for yellow include C.I. I. Pigment Yellow 1 (Hansa Yellow G), 2, 3 (Hansa Yellow 10G), 4, 5 (Hansa Yellow 5G), 6, 7, 10, 11, 12 (Disazo Yellow AAA), 13, 14, 16, 17, 24 (flavanthrone yellow), 55 (disazo yellow AAPT), 61, 61: 1, 65, 73, 74 (fast yellow 5GX), 75, 81, 83 (disazo yellow HR), 93 (condensed azo yellow 3G), 94 (condensed azo yellow 6G), 95 (condensed azo yellow GR), 97 (fast yellow FGL), 98, 99 (anthraquinone), 100, 108 (anthrapyrimidine yellow), 109 (isoindolinone yellow 2GLT), 110 ( isoindolinone yellow 3RLT), 113, 117, 120 (benzimidazolone yellow H2G), 123 (anthraquinone yellow), 124, 128 (condensed azo yellow 8
  • Organic pigments for magenta water-based ink include C.I. I. Pigment Red 1 (Para Red), 2, 3 (Toluidine Red), 4, 5 (lTR Red), 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21 , 22, 23, 30, 31, 32, 37, 38 (pyrazolone red B), 40, 41, 42, 88 (thioindigo Bordeaux), 112 (naphthol red FGR), 114 (brilliant carmine BS), 122 (dimethyl quinacridone), 123 (perylene vermillion), 144, 146, 149 (perylene scarred), 150, 166, 168 (anthanthrone orange), 170 (naphthol red F3RK), 171 (benzimidazolone maroon HFM), 175 ( benzimidazolone red HFT), 176 (benzimidazolone carmine HF3C), 177, 178 (perylene red), 179 (perylene maroon), 185 (benzimida
  • Organic pigments for cyan include C.I. I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6 (all of these are phthalocyanine blue), 16 (metal-free phthalocyanine blue), 17:1, 18 (alkali blue toner), 19, 21, 22, 25, 56, 60 (thren blue), 64 (dichloroindanthrone blue), 65 (violanthrone), 66 (indigo) and the like.
  • a black organic pigment such as aniline black (C.I. Pigment Black 1) can be used as aniline black (C.I. Pigment Black 1) can be used.
  • Organic pigments used in color water-based inks other than white pigments, yellow, cyan, or magenta water-based inks include C.I. I. Pigment Orange 1, 2, 5, 7, 13, 14, 15, 16 (Vulcan Orange), 24, 31 (Condensed Azo Orange 4R), 34, 36 (Benzimidazolone Orange HL), 38, 40 (Pyrantrone Orange ), 42 (isoindolinone orange RLT), 43, 51, 60 (benzimidazolone-based insoluble monoazo pigment), 62 (benzimidazolone-based insoluble monoazo pigment), 63; I.
  • Pigment Green 7 (phthalocyanine green), 10 (green gold), 36 (chlorobrominated phthalocyanine green), 37, 47 (violanthrone green); or C.I. I. Pigment Brown 1, 2, 3, 5, 23 (Condensed Azo Brown 5R), 25 (Benzimidazolone Brown HFR), 26 (Perylene Bordeaux), 32 (Benzimidazolone Brown HFL) and the like.
  • the amount of the coloring agent per 100 parts by mass of the non-volatile content of the resin emulsion for aqueous ink used in the aqueous ink of the present disclosure is preferably 30 parts by mass or more from the viewpoint of sufficiently coloring the print or image formed with the aqueous ink.
  • the amount of the white pigment per 100 parts by mass of the non-volatile matter of the resin emulsion for water-based ink is preferably from the viewpoint of sufficiently coloring the print or image formed with the water-based ink and improving the color development.
  • 50 parts by mass or more, more preferably 60 parts by mass or more, and from the viewpoint of forming a uniform coating film and/or improving gloss preferably 500 parts by mass or less, more preferably 400 parts by mass or less ( That is, 50 to 500 parts by mass is preferable, and 60 to 400 parts by mass is more preferable).
  • the water-based ink may contain water and other water-soluble organic solvents from the viewpoints of the ink viscosity of the water-based ink, the control of wetting and spreading on the recording medium to be printed, the improvement of the image quality, and the ejection stability.
  • organic solvents include glycols such as propylene glycol, 1,3-propanediol, glycerin, dipropylene glycol, tripropylene glycol, diethylene glycol, triethylene glycol and tetraethylene glycol; monoethylene glycol monomethyl ether, monoethylene glycol mono Ethers of monoethylene glycol such as ethyl ether, monoethylene glycol monopropyl ether, monoethylene glycol monoisopropyl ether, monoethylene glycol monobutyl ether, monoethylene glycol monoisobutyl ether; monopropylene glycol monomethyl ether, monopropylene glycol monoethyl ether, Ethers of monopropylene glycol such as monopropylene glycol monopropyl ether, monopropylene glycol monoisopropyl ether, monopropylene glycol monobutyl ether, monopropylene glycol monoisobutyl ether; polyethylene glycols such as diethylene glycol monomethyl ether (
  • the amount of the water-soluble organic solvent varies depending on the type and amount of the colorant contained in the water-based ink, it cannot be determined unconditionally. It is preferable to determine it as appropriate.
  • the amount of the organic solvent in 100 mass of the water-based ink may be 5 parts by mass or more from the viewpoint of controlling the wetting and spreading on the recording medium to be printed and improving the image quality.
  • preferably 8 parts by mass or more, more preferably 10 parts by mass or more may be 50 parts by mass or less, preferably 45 parts by mass or less, more preferably 40 parts by mass or less (that is, preferably 5 to 50 parts by mass, 8 ⁇ 45 parts by mass is more preferable, and 10 to 40 parts by mass is even more preferable).
  • the water-based ink of the present disclosure contains the resin emulsion for water-based ink and a colorant.
  • a resin such as a water-dispersible resin may also be included.
  • the water-based ink of the present invention may contain, for example, surfactants, film-forming aids, UV absorbers, UV inhibitors, fillers, leveling agents, dispersants, and thickening agents, as long as the objects of the present invention are not hindered. Additives such as thickeners, wetting agents, plasticizers, stabilizers and antioxidants may be included in appropriate amounts.
  • the solid content of the water-based ink of the present disclosure has a biomass degree of 3% or more, preferably 5% or more, more preferably 10% or more, from the viewpoint of water resistance, weather resistance, and environmental load.
  • the upper limit of the biomass degree is not particularly limited, it is, for example, 50% or less, and may be 30% or less. That is, the biomass degree of the solid content is preferably 3 to 50%, more preferably 5 to 50%, even more preferably 10 to 30%.
  • the water-based ink of the present disclosure obtained as described above has excellent adhesion and excellent scratch resistance. It can be suitably used as an ink such as an ink, gravure printing ink, or screen printing ink, especially as an aqueous inkjet ink.
  • a laminate can be produced by including a step of applying the ink composition or water-based ink of the present disclosure onto a printing substrate.
  • printing or an image having a predetermined pattern can be formed by ejecting water-based ink onto a printing base material in a predetermined pattern using an inkjet recording apparatus or the like.
  • printing substrates include paper, paper laminated with resin films such as polyethylene, polypropylene, and polystyrene (coated paper, etc.), metal plates such as aluminum, zinc, and copper, cellulose, polyethylene terephthalate, polystyrene, and olefin. base resins, polycarbonate, polyvinyl acetal, polyvinyl chloride, polyamide, nylon, resin films such as acrylic resins, paper having a metal coating, resin films having a metal coating, and the like.
  • a resin film is preferable as a printing substrate for printing the water-based ink of the present disclosure, and application to polyethylene terephthalate and olefin-based resin is particularly preferable.
  • olefinic resins include polyethylene and polypropylene, and application to polypropylene such as biaxially oriented polypropylene film (OPP) and non-oriented polypropylene film (CPP) is particularly preferred.
  • the water-based ink of the present disclosure is preferably formed on a resin film, and its embodiment is a laminate having a printed layer formed from the water-based ink on the resin film.
  • the laminate of the present disclosure may or may not have a primer layer between the resin film and the printed layer, but it is preferable not to have it from the viewpoint of productivity, and printing is performed directly on the resin film. Layer formation is preferred.
  • the laminate of the present disclosure is laminated in the order of a resin film and a printed layer, and may or may not have a protective film (laminate layer) on the printed layer, but does not have it from the viewpoint of productivity.
  • the water-based ink of the present disclosure it is possible to obtain a laminate that has excellent adhesion to a substrate and good scratch resistance even without a primer layer or a protective film (laminate layer). can be expected.
  • the laminate of the present disclosure can be suitably used for various printed matter.
  • Tg glass transition temperature of polymer component
  • Wm is the content (% by mass) of the monomer m in the monomer component constituting the polymer component
  • Tgm glass transition temperature (absolute temperature: K) of the homopolymer of the monomer m.
  • the acid value derived from the carboxyl groups of the resin emulsion particles means the number of mg of potassium hydroxide required to neutralize the carboxyl groups present in 1 g of the monomer component used in the production of the particles.
  • the minimum film-forming temperature of the resin emulsion was measured according to JISK6828-2:2003.
  • the contents of the flask were maintained at 70° C. for 60 minutes, and the pH was adjusted to 8 by adding 25% aqueous ammonia to complete the polymerization. After cooling the resulting reaction solution to room temperature, it was filtered through a wire mesh of 300 mesh to prepare a resin emulsion.
  • the content of non-volatile matter in this resin emulsion is 50%, the acid value derived from the carboxyl groups of the resin emulsion particles is 0 mgKOH/g, and the inner layer constituting the particles contained in the resin emulsion (resin emulsion particles)
  • the glass transition temperature of the resin was 38°C, and the glass transition temperature of the outer layer resin was 38°C.
  • the minimum film growth temperature was 50° C., the average particle size was 150 nm, and the biomass content in the non-volatile matter was 46%.
  • Production Example 5 a polymer was prepared in the same manner as in Production Example 1, except that the monomer components shown in Table 1 were used for polymerization, and a resin emulsion of Production Example 5 was obtained. Table 1 shows the properties of the obtained resin emulsion.
  • a dropping funnel 326 parts of deionized water, 160 parts of a 25% aqueous solution of emulsifier [manufactured by ADEKA Co., Ltd., trade name: Adekari Sorb SR-10], isobornyl acrylate (IBOA) (biomass degree 73%) 632 parts, 2 -Ethylhexyl acrylate (2EHA) 208 parts, 2-hydroxyethyl methacrylate (HEMA) 150 parts, 4-(meth)acryloyloxy-2,2,6,6-tetramethylpiperidine [manufactured by ADEKA Corporation, trade name: Adekastab LA-87] 10 parts of a pre-emulsion for the first stage dropping was prepared, of which 74 parts corresponding to 5% of the total amount of all monomer components was added to the flask, and the mixture was heated to 70°C while slowly blowing nitrogen gas.
  • emulsifier manufactured by ADEKA Co., Ltd., trade name: Ad
  • the temperature was raised, and 30 parts of a 5% aqueous ammonium persulfate solution was added to initiate polymerization. Thereafter, the remainder of the pre-emulsion for dropping and 30 parts of a 5% aqueous ammonium persulfate solution were uniformly dropped into the flask over 180 minutes. After the dropwise addition was completed, the contents of the flask were maintained at 70° C. for 60 minutes, and the pH was adjusted to 8 by adding 25% aqueous ammonia to complete the polymerization. After cooling the resulting reaction solution to room temperature, it was filtered through a wire mesh of 300 mesh to prepare a resin emulsion.
  • the content of non-volatile matter in this resin emulsion is 50%, the acid value derived from the carboxyl groups of the resin emulsion particles is 0 mgKOH/g, and the resin constituting the particles (resin emulsion particles) contained in the resin emulsion is
  • the glass transition temperature was 38°C.
  • the minimum film growth temperature was 40° C.
  • the average particle size was 150 nm
  • the biomass content in the non-volatile matter was 46%.
  • Production Example 6-9 A polymer was prepared in the same manner as in Production Example 2, except that in Production Example 6-9, the monomer components shown in Table 2 were used for polymerization to obtain a resin emulsion of Production Example 6-9. Table 2 shows the properties of the obtained resin emulsion.
  • the composition of the white paste is given in Table 3.
  • Example 1 To 19.8 parts of the resin emulsion obtained in Production Example 1, 2.8 parts of ST200 (manufactured by Nippon Shokubai Co., Ltd.) as a WAX emulsion was added, and while stirring with a homodisper at a rotation speed of 1000 min -1 , 30 parts of a white paste, 20 parts of propylene glycol (PG), 10 parts of diethylene glycol monobutyl ether (BDG, SP value 9.5), 0.4 parts of surfactant [KF-6011 manufactured by Shin-Etsu Chemical Co., Ltd.], and 100 parts in total Ion-exchanged water was added in the manner described above, and the mixture was further stirred for 30 minutes, followed by filtration through a 3 ⁇ m filter [MCP-3-C10S, manufactured by Advantech] to prepare an aqueous ink.
  • ST200 manufactured by Nippon Shokubai Co., Ltd.
  • BDG diethylene glycol monobutyl ether
  • surfactant KF-6011 manufactured by
  • Examples 2-12, Comparative Examples 1-2 Water-based inks of Examples 2-12 and Comparative Examples 1-2 were obtained in the same manner as in Example 1 except that the compositions shown in Tables 4-5 were used.
  • the head voltage was set to 26 V
  • the frequency was set to 4 kHz
  • the ejected droplet volume was set to 12 pL (picoliters)
  • the head temperature was set to 32° C.
  • the resolution was set to 600 dpi
  • the negative pressure was set to ⁇ 4.0 kPa. set to A corona-treated polyester film (PET) [manufactured by Futamura Chemical Co., Ltd., trade name: Taiko polyester film FE2001] was used as a recording medium, and the corona-treated polyester film was conveyed so that the longitudinal direction and the conveying direction were the same. fixed to the table.
  • PET corona-treated polyester film
  • a print command is transferred to the print evaluation device, and a solid image is printed on a corona-treated polyester film with an ink-jet recording method at a printing amount of 100% (12 pL, 600 x 600 dpi).
  • a test sheet (PET) was obtained by drying the corona-treated polyester film at for 10 seconds.
  • test sheet (OPP) ⁇ Production of inkjet printed matter 2 (test sheet (OPP)> Except for changing the recording medium from corona-treated polyester film (PET) [manufactured by Futamura Chemical Co., Ltd., trade name: Taiko Polyester Film FE2001] to corona-treated OPP film [manufactured by Futamura Chemical Co., Ltd., trade name: FOR-AQ].
  • a test sheet (OPP) was obtained in the same manner as in Preparation 1 of inkjet printed matter (test sheet (PET)).
  • ⁇ Biomass degree> The biomass degree in the non-volatile content of the resin emulsions of Production Examples 1 to 9 and the biomass degree in the non-volatile content (ink solid content) of the water-based inks of Examples and Comparative Examples were calculated from the biomass component content (% by mass). Calculated and obtained.
  • Tables 1 and 2 show the biomass content in the nonvolatile matter of the resin emulsion in each production example.
  • the calculation of the biomass degree in Example 1 is as follows.
  • the water resistance was determined by measuring the 60° specular gloss of the test sheet (PET) before and after immersion in water resistance with a gloss meter (manufactured by Nippon Denshoku Industries Co., Ltd., product number: VG-7000). Specifically, the test sheet (PET) is immersed in hot water at 40 ° C. for 24 hours (water resistance test), the water is wiped off sufficiently, and the gloss of the test sheet (PET) is measured with the gloss meter.
  • [gloss retention (%)] [[gloss after water resistance test] ⁇ [gloss before water resistance test]]] ⁇ 100
  • the gloss retention rate was determined based on. Based on the value of this gloss retention rate, the water resistance was evaluated based on the following evaluation criteria. 5: Gloss retention rate is 80% or more 3: Gloss retention rate is 70 or more and less than 80% 1: Gloss retention rate is less than 70%
  • the weather resistance was determined by measuring the 60° specular gloss of the test sheet (PET) before and after the following weather resistance test with a gloss meter (manufactured by Nippon Denshoku Industries Co., Ltd., product number: VG-7000). Weather resistance test conditions Installation conditions: South facing 30 degrees, direct exposure (Exposure site: Suita City, Osaka / Nippon Shokubai Co., Ltd.
  • the acrylic resin for ink of the present invention is suitably used as a resin to be contained in ink such as inkjet ink, flexographic printing ink, offset printing ink, lithographic printing ink, gravure printing ink, and screen printing ink. be able to.

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Abstract

The purpose of the present invention is to provide a resin for inks which has satisfactory water resistance and weatherability and has a high biomass ratio. This resin for inks is characterized by being an acrylic resin for inks which has a biomass ratio of 10% or higher.

Description

インク用アクリル系樹脂Acrylic resin for ink
　本発明は、インク用アクリル系樹脂に関する。本発明のインク用アクリル系樹脂を用いたインク組成物は、例えば、インクジェット用インク、フレキソ印刷用インク、オフセット印刷用インク、リソグラフ印刷用インク、グラビア印刷用インク、スクリーン印刷用インクなどのインクとして好適に使用することができる。本発明のインク用アクリル系樹脂は、特にインクジェット用水性インク、グラビア印刷用インクとして好適に使用することができる。 The present invention relates to an acrylic resin for ink. Ink compositions using the acrylic resin for ink of the present invention can be used as inks such as inkjet inks, flexographic printing inks, offset printing inks, lithographic printing inks, gravure printing inks, and screen printing inks. It can be used preferably. The acrylic resin for ink of the present invention can be suitably used particularly as a water-based ink for inkjet and an ink for gravure printing.
　エネルギーおよび環境の政策、原油価格の上昇および不安定化、化石資源の枯渇に対する公的／政治的な認識から、生体材料から誘導される持続可能なモノマーを見出す必要性が生じてきている。生体再生可能な原料を用いることによって、製造業者は、二酸化炭素排出量を減らすことができ、ゼロカーボンへ、またはさらにカーボンニュートラルな二酸化炭素排出量へと移行することができ、近年その重要性が高まっている。 Public/political perceptions of energy and environmental policies, rising and destabilizing oil prices, and depletion of fossil resources have created a need to find sustainable monomers derived from biomaterials. By using bio-renewable raw materials, manufacturers can reduce their carbon footprint and move to a zero carbon or even carbon neutral carbon footprint, which has gained importance in recent years. rising.
　例えば特許文献１にはバイオポリオール成分（Ａ）と、イソシアネート成分（Ｂ）とを反応させてなるバイオポリウレタン樹脂が記載されている。前記バイオポリオール成分（Ａ）は、植物由来の成分を含むジオール成分（ａ）と、植物由来の成分を含むジカルボン酸成分（ｂ）とを原料に含んでなる、多官能アルコール成分と多官能カルボン酸成分との重合物のバイオポリエステルポリオールである。前記ジオール成分（ａ）が、植物由来の、１，２－プロパンジオール及び／又は１，３－プロパンジオールを含み、前記ジカルボン酸成分（ｂ）が、アジピン酸又はダイマー酸と、植物由来のコハク酸とを含み、バイオポリウレタン樹脂１００質量％に対して、植物由来成分の含有量が３５質量％以上であることを特徴とする。このバイオマス度が高いバイオポリウレタン樹脂をバインダーに適用してなる印刷インキが各種プラスチック基材、特にバイオマスプラスチック基材に対して優れた接着性能を示すことが記載されている。 For example, Patent Document 1 describes a biopolyurethane resin obtained by reacting a biopolyol component (A) and an isocyanate component (B). The biopolyol component (A) comprises, as raw materials, a diol component (a) containing a plant-derived component and a dicarboxylic acid component (b) containing a plant-derived component. It is a biopolyester polyol polymerized with an acid component. The diol component (a) contains plant-derived 1,2-propanediol and/or 1,3-propanediol, and the dicarboxylic acid component (b) contains adipic acid or dimer acid and plant-derived succinate. and an acid, and the content of the plant-derived component is 35% by mass or more with respect to 100% by mass of the biopolyurethane resin. It is described that a printing ink obtained by applying this bio-polyurethane resin having a high degree of biomass as a binder exhibits excellent adhesion performance to various plastic substrates, especially biomass plastic substrates.
特開２０１９－１７２９７７号公報JP 2019-172977 A
　しかしながらポリウレタン樹脂を印刷インクに用いた際には、耐水性及び耐候性が不足するという課題が存在することが判明した。耐水性及び耐候性に優れ、バイオマス度の高い樹脂を得ることは困難であった。
　本発明の目的は、良好な耐水性、耐候性を有し、かつバイオマス度の高いインク用樹脂を提供することである。 However, when a polyurethane resin is used as a printing ink, it has been found that there is a problem of insufficient water resistance and weather resistance. It has been difficult to obtain a resin that is excellent in water resistance and weather resistance and has a high degree of biomass.
An object of the present invention is to provide an ink resin having good water resistance and weather resistance and a high degree of biomass.
　本発明者らは、上記のような問題点に鑑み検討を行い、バイオマス度１０％以上のインク用アクリル系樹脂が、良好な耐水性、耐候性を有することを見出し、本発明を完成させた。
　本発明の構成は以下の通りである。
［１］　バイオマス度１０％以上のインク用アクリル系樹脂。
［２］　環状脂肪族基を有する（メタ）アクリレート由来の構造単位を有する［１］に記載のインク用アクリル系樹脂。
［３］　前記環状脂肪族基を有する（メタ）アクリレートが、１つの水酸基を有する環状脂肪族炭化水素と（メタ）アクリル酸とのエステルである［２］に記載のインク用アクリル系樹脂。
［４］　ポリマー１００質量部に対する環状脂肪族基を有する（メタ）アクリレート由来の構造単位の割合が３０質量部以上８０質量部以下である［２］又は［３］に記載のインク用アクリル系樹脂。
［５］　前記環状脂肪族基がテルペン由来の基である［２］又は［３］に記載のインク用アクリル系樹脂。
［６］　酸価が２０ｍｇＫＯＨ／ｇ以下である［１］～［３］のいずれかに記載のインク用アクリル系樹脂。
［７］　［１］～［６］のいずれかに記載のインク用アクリル系樹脂を含む水性分散体。
［８］　［１］～［６］のいずれかに記載のアクリル系樹脂、または［７］に記載の水性分散体を含むインク組成物。
［９］　さらに高分子ワックスを含む［８］に記載のインク組成物。
［１０］　印刷用基材上に［１］～［６］のいずれかに記載のインク用アクリル系樹脂を含む層を有する積層体。
［１１］　［８］に記載のインク組成物を印刷基材上に塗布する工程を含む積層体の製造方法。 The inventors of the present invention conducted studies in view of the above problems, and found that an ink acrylic resin having a biomass content of 10% or more has good water resistance and weather resistance, and completed the present invention. .
The configuration of the present invention is as follows.
[1] Acrylic resin for ink having a biomass content of 10% or more.
[2] The acrylic resin for ink according to [1], which has a (meth)acrylate-derived structural unit having a cycloaliphatic group.
[3] The acrylic resin for ink according to [2], wherein the (meth)acrylate having a cycloaliphatic group is an ester of a cycloaliphatic hydrocarbon having one hydroxyl group and (meth)acrylic acid.
[4] The acrylic resin for ink according to [2] or [3], wherein the ratio of the (meth)acrylate-derived structural unit having a cycloaliphatic group to 100 parts by mass of the polymer is 30 parts by mass or more and 80 parts by mass or less. .
[5] The acrylic resin for ink according to [2] or [3], wherein the cycloaliphatic group is a terpene-derived group.
[6] The acrylic resin for ink according to any one of [1] to [3], which has an acid value of 20 mgKOH/g or less.
[7] An aqueous dispersion containing the acrylic resin for ink according to any one of [1] to [6].
[8] An ink composition comprising the acrylic resin according to any one of [1] to [6] or the aqueous dispersion according to [7].
[9] The ink composition according to [8], further comprising polymeric wax.
[10] A laminate having a layer containing the acrylic resin for ink according to any one of [1] to [6] on a substrate for printing.
[11] A method for producing a laminate, comprising the step of applying the ink composition according to [8] onto a printing substrate.
　本発明によれば、良好な耐水性、耐候性を有し、かつ環境負荷の少ないインク用アクリル系樹脂が提供できる。
　さらに本発明によれば、基材への密着性が良好なインク用アクリル系樹脂が提供される。好ましい態様においては、二軸延伸ポリプロピレン（ＯＰＰ）などのオレフィン系基材への密着性に優れると共に耐引っ掻き傷性も良好なインク用アクリル系樹脂が提供される。 ADVANTAGE OF THE INVENTION According to this invention, the acrylic resin for ink which has favorable water resistance and weather resistance, and has little environmental load can be provided.
Furthermore, according to the present invention, an acrylic resin for ink is provided which has good adhesion to a substrate. In a preferred embodiment, an acrylic resin for ink is provided which has excellent adhesion to olefinic substrates such as biaxially oriented polypropylene (OPP) and has good scratch resistance.
　本開示のインク用アクリル系樹脂はバイオマス度が１０％以上のアクリル系樹脂である。本開示のバイオマス度とは、以下に示す式による。
　バイオマス度（％）＝（バイオマス由来の炭素質量／全炭素質量）×１００
　この測定は、放射性炭素年代測定法を応用して、加速器質量分析法（ＡＭＳ法）により、行うことができる。すなわち、全炭素元素中の放射性同位元素１４Ｃの比率を測定して、換算して求めることができる。また、バイオマス度が既知の原料を用いた場合は、樹脂組成よりバイオマス度を算出することも可能である。
　本開示のアクリル系樹脂は耐水性、耐候性、環境負荷の観点からバイオマス度が１０％以上であり、２０％以上が好ましく、３０％以上がより好ましく、４０％以上がさらに好ましい。バイオマス度の上限は特に限定されず、１００％であってもよいが、例えば９０％以下、特に８０％以下でもよい。すなわちバイオマス度は、２０～１００％が好ましく、３０～９０％がより好ましく、４０～８０％がよりさらに好ましい。 The acrylic resin for ink of the present disclosure is an acrylic resin having a biomass degree of 10% or more. The degree of biomass in the present disclosure is based on the formula shown below.
Biomass degree (%) = (biomass-derived carbon mass/total carbon mass) x 100
This measurement can be performed by the accelerator mass spectrometry (AMS method) by applying the radiocarbon dating method. That is, it can be obtained by measuring the ratio of the radioactive isotope 14 C in all carbon elements and converting it. Moreover, when using raw materials with a known biomass content, it is also possible to calculate the biomass content from the resin composition.
The acrylic resin of the present disclosure has a biomass degree of 10% or more, preferably 20% or more, more preferably 30% or more, and even more preferably 40% or more, from the viewpoint of water resistance, weather resistance, and environmental load. The upper limit of the biomass degree is not particularly limited, and may be 100%, but may be, for example, 90% or less, particularly 80% or less. That is, the biomass degree is preferably 20-100%, more preferably 30-90%, and even more preferably 40-80%.
　＜アクリル系樹脂＞
　本明細書において、「樹脂」は「ポリマー（重合体）」よりも広い概念である。樹脂は、例えば１種または２種以上のポリマーからなってもよいし、必要に応じて、ポリマー以外の材料、例えば紫外線吸収剤、酸化防止剤、フィラーなどの添加剤、相溶化剤、安定化剤などの添加剤（好ましくは、固形剤）を含んでいてもよい。
　本開示のアクリル系樹脂とは、エチレン性二重結合を有するモノマーに由来する構造単位を有する樹脂に属し、前記エチレン性二重結合を有するモノマーに由来する構造単位として少なくともアクリル系モノマー由来の構造単位の１種または２種以上を有するポリマー（アクリル系ポリマー）を含む。上記アクリル系モノマーとは、アクリロイル基若しくはメタクリロイル基、又は、これらの基における水素原子が他の原子若しくは原子団に置き換わった基（前記置き換わった基としては、例えば、マレノイル基、フマロイル基、クロトノイル基、イタコノイル基、シトラコノイル基など）を有するモノマー又はそのようなモノマーの誘導体を言う。
　本開示のアクリル系モノマーとしては、アクロイル基又はメタクリロイル基を有するモノマーであって、これらの基における水素原子が他の原子若しくは原子団に置き換わったものではない基が好ましく、該好ましいモノマーには、（メタ）アクリル酸、（メタ）アクリル酸エステルが含まれる。
　本開示のアクリル系樹脂は、アクリル系ポリマーを１種または２種以上含んでいても良い。
　本開示のアクリル系樹脂１００質量部あたり、アクリル系ポリマーの含有量は５０質量部以上が好ましく、７０質量部以上がより好ましく、９０質量部以上がさらに好ましい。 <Acrylic resin>
As used herein, "resin" is a broader concept than "polymer". The resin may be composed of, for example, one or more polymers, and if necessary, materials other than polymers, such as UV absorbers, antioxidants, additives such as fillers, compatibilizers, stabilizers, etc. Additives such as agents (preferably solid agents) may be included.
The acrylic resin of the present disclosure belongs to resins having a structural unit derived from a monomer having an ethylenic double bond, and at least a structure derived from an acrylic monomer as a structural unit derived from the monomer having an ethylenic double bond It includes a polymer having one or more units (acrylic polymer). The above acrylic monomer means an acryloyl group or a methacryloyl group, or a group in which a hydrogen atom in these groups is replaced with another atom or atomic group (the substituted group includes, for example, a malenoyl group, a fumaroyl group, a crotonoyl group , an itaconoyl group, a citraconyl group, etc.) or a derivative of such a monomer.
The acrylic monomers of the present disclosure are preferably monomers having an acroyl group or a methacryloyl group, in which the hydrogen atoms in these groups are not replaced by other atoms or atomic groups. (Meth)acrylic acid and (meth)acrylic acid esters are included.
The acrylic resin of the present disclosure may contain one or more acrylic polymers.
The acrylic polymer content is preferably 50 parts by mass or more, more preferably 70 parts by mass or more, and even more preferably 90 parts by mass or more per 100 parts by mass of the acrylic resin of the present disclosure.
　本開示のアクリル系樹脂に含まれるアクリル系ポリマーとしては、耐水性、耐候性の観点から、ポリマー１００質量部中にアクリル系モノマー由来の構造単位を５０質量部以上有するポリマーであってよく、６０質量部以上有することが好ましく、７０質量部以上がより好ましく、８０質量部以上がさらに好ましい。
　エチレン性二重結合を有するモノマーに由来する構造単位とは、エチレン性不飽和二重結合が開いた構造（二重結合（Ｃ＝Ｃ）が単結合（－Ｃ－Ｃ－）となった構造）に相当する。 From the viewpoint of water resistance and weather resistance, the acrylic polymer contained in the acrylic resin of the present disclosure may be a polymer having 50 parts by mass or more of structural units derived from an acrylic monomer in 100 parts by mass of the polymer. It is preferably at least 70 parts by mass, even more preferably at least 80 parts by mass.
A structural unit derived from a monomer having an ethylenic double bond is a structure in which an ethylenically unsaturated double bond is open (a structure in which a double bond (C=C) becomes a single bond (-C-C-) ).
　アクリル系モノマー由来の構造単位とは、例えばアクリル系モノマーの重合反応によって、各モノマーのエチレン性不飽和二重結合が開いた構造（二重結合（Ｃ＝Ｃ）が単結合（－Ｃ－Ｃ－）となった構造）に相当する。
　本発明において、「（メタ）アクリレート」は、「アクリレート」または「メタクリレート」を意味する。「（メタ）アクリル酸」は、「アクリル酸」または「メタクリル酸」を意味する。「（メタ）アクリル」は、「アクリル」または「メタクリル」を意味する。また、「（メタ）アクリロイル」は、「アクリロイル」または「メタクリロイル」を意味する。 Structural units derived from acrylic monomers are structures in which the ethylenically unsaturated double bonds of each monomer are opened by, for example, a polymerization reaction of acrylic monomers (double bonds (C=C) are replaced with single bonds (-C-C -) structure).
In the present invention, "(meth)acrylate" means "acrylate" or "methacrylate". "(Meth)acrylic acid" means "acrylic acid" or "methacrylic acid". "(Meth)acryl" means "acryl" or "methacryl". Moreover, "(meth)acryloyl" means "acryloyl" or "methacryloyl."
　本開示のアクリル系ポリマーは、エチレン性二重結合を有するモノマー由来の構造単位を有しており、該エチレン性二重結合を有するモノマーは少なくとも１種以上のアクリル系モノマーを有する限り、アクリル系モノマー以外のモノマーを含んでも含んでいなくてもよい。
　本開示のエチレン性二重結合を有するモノマーやその一態様であるアクリル系モノマーには、それぞれ、単官能モノマーおよび多官能モノマーが含まれるが、本発明では、これらをいずれも用いることができる。少なくとも単官能モノマーを含むことが好ましい。単官能モノマーおよび多官能モノマーは、それぞれ単独で用いてもよく、併用してもよい。単官能モノマーと多官能モノマーの割合（単官能モノマー／多官能モノマー）は、１００／０～５０／５０が好ましく、１００／０～９０／１０がより好ましく、１００／０～９５／５がよりさらに好ましく、１００／０であってもよい。 The acrylic polymer of the present disclosure has a structural unit derived from a monomer having an ethylenic double bond, and as long as the monomer having an ethylenic double bond has at least one or more acrylic monomers, the acrylic It may or may not contain monomers other than monomers.
Monofunctional monomers and polyfunctional monomers are included in the monomers having an ethylenic double bond of the present disclosure and the acrylic monomers that are one aspect thereof, and both of these can be used in the present invention. It preferably contains at least a monofunctional monomer. Monofunctional monomers and polyfunctional monomers may be used alone or in combination. The ratio of the monofunctional monomer and the polyfunctional monomer (monofunctional monomer/polyfunctional monomer) is preferably 100/0 to 50/50, more preferably 100/0 to 90/10, more preferably 100/0 to 95/5. More preferably, it may be 100/0.
　＜単官能モノマー＞
　以下、エチレン性二重結合を有するモノマーの各具体例のうち単官能モノマーに該当するものについて説明する。
　本開示のエチレン性二重結合を有するモノマーのうち単官能モノマーとしては、例えば、酸基含有モノマー、アルキル又はアルケニル（メタ）アクリレート、芳香族基を有する（メタ）アクリレート、水酸基含有（メタ）アクリレート、ピペリジン基含有モノマー、オキソ基含有モノマー、フッ素原子又は塩素原子含有モノマー、窒素原子含有モノマー、エポキシ基含有モノマー、アルコキシアルキル（メタ）アクリレート、シラン基含有モノマー、カルボニル基含有モノマー、アジリジニル基含有モノマー、スチレン系モノマー、付加重合性オキサゾリンなどが挙げられるが、かかる例示のみに限定されるものではない。これらのエチレン性二重結合を有するモノマーは、それぞれ単独で用いてもよく、２種類以上を併用してもよい。
　前記アルキル又はアルケニル（メタ）アクリレート、前記芳香族基を有する（メタ）アクリレート、前記水酸基含有（メタ）アクリレート、前記アルコキシアルキル（メタ）アクリレート、前記アラルキル（メタ）アクリレートはアクリル系モノマーに相当する。
　前記酸基含有モノマー、前記ピペリジン基含有モノマー、前記オキソ基含有モノマー、前記フッ素原子又は塩素原子含有モノマー、前記窒素原子含有モノマー、前記エポキシ基含有モノマー、前記シラン基含有モノマー、前記カルボニル基含有モノマー、前記アジリジニル基含有モノマーなどは、アクリル系モノマーに相当するものと、アクリル系モノマーに相当しないがエチレン性二重結合を有するモノマーとを含む。
　前記スチレン系モノマー、前記付加重合性オキサゾリンなどは、アクリル系モノマーに相当しないがエチレン性二重結合を有するモノマーに相当する。 <Monofunctional monomer>
Specific examples of monomers having an ethylenic double bond, which correspond to monofunctional monomers, are described below.
Examples of monofunctional monomers among monomers having an ethylenic double bond of the present disclosure include acid group-containing monomers, alkyl or alkenyl (meth)acrylates, aromatic group-containing (meth)acrylates, and hydroxyl group-containing (meth)acrylates. , piperidine group-containing monomer, oxo group-containing monomer, fluorine atom or chlorine atom-containing monomer, nitrogen atom-containing monomer, epoxy group-containing monomer, alkoxyalkyl (meth)acrylate, silane group-containing monomer, carbonyl group-containing monomer, aziridinyl group-containing monomer , styrene-based monomers, addition-polymerizable oxazolines, etc., but are not limited to these examples. Each of these ethylenic double bond-containing monomers may be used alone, or two or more of them may be used in combination.
The alkyl or alkenyl (meth)acrylates, the aromatic group-containing (meth)acrylates, the hydroxyl group-containing (meth)acrylates, the alkoxyalkyl (meth)acrylates, and the aralkyl (meth)acrylates correspond to acrylic monomers.
The acid group-containing monomer, the piperidine group-containing monomer, the oxo group-containing monomer, the fluorine atom- or chlorine atom-containing monomer, the nitrogen atom-containing monomer, the epoxy group-containing monomer, the silane group-containing monomer, and the carbonyl group-containing monomer. The aziridinyl group-containing monomers and the like include those corresponding to acrylic monomers and monomers not corresponding to acrylic monomers but having an ethylenic double bond.
The styrene-based monomer, the addition-polymerizable oxazoline, and the like do not correspond to acrylic monomers, but correspond to monomers having an ethylenic double bond.
　本開示の酸基含有モノマーのうちアクリル系モノマーに相当するモノマーとしては、例えば、（メタ）アクリル酸、マレイン酸、フマル酸、クロトン酸、イタコン酸、シトラコン酸、無水マレイン酸などのビニル脂肪族モノ又はジカルボン酸類；マレイン酸モノメチルエステル、マレイン酸モノブチルエステル、イタコン酸モノメチルエステル、イタコン酸モノブチルエステルなどのビニル脂肪族ジカルボン酸モノエステル類などのカルボキシル基含有脂肪族系モノマーなどが挙げられるが、本発明は、かかる例示のみに限定されるものではない。本発明開示の酸基含有モノマーのうちアクリル系モノマーに相当しないモノマーとしては、ビニル安息香酸などのビニル芳香族カルボン酸類などが挙げられるが、本発明は、かかる例示のみに限定されるものではない。これらの酸基含有モノマーは、それぞれ単独で用いてもよく、２種類以上を併用してもよい。これらの酸基含有モノマーのなかでは、エマルション粒子の分散安定性を向上させる観点から、アクリル酸、メタクリル酸およびイタコン酸などのビニル脂肪族モノ又はジカルボン酸類が好ましく、アクリル酸およびメタクリル酸などのビニル脂肪族モノカルボン酸類がより好ましい。 Among the acid group-containing monomers of the present disclosure, monomers corresponding to acrylic monomers include, for example, (meth)acrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, maleic anhydride, and other vinyl aliphatic mono- or dicarboxylic acids; vinyl aliphatic dicarboxylic acid monoesters such as monomethyl maleate, monobutyl maleate, monomethyl itaconate, and monobutyl itaconate, and carboxyl group-containing aliphatic monomers; , the invention is not limited to such examples only. Of the acid group-containing monomers disclosed in the present invention, monomers that do not correspond to acrylic monomers include vinyl aromatic carboxylic acids such as vinyl benzoic acid, but the present invention is not limited only to such examples. . These acid group-containing monomers may be used alone or in combination of two or more. Among these acid group-containing monomers, from the viewpoint of improving the dispersion stability of emulsion particles, vinyl aliphatic mono- or dicarboxylic acids such as acrylic acid, methacrylic acid and itaconic acid are preferred, and vinyl monomers such as acrylic acid and methacrylic acid are preferred. Aliphatic monocarboxylic acids are more preferred.
　酸基含有モノマー以外のモノマーが所定のバイオマス度を有していれば、本開示の酸基含有モノマー（特にアクリル系モノマーとしての酸基含有モノマー）のバイオマス度は０％であってもよいが、環境負荷の観点から酸基含有モノマーのバイオマス度は２０％以上が好ましく、３０％以上がより好ましく、４０％以上がさらに好ましく、密着性、耐スクラッチ性および環境負荷の観点から上記バイオマス度を有する（メタ）アクリル酸、イタコン酸がより好ましい。 If the monomer other than the acid group-containing monomer has a predetermined biomass degree, the acid group-containing monomer of the present disclosure (especially the acid group-containing monomer as an acrylic monomer) may have a biomass degree of 0%. , From the viewpoint of environmental load, the biomass degree of the acid group-containing monomer is preferably 20% or more, more preferably 30% or more, and still more preferably 40% or more. (Meth)acrylic acid and itaconic acid having
　本開示のアルキル又はアルケニル（メタ）アクリレートとしては、直鎖状アルキル基を有する（メタ）アクリレート、分岐状アルキル基を有する（メタ）アクリレート、環状脂肪族基を有する（メタ）アクリレートなどが挙げられる。アルキル又はアルケニル（メタ）アクリレートとしては、基材への密着性、特に二軸延伸ポリプロピレン（ＯＰＰ）などのオレフィン系基材への密着性の観点から環状脂肪族基を有する（メタ）アクリレートを用いることが好ましい。
　アルキル又はアルケニル（メタ）アクリレート以外のモノマーが所定のバイオマス度を有していれば、本開示のアルキル又はアルケニル（メタ）アクリレートのバイオマス度は０％であってもよいが、環境負荷の観点からバイオマス度は２０％以上が好ましく、３０％以上がより好ましく、４０％以上がさらに好ましい。上記範囲を満たすことにより、耐水性、耐候性、基材への密着性に優れると共に、環境負荷の観点からも好ましいインクを得ることができる。 Alkyl or alkenyl (meth)acrylates of the present disclosure include (meth)acrylates with linear alkyl groups, (meth)acrylates with branched alkyl groups, (meth)acrylates with cycloaliphatic groups, and the like. . As the alkyl or alkenyl (meth)acrylate, a (meth)acrylate having a cycloaliphatic group is used from the viewpoint of adhesion to substrates, particularly adhesion to olefinic substrates such as biaxially oriented polypropylene (OPP). is preferred.
If the monomer other than the alkyl or alkenyl (meth)acrylate has a predetermined biomass degree, the alkyl or alkenyl (meth)acrylate of the present disclosure may have a biomass degree of 0%, but from the viewpoint of environmental load The degree of biomass is preferably 20% or higher, more preferably 30% or higher, even more preferably 40% or higher. By satisfying the above range, it is possible to obtain an ink that is excellent in water resistance, weather resistance, and adhesion to a substrate, and is also preferable from the viewpoint of environmental load.
　本開示の直鎖状アルキル基を有する（メタ）アクリレートとしては、例えば炭素数１～３０の直鎖状アルキル基を有することが好ましく、炭素数１～２５の直鎖状アルキル基を有することがより好ましく、炭素数１～２０の直鎖状アルキル基を有することがさらに好ましい。具体的には、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、ペンチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、オクチル（メタ）アクリレート、デシル（メタ）アクリレート、ウンデシル（メタ）アクリレート、ドデシル（メタ）アクリレート（ラウリル（メタ）アクリレートともいう）、トリデシル（メタ）アクリレート、セチル（メタ）アクリレート、ステアリル（メタ）アクリレート、ベヘニル（メタ）アクリレートなどが例示される。密着性、耐スクラッチ性の観点から、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ブチル（メタ）アクリレート、オクチル（メタ）アクリレート、ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート、ベヘニル（メタ）アクリレートが好ましい。 The (meth)acrylate having a linear alkyl group of the present disclosure preferably has, for example, a linear alkyl group having 1 to 30 carbon atoms, and may have a linear alkyl group having 1 to 25 carbon atoms. More preferably, it has a linear alkyl group having 1 to 20 carbon atoms. Specifically, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, decyl (meth)acrylate ) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate (also called lauryl (meth) acrylate), tridecyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, etc. be done. From the viewpoint of adhesion and scratch resistance, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) Acrylates are preferred.
　直鎖状アルキル基を有する（メタ）アクリレートが所定のバイオマス度を有していれば、本開示の直鎖状アルキル基を有する（メタ）アクリレートのバイオマス度は０％であってもよいが、環境負荷の観点からバイオマス度は２０％以上が好ましく、３０％以上がより好ましく、４０％以上がさらに好ましい。密着性、耐スクラッチ性および環境負荷の観点から上記バイオマス度を有するメチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、ペンチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、オクチル（メタ）アクリレート、デシル（メタ）アクリレート、ウンデシル（メタ）アクリレート、ドデシル（メタ）アクリレート（ラウリル（メタ）アクリレートともいう）、トリデシル（メタ）アクリレート、セチル（メタ）アクリレート、ステアリル（メタ）アクリレート、ベヘニル（メタ）アクリレートが好ましく、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ブチル（メタ）アクリレート、オクチル（メタ）アクリレート、ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート、ベヘニル（メタ）アクリレートがより好ましく、エチル（メタ）アクリレート、ブチル（メタ）アクリレートがさらに好ましい。 If the (meth)acrylate having a linear alkyl group has a predetermined biomass degree, the (meth)acrylate having a linear alkyl group of the present disclosure may have a biomass degree of 0%, From the viewpoint of environmental load, the biomass degree is preferably 20% or more, more preferably 30% or more, and even more preferably 40% or more. Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, and hexyl (meth) acrylate having the above biomass degree from the viewpoint of adhesion, scratch resistance and environmental load ) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate (also called lauryl (meth) acrylate), tridecyl (meth) acrylate, cetyl (meth) acrylate, stearyl ( meth)acrylate and behenyl (meth)acrylate are preferred, and methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, octyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, behenyl ( Meth)acrylate is more preferred, and ethyl (meth)acrylate and butyl (meth)acrylate are even more preferred.
　本開示の分岐状アルキル基を有する（メタ）アクリレートとしては、例えば炭素数４～４０の分岐状アルキル基を有することが好ましく、炭素数４～３０の分岐状アルキル基を有することがより好ましく、炭素数４～２０の分岐状アルキル基を有することがさらに好ましい。具体的には、イソプロピル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｓ－ブチル（メタ）アクリレート、ｔ－ブチル（メタ）アクリレート、ネオペンチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、イソデシル（メタ）アクリレート、イソステアリル（メタ）アクリレート、１－メチル－１－エチル－５－メチルヘキシル（メタ）アクリレート（水添リナロールと（メタ）アクリル酸とのエステル）、２－イソプロピル－５－メチルヘキシル（メタ）アクリレート（水添ラバンジュロールと（メタ）アクリル酸とのエステル）、３，７－ジメチルオクチル（メタ）アクリレート（水添ゲラニオール、水添ネロール、又は水添シトロネロールと（メタ）アクリル酸とのエステル）などが例示され、密着性、耐スクラッチ性の観点からイソブチル（メタ）アクリレート、ｓ－ブチル（メタ）アクリレート、ｔ－ブチル（メタ）アクリレート、ネオペンチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、イソデシル（メタ）アクリレート、イソステアリル（メタ）アクリレートが好ましく、イソブチル（メタ）アクリレート、ｔ－ブチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、イソステアリル（メタ）アクリレートがより好ましい。 The (meth)acrylate having a branched alkyl group of the present disclosure preferably has, for example, a branched alkyl group having 4 to 40 carbon atoms, and more preferably has a branched alkyl group having 4 to 30 carbon atoms. It is more preferable to have a branched alkyl group having 4 to 20 carbon atoms. Specifically, isopropyl (meth) acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, neopentyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) ) acrylate, isostearyl (meth) acrylate, 1-methyl-1-ethyl-5-methylhexyl (meth) acrylate (ester of hydrogenated linalool and (meth) acrylic acid), 2-isopropyl-5-methylhexyl ( meth) acrylate (ester of hydrogenated lavandulol and (meth) acrylic acid), 3,7-dimethyloctyl (meth) acrylate (hydrogenated geraniol, hydrogenated nerol, or hydrogenated citronellol and (meth) acrylic acid ester) and the like, and from the viewpoint of adhesion and scratch resistance, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, neopentyl (meth) acrylate, 2-ethylhexyl (meth) ) acrylate, isodecyl (meth)acrylate and isostearyl (meth)acrylate are preferable, and isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate and isostearyl (meth)acrylate are more preferable.
　分岐状アルキル基を有する（メタ）アクリレート以外のモノマーが所定のバイオマス度を有していれば、本開示の分岐状アルキル基を有する（メタ）アクリレートのバイオマス度は０％であってもよいが、環境負荷の観点からバイオマス度は２０％以上が好ましく、３０％以上がより好ましく、４０％以上がさらに好ましい。 If the monomer other than the (meth)acrylate having a branched alkyl group has a predetermined biomass degree, the (meth)acrylate having a branched alkyl group of the present disclosure may have a biomass degree of 0%. From the viewpoint of environmental load, the biomass degree is preferably 20% or more, more preferably 30% or more, and even more preferably 40% or more.
　本開示の環状脂肪族基を有する（メタ）アクリレートとしては、例えば炭素数５～２０の環状脂肪族基を有することが好ましく、炭素数５～１５の環状脂肪族基を有することがより好ましく、炭素数５～１２の環状脂肪族基を有することがさらに好ましい。環状脂肪族基を有する（メタ）アクリレートは、１つの水酸基を有する環状脂肪族炭化水素と（メタ）アクリル酸とのエステルが好ましく、具体的には、シクロペンチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ｔ－ブチルシクロヘキシル（メタ）アクリレート、ボルニル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ツヤニル（メタ）アクリレート、１－イソプロピル－４－メチルシクロヘキシル（メタ）アクリレート（水添テルピネン－４－オールと（メタ）アクリル酸とのエステル）、１－メチル－４－イソプロピルシクロヘキシル（メタ）アクリレート（水添テルペネオールと（メタ）アクリル酸とのエステル）、２－イソプロピル－５－メチルシクロヘキシル（メタ）アクリレート（水添メントールと（メタ）アクリル酸とのエステル）、ジシクロペンタニル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート等が挙げられる。環状飽和脂肪族基を有する（メタ）アクリレート、特にシクロペンチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ボルニル（メタ）アクリレート、イソボルニル（メタ）アクリレートなどが好ましく、シクロヘキシル（メタ）アクリレート、ボルニル（メタ）アクリレート、イソボルニル（メタ）アクリレートがより好ましい。これらの環状脂肪族基を有する（メタ）アクリレートは、単独または数種類混合して使用することができる。 The (meth)acrylate having a cyclic aliphatic group of the present disclosure preferably has, for example, a cyclic aliphatic group having 5 to 20 carbon atoms, and more preferably has a cyclic aliphatic group having 5 to 15 carbon atoms, It is more preferable to have a cycloaliphatic group with 5 to 12 carbon atoms. The (meth)acrylate having a cyclic aliphatic group is preferably an ester of a cyclic aliphatic hydrocarbon having one hydroxyl group and (meth)acrylic acid, specifically cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate. , t-butyl cyclohexyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, thuyanyl (meth) acrylate, 1-isopropyl-4-methylcyclohexyl (meth) acrylate (hydrogenated terpinen-4-ol and ( meth)ester with acrylic acid), 1-methyl-4-isopropylcyclohexyl (meth)acrylate (ester of hydrogenated terpeneol and (meth)acrylic acid), 2-isopropyl-5-methylcyclohexyl (meth)acrylate (water ester of added menthol and (meth)acrylic acid), dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and the like. (Meth)acrylates having a cyclic saturated aliphatic group, particularly cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, bornyl (meth)acrylate, isobornyl (meth)acrylate, etc. are preferred, and cyclohexyl (meth)acrylate, bornyl (meth)acrylate, etc. Acrylates and isobornyl (meth)acrylates are more preferred. These (meth)acrylates having a cycloaliphatic group can be used alone or in combination.
　環状脂肪族基を有する（メタ）アクリレート以外のモノマーが所定のバイオマス度を有していれば、本開示の環状脂肪族基を有する（メタ）アクリレートのバイオマス度は０％であってもよいが、環境負荷の観点からバイオマス度は２０％以上が好ましく、３０％以上がより好ましく、４０％以上がさらに好ましい。耐水性、耐候性、基材への密着性および環境負荷の観点から上記バイオマス度を有するシクロペンチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレートが好ましく、シクロヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレートがより好ましい。 If the monomer other than the (meth)acrylate having a cycloaliphatic group has a predetermined biomass degree, the (meth)acrylate having a cycloaliphatic group of the present disclosure may have a biomass degree of 0%. From the viewpoint of environmental load, the biomass degree is preferably 20% or more, more preferably 30% or more, and even more preferably 40% or more. Cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, and isobornyl (meth)acrylate having the above biomass degree are preferable from the viewpoint of water resistance, weather resistance, adhesion to substrates, and environmental load, and cyclohexyl (meth)acrylate and isobornyl (Meth)acrylates are more preferred.
　本開示の芳香族基を有する（メタ）アクリレートとしては、例えば、ベンジル（メタ）アクリレート、フェニルエチル（メタ）アクリレート、メチルベンジル（メタ）アクリレート、ナフチルメチル（メタ）アクリレートなどのアラルキル（メタ）アクリレート；フェノキシエチル（メタ）アクリレート；などが挙げられるが、かかる例示のみに限定されるものではない。これらの芳香族基を有する（メタ）アクリレートは、それぞれ単独で用いてもよく、２種類以上を併用してもよい。芳香族基を有する（メタ）アクリレートとしては、アラルキル（メタ）アクリレートが好ましく、炭素数が７～１８のアラルキル基を有するアラルキル（メタ）アクリレートがより好ましい。
　芳香族基を有する（メタ）アクリレート以外のモノマーが所定のバイオマス度を有していれば、本開示の芳香族基を有する（メタ）アクリレートのバイオマス度は０％であってもよいが、環境負荷の観点からバイオマス度は１％以上が好ましく、５％以上がより好ましく、１０％以上がさらに好ましい。 (Meth)acrylates having an aromatic group of the present disclosure include, for example, aralkyl (meth)acrylates such as benzyl (meth)acrylate, phenylethyl (meth)acrylate, methylbenzyl (meth)acrylate, and naphthylmethyl (meth)acrylate. ; phenoxyethyl (meth)acrylate; and the like, but are not limited to these examples. These aromatic group-containing (meth)acrylates may be used alone or in combination of two or more. The (meth)acrylate having an aromatic group is preferably an aralkyl (meth)acrylate, more preferably an aralkyl (meth)acrylate having an aralkyl group having 7 to 18 carbon atoms.
If the monomer other than the (meth)acrylate having an aromatic group has a predetermined biomass degree, the (meth)acrylate having an aromatic group of the present disclosure may have a biomass degree of 0%, but environmental From the viewpoint of load, the biomass degree is preferably 1% or more, more preferably 5% or more, and even more preferably 10% or more.
　本開示の水酸基含有（メタ）アクリレートとしては、例えば、２－ヒドロキシエチル（メタ）アクリレート（エチレングリコール（メタ）アクリレートともいう）、２－ヒドロキシプロピル（メタ）アクリレート、３－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレートなどのエステル基の炭素数が１～１８の水酸基含有（メタ）アクリレートなどが挙げられるが、かかる例示のみに限定されるものではない。これらの水酸基含有（メタ）アクリレートは、それぞれ単独で用いてもよく、２種類以上を併用してもよい。
　なお本明細書でエステル基の炭素数とは、カルボン酸とアルコールとから構成されるエステルのうちアルコールに由来する部分の炭素数を意味する。
　水酸基含有（メタ）アクリレート以外のモノマーが所定のバイオマス度を有していれば、本開示の水酸基含有（メタ）アクリレートのバイオマス度は０％であってもよいが、環境負荷の観点からバイオマス度は２０％以上が好ましく、３０％以上がより好ましく、４０％以上がさらに好ましい。 Examples of hydroxyl group-containing (meth)acrylates of the present disclosure include 2-hydroxyethyl (meth)acrylate (also referred to as ethylene glycol (meth)acrylate), 2-hydroxypropyl (meth)acrylate, and 3-hydroxypropyl (meth)acrylate. , 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and other hydroxyl group-containing (meth) acrylates having 1 to 18 carbon atoms in the ester group, but are limited only to these examples. is not. These hydroxyl group-containing (meth)acrylates may be used alone or in combination of two or more.
In this specification, the number of carbon atoms in the ester group means the number of carbon atoms in the portion derived from alcohol in the ester composed of carboxylic acid and alcohol.
If the monomer other than the hydroxyl group-containing (meth)acrylate has a predetermined biomass degree, the hydroxyl group-containing (meth)acrylate of the present disclosure may have a biomass degree of 0%, but from the viewpoint of environmental load, the biomass degree is preferably 20% or more, more preferably 30% or more, even more preferably 40% or more.
　本開示のピペリジン基含有モノマーのうちアクリル系モノマーに相当するモノマーとしては、例えば、４－（メタ）アクリロイルオキシ－２，２，６，６－テトラメチルピペリジン、４－（メタ）アクリロイルアミノ－２，２，６，６－テトラメチルピペリジン、４－（メタ）アクリロイルオキシ－１，２，２，６，６－ペンタメチルピペリジン、４－（メタ）アクリロイル－１－メトキシ－２，２，６，６－テトラメチルピペリジン、４－シアノ－４－（メタ）アクリロイルオキシ－２，２，６，６－テトラメチルピペリジン、１－（メタ）アクリロイル－４－（メタ）アクリロイルアミノ－２，２，６，６－テトラメチルピペリジン、４－クロトノイルアミノ－２，２，６，６－テトラメチルピペリジン、４－（メタ）アクリロイルアミノ－１，２，２，６，６－ペンタメチルピペリジン、４－シアノ－４－（メタ）アクリロイルアミノ－２，２，６，６－テトラメチルピペリジン、４－クロトノイルオキシ－２，２，６，６－テトラメチルピペリジン、１－（メタ）アクリロイル－４－シアノ－４－（メタ）アクリロイルアミノ－２，２，６，６－テトラメチルピペリジン、１－クロトノイル－４－クロトノイルオキシ－２，２，６，６－テトラメチルピペリジンなどの２位と６位に４つのメチル基を有するピペリジン基含有（メタ）アクリレートが挙げられるが、かかる例示のみに限定されるものではない。本開示のピペリジン基含有モノマーのうちアクリル系モノマーに相当しないモノマーとしては、２，２，６，６－テトラメチル－４－ビニルオキシピペリジンなどの２位と６位に４つのメチル基を有するピペリジン基含有モノマーなどが挙げられるが、かかる例示のみに限定されるものではない。これらのピペリジン基含有モノマーは、それぞれ単独で用いてもよく、２種類以上を併用してもよい。本開示のアクリル系ポリマーがピペリジン基含有モノマーを用いる際には、ピペリジン基含有モノマーは窒素原子含有モノマーには含めないものとする。
　ピペリジン基含有モノマー以外のモノマーが所定のバイオマス度を有していれば、本開示のピペリジン基含有モノマー（特にアクリル系モノマーとしてのピペリジン基含有モノマー）のバイオマス度は０％であってもよいが、環境負荷の観点からバイオマス度は１％以上が好ましく、５％以上がより好ましく、１０％以上がさらに好ましい。 Of the piperidine group-containing monomers of the present disclosure, monomers corresponding to acrylic monomers include, for example, 4-(meth)acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-(meth)acryloylamino-2 , 2,6,6-tetramethylpiperidine, 4-(meth)acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4-(meth)acryloyl-1-methoxy-2,2,6, 6-tetramethylpiperidine, 4-cyano-4-(meth)acryloyloxy-2,2,6,6-tetramethylpiperidine, 1-(meth)acryloyl-4-(meth)acryloylamino-2,2,6 ,6-tetramethylpiperidine, 4-crotonoylamino-2,2,6,6-tetramethylpiperidine, 4-(meth)acryloylamino-1,2,2,6,6-pentamethylpiperidine, 4-cyano -4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, 1-(meth)acryloyl-4-cyano- 4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine, 1-crotonoyl-4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, etc. piperidine group-containing (meth)acrylates having two methyl groups, but are not limited to such examples. Of the piperidine group-containing monomers of the present disclosure, monomers that do not correspond to acrylic monomers include piperidines having four methyl groups at the 2- and 6-positions, such as 2,2,6,6-tetramethyl-4-vinyloxypiperidine. Examples include group-containing monomers, but are not limited to these examples. These piperidine group-containing monomers may be used alone or in combination of two or more. When the acrylic polymer of the present disclosure uses a piperidine group-containing monomer, the piperidine group-containing monomer is not included in the nitrogen atom-containing monomer.
If the monomer other than the piperidine group-containing monomer has a predetermined biomass degree, the piperidine group-containing monomer of the present disclosure (especially the piperidine group-containing monomer as an acrylic monomer) may have a biomass degree of 0%. From the viewpoint of environmental load, the biomass degree is preferably 1% or more, more preferably 5% or more, and even more preferably 10% or more.
　本開示のオキソ基含有モノマーのうちアクリル系モノマーに相当するモノマーとしては、例えば、エチレングリコールメトキシ（メタ）アクリレート、ジエチレングリコール（メタ）アクリレート、ジエチレングリコールメトキシ（メタ）アクリレート、ジエチレングリコールエトキシ（メタ）アクリレート（エチルカルビトール（メタ）アクリレートともいう）、ポリエチレングリコールエトキシ（メタ）アクリレート（エトキシポリエチレングリコール（メタ）アクリレートともいう）などの（ジ又はポリ）エチレングリコール（メトキシ又はエトキシ）（メタ）アクリレートなどが挙げられるが、かかる例示のみに限定されるものではない。本開示のオキソ基含有モノマーのうちアクリル系モノマーに相当しないモノマーとしては、（２－メトキシエチル）ビニルエーテルなどが挙げられるが、かかる例示のみに限定されるものではない。これらのオキソ基含有モノマーは、それぞれ単独で用いてもよく、２種類以上を併用してもよい。なお本開示のオキソ基含有モノマーには、上記水酸基含有モノマー、及び後述するアルコキシアルキル（メタ）アクリレートなどは含まれない。
　オキソ基含有モノマー以外のモノマーが所定のバイオマス度を有していれば、本開示のオキソ基含有モノマー（特にアクリル系モノマーとしてのオキソ基含有モノマー）のバイオマス度は０％であってもよいが、環境負荷の観点からバイオマス度は２０％以上が好ましく、３０％以上がより好ましく、４０％以上がさらに好ましい。 Among the oxo group-containing monomers of the present disclosure, monomers corresponding to acrylic monomers include, for example, ethylene glycol methoxy (meth) acrylate, diethylene glycol (meth) acrylate, diethylene glycol methoxy (meth) acrylate, diethylene glycol ethoxy (meth) acrylate (ethyl Carbitol (meth)acrylate), polyethylene glycol ethoxy (meth)acrylate (also referred to as ethoxypolyethylene glycol (meth)acrylate) (di- or poly)ethylene glycol (methoxy or ethoxy) (meth)acrylate, etc. However, it is not limited only to such examples. Of the oxo group-containing monomers of the present disclosure, monomers that do not correspond to acrylic monomers include (2-methoxyethyl) vinyl ether and the like, but are not limited to such examples. These oxo group-containing monomers may be used alone or in combination of two or more. The oxo group-containing monomers of the present disclosure do not include the hydroxyl group-containing monomers described above and alkoxyalkyl (meth)acrylates described later.
If the monomer other than the oxo group-containing monomer has a predetermined biomass degree, the oxo group-containing monomer of the present disclosure (especially the oxo group-containing monomer as an acrylic monomer) may have a biomass degree of 0%. From the viewpoint of environmental load, the biomass degree is preferably 20% or more, more preferably 30% or more, and even more preferably 40% or more.
　本開示のフッ素原子又は塩素原子含有モノマーのうちアクリル系モノマーに相当するモノマーとしては、例えば、トリフルオロエチル（メタ）アクリレート、テトラフルオロプロピル（メタ）アクリレート、オクタフルオロペンチル（メタ）アクリレート、ヘプタデカフルオロオクチルエチル（メタ）アクリレートなどのエステル基の炭素数が２～１０（好ましくは２～６）のフッ素原子含有アルキル（メタ）アクリレート；クロロエチル（メタ）アクリレートなどのエステル基の炭素数が２～６の塩素原子含有アルキル（メタ）アクリレートなどが挙げられるが、かかる例示のみに限定されるものではない。フッ素原子又は塩素原子含有モノマーのうちアクリル系モノマーに相当しないモノマーとしては、ペンタフルオロエチルトリフルオロビニルエーテルなどが挙げられるが、かかる例示のみに限定されるものではない。これらのフッ素原子又は塩素原子含有モノマーは、それぞれ単独で用いてもよく、２種類以上を併用してもよい。
　フッ素原子又は塩素原子含有モノマー以外のモノマーが所定のバイオマス度を有していれば、本開示のフッ素原子又は塩素原子含有モノマー（特にアクリル系モノマーとしてのフッ素原子又は塩素原子含有モノマー）のバイオマス度は０％であってもよいが、環境負荷の観点からバイオマス度は１％以上が好ましく、５％以上がより好ましく、１０％以上がさらに好ましい。 Among the fluorine atom- or chlorine atom-containing monomers of the present disclosure, monomers corresponding to acrylic monomers include, for example, trifluoroethyl (meth)acrylate, tetrafluoropropyl (meth)acrylate, octafluoropentyl (meth)acrylate, heptadeca A fluorine atom-containing alkyl (meth)acrylate having an ester group having 2 to 10 carbon atoms (preferably 2 to 6) such as fluorooctylethyl (meth)acrylate; and an ester group having 2 to 2 carbon atoms such as chloroethyl (meth)acrylate 6 chlorine atom-containing alkyl (meth)acrylates, etc., but are not limited to these examples. Examples of monomers containing fluorine atoms or chlorine atoms that do not correspond to acrylic monomers include pentafluoroethyltrifluorovinyl ether, but are not limited to these examples. These fluorine atom- or chlorine atom-containing monomers may be used alone, respectively, or two or more of them may be used in combination.
If the monomer other than the fluorine atom- or chlorine atom-containing monomer has a predetermined biomass degree, the biomass degree of the fluorine atom- or chlorine atom-containing monomer of the present disclosure (especially the fluorine atom- or chlorine atom-containing monomer as an acrylic monomer) may be 0%, but from the viewpoint of environmental load, the biomass degree is preferably 1% or more, more preferably 5% or more, and even more preferably 10% or more.
　本開示の窒素原子含有モノマーのうちアクリル系モノマーに相当するモノマーとしては、例えば、（メタ）アクリルアミド；Ｎ－モノメチル（メタ）アクリルアミド、Ｎ－モノエチル（メタ）アクリルアミド、Ｎ，Ｎ－ジメチル（メタ）アクリルアミド、Ｎ－ｎ－プロピル（メタ）アクリルアミド、Ｎ－イソプロピル（メタ）アクリルアミドなどのＮ－モノＣ１－６アルキル（メタ）アクリルアミド又はＮ，Ｎ－ジＣ１－６アルキル（メタ）アクリルアミド；メチレンビス（メタ）アクリルアミドなどのＣ１－４アルキレンビス（メタ）アクリルアミド；Ｎ－メチロール（メタ）アクリルアミド、Ｎ－ブトキシメチル（メタ）アクリルアミド、ジメチルアミノエチル（メタ）アクリルアミド、Ｎ，Ｎ－ジメチルアミノプロピル（メタ）アクリルアミド、ジアセトン（メタ）アクリルアミドなどのＮ－モノＣ１－６アルキル（メタ）アクリルアミドであってヒドロキシ基、Ｃ１－６アルコキシ基、ジＣ１－２アルキルアミノ基、又はＣ２－４アシル基が前記Ｃ１－６アルキル基に結合した化合物などの（メタ）アクリルアミド化合物、
　アミノエチル（メタ）アクリレート、ジメチルアミノエチル（メタ）アクリレート、ジエチルアミノエチル（メタ）アクリレートなどのＣ２－６アルキル（メタ）アクリレートであって、モノ又はジＣ１－４アルキルアミノ基が前記Ｃ２－６アルキル基に結合した化合物、
　などの窒素原子含有（メタ）アクリレート化合物などが挙げられ、かかる例示のみに限定されるものではない。本開示の窒素原子含有モノマーのうちアクリル系モノマーに相当しないモノマーとしては、Ｎ－ビニルピロリドン、（メタ）アクリロニトリル、などが挙げられるが、かかる例示のみに限定されるものではない。これらの窒素原子含有モノマーは、それぞれ単独で用いてもよく、２種類以上を併用してもよい。なお本開示の窒素原子含有モノマーには上記ピペリジン基含有モノマーは含まれない。
　窒素原子含有モノマー以外のモノマーが所定のバイオマス度を有していれば、本開示の窒素原子含有モノマー（特にアクリル系モノマーとしての窒素原子含有モノマー）のバイオマス度は０％であってもよいが、環境負荷の観点からバイオマス度は１％以上が好ましく、５％以上がより好ましく、１０％以上がさらに好ましい。 Among the nitrogen atom-containing monomers of the present disclosure, monomers corresponding to acrylic monomers include, for example, (meth)acrylamide; N-monomethyl(meth)acrylamide, N-monoethyl(meth)acrylamide, N,N-dimethyl(meth) N-mono C 1-6 alkyl (meth)acrylamide or N,N-di C 1-6 alkyl (meth)acrylamide such as acrylamide, Nn-propyl (meth)acrylamide, N-isopropyl (meth)acrylamide; C 1-4 alkylene bis(meth)acrylamides such as (meth)acrylamide; N-methylol (meth)acrylamide, N-butoxymethyl (meth)acrylamide, dimethylaminoethyl (meth)acrylamide, N,N-dimethylaminopropyl ( N-mono C 1-6 alkyl (meth)acrylamide such as meth)acrylamide, diacetone (meth)acrylamide, which is a hydroxy group, a C 1-6 alkoxy group, a di-C 1-2 alkylamino group, or a C 2-4 (meth)acrylamide compounds such as compounds in which an acyl group is bound to said C 1-6 alkyl group;
C 2-6 alkyl (meth)acrylates such as aminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, wherein the mono- or di-C 1-4 alkylamino group is said C 2 a compound bound to a -6 alkyl group,
Nitrogen atom-containing (meth)acrylate compounds such as and the like, and are not limited only to such examples. Of the nitrogen atom-containing monomers of the present disclosure, monomers that do not correspond to acrylic monomers include N-vinylpyrrolidone, (meth)acrylonitrile, and the like, but are not limited to these examples. Each of these nitrogen atom-containing monomers may be used alone, or two or more of them may be used in combination. The nitrogen atom-containing monomers of the present disclosure do not include the piperidine group-containing monomers.
If the monomer other than the nitrogen atom-containing monomer has a predetermined biomass degree, the nitrogen atom-containing monomer of the present disclosure (especially the nitrogen atom-containing monomer as an acrylic monomer) may have a biomass degree of 0%. From the viewpoint of environmental load, the biomass degree is preferably 1% or more, more preferably 5% or more, and even more preferably 10% or more.
　本開示のエポキシ基含有モノマーのうちアクリル系モノマーに相当するモノマーとしては、例えば、グリシジル（メタ）アクリレート、α－メチルグリシジル（メタ）アクリレートなどのエポキシ基含有（メタ）アクリレートなどが挙げられるが、かかる例示のみに限定されるものではない。本開示のエポキシ基含有モノマーのうちアクリル系モノマーに相当しないモノマーとしては、グリシジルアリルエーテルなどが挙げられるが、かかる例示のみに限定されるものではない。これらのエポキシ基含有モノマーは、それぞれ単独で用いてもよく、２種類以上を併用してもよい。
　エポキシ基含有モノマー以外のモノマーが所定のバイオマス度を有していれば、本開示のエポキシ基含有モノマー（特にアクリル系モノマーとしてのエポキシ基含有モノマー）のバイオマス度は０％であってもよいが、環境負荷の観点からバイオマス度は１％以上が好ましく、５％以上がより好ましく、１０％以上がさらに好ましい。 Of the epoxy group-containing monomers of the present disclosure, monomers corresponding to acrylic monomers include, for example, epoxy group-containing (meth)acrylates such as glycidyl (meth)acrylate and α-methylglycidyl (meth)acrylate. It is not limited only to such examples. Of the epoxy group-containing monomers of the present disclosure, monomers that do not correspond to acrylic monomers include glycidyl allyl ether, but are not limited to such examples. These epoxy group-containing monomers may be used alone, respectively, or two or more of them may be used in combination.
If the monomer other than the epoxy group-containing monomer has a predetermined biomass degree, the epoxy group-containing monomer of the present disclosure (especially the epoxy group-containing monomer as an acrylic monomer) may have a biomass degree of 0%. From the viewpoint of environmental load, the biomass degree is preferably 1% or more, more preferably 5% or more, and even more preferably 10% or more.
　本開示のアルコキシアルキル（メタ）アクリレートとしては、例えば、メトキシエチル（メタ）アクリレート、メトキシブチル（メタ）アクリレート（好ましくは３－メトキシブチル（メタ）アクリレート）、エトキシブチル（メタ）アクリレートなどのＣ１－４アルキル（メタ）アクリレートであって、Ｃ１－４アルコキシが前記Ｃ１－４アルキル基に結合した化合物などが挙げられるが、かかる例示のみに限定されるものではない。これらのアルコキシアルキル（メタ）アクリレートは、それぞれ単独で用いてもよく、２種類以上を併用してもよい。
　アルコキシアルキル（メタ）アクリレート以外のモノマーが所定のバイオマス度を有していれば、本開示のアルコキシアルキル（メタ）アクリレートのバイオマス度は０％であってもよいが、環境負荷の観点からバイオマス度は２０％以上が好ましく、３０％以上がより好ましく、４０％以上がさらに好ましい。 Alkoxyalkyl (meth)acrylates of the present disclosure include, for example, C 1 Examples include -4 alkyl (meth)acrylates in which C 1-4 alkoxy is bonded to the C 1-4 alkyl group, but are not limited to these examples. These alkoxyalkyl (meth)acrylates may be used alone or in combination of two or more.
If the monomer other than the alkoxyalkyl (meth)acrylate has a predetermined biomass degree, the alkoxyalkyl (meth)acrylate of the present disclosure may have a biomass degree of 0%. is preferably 20% or more, more preferably 30% or more, even more preferably 40% or more.
　本開示のシラン基含有モノマーのうちアクリル系モノマーに相当するモノマーとしては、例えば、γ－（メタ）アクリロイルオキシプロピルトリメトキシシラン、γ－（メタ）アクリロイルオキシプロピルヒドロキシシラン、γ－（メタ）アクリロイルオキシプロピルメチルヒドロキシシランなどの（メタ）アクリロイルオキシＣ２－６アルキルシラン化合物が挙げられるが、かかる例示のみに限定されるものではない。本開示のシラン基含有モノマーのうちアクリル系モノマーに相当しないモノマーとしては、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリ（メトキシエトキシ）シラン、２－スチリルエチルトリメトキシシラン、ビニルトリクロロシランなどが挙げられるが、かかる例示のみに限定されるものではない。これらのシラン基含有モノマーは、それぞれ単独で用いてもよく、２種類以上を併用してもよい。
　シラン基含有モノマー以外のモノマーが所定のバイオマス度を有していれば、本開示のシラン基含有モノマー（特にアクリル系モノマーとしてのシラン基含有モノマー）のバイオマス度は０％であってもよいが、環境負荷の観点からバイオマス度は１％以上が好ましく、５％以上がより好ましく、１０％以上がさらに好ましい。 Among the silane group-containing monomers of the present disclosure, monomers corresponding to acrylic monomers include, for example, γ-(meth)acryloyloxypropyltrimethoxysilane, γ-(meth)acryloyloxypropylhydroxysilane, γ-(meth)acryloyl (Meth)acryloyloxy C 2-6 alkylsilane compounds such as oxypropylmethylhydroxysilane, but are not limited to such examples. Among the silane group-containing monomers of the present disclosure, monomers that do not correspond to acrylic monomers include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri(methoxyethoxy)silane, 2-styrylethyltrimethoxysilane, vinyltrichlorosilane, and the like. However, it is not limited only to such examples. These silane group-containing monomers may be used alone or in combination of two or more.
If the monomer other than the silane group-containing monomer has a predetermined biomass degree, the silane group-containing monomer of the present disclosure (especially the silane group-containing monomer as an acrylic monomer) may have a biomass degree of 0%. From the viewpoint of environmental load, the biomass degree is preferably 1% or more, more preferably 5% or more, and even more preferably 10% or more.
　本開示のカルボニル基含有モノマーのうちアクリル系モノマーに相当するモノマーとしては、例えば、（メタ）アクリルオキシアルキルプロペナール、アセトニル（メタ）アクリレート、ジアセトン（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレートアセチルアセテート、ブタンジオール－１，４－アクリレートアセチルアセテート、２－（アセトアセトキシ）エチル（メタ）アクリレートなどが挙げられるが、かかる例示のみに限定されるものではない。本開示のカルボニル基含有モノマーのうちアクリル系モノマーに相当しないモノマーとしては、アクロレイン、ホウミルスチロール、ビニルエチルケトンなどが挙げられるが、かかる例示のみに限定されるものではない。これらのカルボニル基含有モノマーは、それぞれ単独で用いてもよく、２種類以上を併用してもよい。
　カルボニル基含有モノマー以外のモノマーが所定のバイオマス度を有していれば、本開示のカルボニル基含有モノマー（特にアクリル系モノマーとしてのカルボニル基含有モノマー）のバイオマス度は０％であってもよいが、環境負荷の観点からバイオマス度は２０％以上が好ましく、３０％以上がより好ましく、４０％以上がさらに好ましい。 Examples of monomers corresponding to acrylic monomers among the carbonyl group-containing monomers of the present disclosure include (meth)acryloxyalkylpropenal, acetonyl (meth)acrylate, diacetone (meth)acrylate, and 2-hydroxypropyl (meth)acrylate. Acetylacetate, butanediol-1,4-acrylate acetylacetate, 2-(acetoacetoxy)ethyl (meth)acrylate and the like, but are not limited to these examples. Of the carbonyl group-containing monomers of the present disclosure, monomers that do not correspond to acrylic monomers include acrolein, bormylstyrene, vinyl ethyl ketone, and the like, but are not limited to these examples. These carbonyl group-containing monomers may be used alone or in combination of two or more.
If the monomer other than the carbonyl group-containing monomer has a predetermined biomass degree, the carbonyl group-containing monomer of the present disclosure (especially the carbonyl group-containing monomer as an acrylic monomer) may have a biomass degree of 0%. From the viewpoint of environmental load, the biomass degree is preferably 20% or more, more preferably 30% or more, and even more preferably 40% or more.
　本開示のアジリジニル基含有モノマーのうちアクリル系モノマーに相当するモノマーとしては、例えば、（メタ）アクリロイルアジリジン、（メタ）アクリル酸２－アジリジニルエチルなどが挙げられるが、かかる例示のみに限定されるものではない。これらのアジリジニル基含有モノマーは、それぞれ単独で用いてもよく、２種類以上を併用してもよい。
　アジリジニル基含有モノマー以外のモノマーが所定のバイオマス度を有していれば、本開示のアジリジニル基含有モノマー（特にアクリル系モノマーとしてのアジリジニル基含有モノマー）のバイオマス度は０％であってもよいが、環境負荷の観点からバイオマス度は１％以上が好ましく、５％以上がより好ましく、１０％以上がさらに好ましい。 Examples of monomers corresponding to acrylic monomers among the aziridinyl group-containing monomers of the present disclosure include (meth)acryloylaziridine, (meth)acrylic acid 2-aziridinylethyl, etc., but are limited only to such examples. not something. These aziridinyl group-containing monomers may be used alone or in combination of two or more.
If the monomer other than the aziridinyl group-containing monomer has a predetermined biomass degree, the biomass degree of the aziridinyl group-containing monomer of the present disclosure (especially the aziridinyl group-containing monomer as an acrylic monomer) may be 0%. From the viewpoint of environmental load, the biomass degree is preferably 1% or more, more preferably 5% or more, and even more preferably 10% or more.
　本開示のスチレン系モノマーとしては、例えば、スチレン、α－メチルスチレン、ｐ－メチルスチレン、ｔｅｒｔ－メチルスチレン、クロロスチレン、ビニルトルエンなどが挙げられるが、かかる例示のみに限定されるものではない。これらのスチレン系モノマーは、それぞれ単独で用いてもよく、２種類以上を併用してもよい。スチレン系モノマーは、ベンゼン環にメチル基、ｔｅｒｔ－ブチル基などのアルキル基、ニトロ基、ニトリル基、アルコキシル基、アシル基、スルホン基、ヒドロキシル基、ハロゲン原子などの官能基が存在していてもよい。スチレン系モノマーのなかでは、耐水性を高める観点から、スチレンが好ましい。
　スチレン系モノマー以外のモノマーが所定のバイオマス度を有していれば、本開示のスチレン系モノマーのバイオマス度は０％であってもよい。 Styrenic monomers of the present disclosure include, for example, styrene, α-methylstyrene, p-methylstyrene, tert-methylstyrene, chlorostyrene, vinyltoluene, and the like, but are not limited to these examples. These styrenic monomers may be used alone, respectively, or two or more of them may be used in combination. Styrene-based monomers may have functional groups such as alkyl groups such as methyl groups and tert-butyl groups, nitro groups, nitrile groups, alkoxyl groups, acyl groups, sulfone groups, hydroxyl groups, and halogen atoms on the benzene ring. good. Among the styrenic monomers, styrene is preferred from the viewpoint of enhancing water resistance.
The biomass degree of the styrene-based monomer of the present disclosure may be 0% as long as the monomer other than the styrene-based monomer has a predetermined biomass degree.
　本開示の付加重合性オキサゾリンとしては、例えば、２－ビニル－２－オキサゾリン、２－ビニル－４－メチル－２－オキサゾリン、２－ビニル－５－メチル－２－オキサゾリン、２－イソプロペニル－２－オキサゾリン、２－イソプロペニル－４－メチル－２－オキサゾリン、２－イソプロペニル－５－メチル－２－オキサゾリン、２－イソプロペニル－５－エチル－２－オキサゾリンなどが挙げられるが、かかる例示のみに限定されるものではない。これらの付加重合性オキサゾリンは、それぞれ単独で用いてもよく、２種類以上を併用してもよい。これらの付加重合性オキサゾリンのなかでは、入手が容易であることから、２－イソプロペニル－２－オキサゾリンが好ましい。
　付加重合性オキサゾリン以外のモノマーが所定のバイオマス度を有していれば、本開示の付加重合性オキサゾリンのバイオマス度は０％であってもよい。 Examples of addition polymerizable oxazolines of the present disclosure include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2 -oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline, etc., but only such examples is not limited to Each of these addition-polymerizable oxazolines may be used alone, or two or more of them may be used in combination. Among these addition-polymerizable oxazolines, 2-isopropenyl-2-oxazoline is preferred because of its easy availability.
The biomass degree of the addition polymerizable oxazoline of the present disclosure may be 0% as long as the monomer other than the addition polymerizable oxazoline has a predetermined biomass degree.
　前記単官能モノマーのうち少なくとも１つが０％超（例えば、１０％以上、好ましくは３０％以上、より好ましくは５０％以上）のバイオマス度を有することが好ましい。０％超のバイオマス度を有する単官能モノマーは、酸基含有モノマー、アルキル又はアルケニル（メタ）アクリレート、芳香族基を有する（メタ）アクリレート、水酸基含有（メタ）アクリレート、ピペリジン基含有モノマー、オキソ基含有モノマー、フッ素原子又は塩素原子含有モノマー、窒素原子含有モノマー、エポキシ基含有モノマー、アルコキシアルキル（メタ）アクリレート、シラン基含有モノマー、カルボニル基含有モノマー、アジリジニル基含有モノマーなどから選ばれる少なくとも１種であることが好ましく、酸基含有モノマー、アルキル又はアルケニル（メタ）アクリレート、水酸基含有（メタ）アクリレート、オキソ基含有モノマー、アルコキシアルキル（メタ）アクリレート、及びカルボニル基含有モノマーから選ばれる少なくとも１種であることがより好ましく、酸基含有モノマー及びアルキル（メタ）アクリレートであることがよりさらに好ましく、アルキル（メタ）アクリレートであることが特に好ましい。 At least one of the monofunctional monomers preferably has a biomass degree of more than 0% (for example, 10% or more, preferably 30% or more, more preferably 50% or more). Monofunctional monomers having a biomass degree of more than 0% include acid group-containing monomers, alkyl or alkenyl (meth)acrylates, aromatic group-containing (meth)acrylates, hydroxyl group-containing (meth)acrylates, piperidine group-containing monomers, oxo groups at least one selected from containing monomers, fluorine atom- or chlorine atom-containing monomers, nitrogen atom-containing monomers, epoxy group-containing monomers, alkoxyalkyl (meth)acrylates, silane group-containing monomers, carbonyl group-containing monomers, aziridinyl group-containing monomers, etc. is preferably at least one selected from acid group-containing monomers, alkyl or alkenyl (meth)acrylates, hydroxyl group-containing (meth)acrylates, oxo group-containing monomers, alkoxyalkyl (meth)acrylates, and carbonyl group-containing monomers are more preferred, acid group-containing monomers and alkyl (meth)acrylates are even more preferred, and alkyl (meth)acrylates are particularly preferred.
　また０％超のバイオマス度を有する単官能モノマーは、前記各単官能モノマーのうち植物由来の（メタ）アクリロイル基（以下、バイオ（メタ）アクリロイル基という）を有するモノマー、植物由来のアルコール（以下、バイオアルコールという）に由来する基を有するモノマーなどに該当するモノマーであることも好ましい一態様である。これらモノマーを使用すると、アクリル系ポリマーのバイオマス度を高めても、良好なインク特性を保つことができる。バイオ（メタ）アクリロイル基は、植物由来のグリセリンから導入可能な基である。バイオアルコールには、バイオエタノール、バイオプロパノール、バイオブタノールなどのバイオアルカノール、テルペン由来のアルコールなどが含まれ、これらはいずれも市場から入手可能である。バイオ（メタ）アクリロイル基を有するモノマーとしては、前記単官能モノマーのうちアクリル系モノマーに分類されるものが挙げられる。バイオアルコール由来の基を有するモノマーとしては、バイオアルコールと（メタ）アクリル酸とのエステルが挙げられ、具体的には直鎖状アルキル基又は分岐状アルキル基を有する（メタ）アクリレートであって前記直鎖状アルキル基又は分岐状アルキル基がバイオアルカノールに由来するもの、分岐状アルキル基又は環状脂肪族基を有する（メタ）アクリレートであって前記分岐状アルキル基又は環状脂肪族基がテルペン由来の基であるものが挙げられる。バイオアルコールとエステルを形成する前記（メタ）アクリル酸は、バイオ（メタ）アクリル酸であってもよく、石油由来の（メタ）アクリル酸であってもよい。 Monofunctional monomers having a biomass degree of more than 0% include monomers having a plant-derived (meth)acryloyl group (hereinafter referred to as a bio (meth)acryloyl group) among the above monofunctional monomers, plant-derived alcohols (hereinafter , bioalcohol) is also a preferred embodiment. By using these monomers, good ink properties can be maintained even if the biomass content of the acrylic polymer is increased. A bio(meth)acryloyl group is a group that can be introduced from plant-derived glycerin. Bioalcohols include bioalkanols such as bioethanol, biopropanol, biobutanol, terpene-derived alcohols, etc., all of which are commercially available. Examples of the monomer having a bio(meth)acryloyl group include those classified as acrylic monomers among the above monofunctional monomers. Examples of the monomer having a bioalcohol-derived group include esters of bioalcohol and (meth)acrylic acid, specifically a (meth)acrylate having a linear alkyl group or a branched alkyl group. A linear alkyl group or branched alkyl group derived from a bioalkanol, a (meth)acrylate having a branched alkyl group or a cyclic aliphatic group, wherein the branched alkyl group or cyclic aliphatic group is derived from a terpene Those which are groups are mentioned. The (meth)acrylic acid that forms an ester with bioalcohol may be bio(meth)acrylic acid or petroleum-derived (meth)acrylic acid.
　０％超のバイオマス度を有する単官能モノマーとしては、バイオ（メタ）アクリロイル基を有するモノマー、テルペン由来の分岐状アルキル基を有する（メタ）アクリレート、テルペン由来の環状脂肪族基を有する（メタ）アクリレートであることが好ましい。アクリロイル基に植物由来のものを使用すると、複数のアクリル系モノマーから構成される共重合ポリマーでアクリル系ポリマーを形成するとき、多くの種類の単量体成分のバイオマス度を高めることができ、バイオマス度の向上が簡便である。またテルペン由来の基を有する（メタ）アクリレートの場合は、テルペンの炭素数が大きいために１つの化学種を植物由来にするだけで多くの炭素を植物由来にすることができ、簡便にバイオマス度を高めることができる。 Examples of monofunctional monomers having a biomass degree of more than 0% include monomers having a bio (meth)acryloyl group, (meth)acrylates having a terpene-derived branched alkyl group, and (meth) having a terpene-derived cycloaliphatic group. Acrylate is preferred. Using a plant-derived acryloyl group can increase the biomass content of many types of monomer components when forming an acrylic polymer with a copolymer composed of multiple acrylic monomers, resulting in biomass production. It is easy to improve the degree. In addition, in the case of (meth)acrylates having terpene-derived groups, since the terpene has a large number of carbon atoms, it is possible to make many carbons plant-derived simply by making one chemical species plant-derived, and the biomass degree can be easily improved. can increase
　０％超のバイオマス度を有する単官能モノマーとしては、テルペン由来の分岐状アルキル基を有する（メタ）アクリレート、テルペン由来の環状脂肪族基を有する（メタ）アクリレートなどがより好ましく、テルペン由来の環状脂肪族基を有する（メタ）アクリレートが特に好ましい。テルペン由来の分岐状アルキル基又は環状脂肪族基を有する（メタ）アクリレートを使用すると、テルペン由来ではないアルキル（メタ）アクリレートを用いた場合に比べて、密着性、耐粘着テープ剥離性、及び耐候性の１つ以上が良好になり、特に密着性が良好になる。 As the monofunctional monomer having a biomass degree of more than 0%, a (meth)acrylate having a terpene-derived branched alkyl group, a (meth)acrylate having a terpene-derived cycloaliphatic group, and the like are more preferable, and a terpene-derived cyclic (Meth)acrylates with aliphatic groups are particularly preferred. When a (meth)acrylate having a terpene-derived branched alkyl group or a cycloaliphatic group is used, adhesion, adhesive tape peelability, and weather resistance are improved compared to the case of using a non-terpene-derived alkyl (meth)acrylate. one or more of the properties are improved, and in particular adhesion is improved.
　テルペン由来の分岐状アルキル基を有する（メタ）アクリレートとしては、１－メチル－１－エチル－５－メチルヘキシル（メタ）アクリレート（水添リナロールと（メタ）アクリル酸とのエステル）、２－イソプロピル－５－メチルヘキシル（メタ）アクリレート（水添ラバンジュロールと（メタ）アクリル酸とのエステル）、３，７－ジメチルオクチル（メタ）アクリレート（水添ゲラニオール、水添ネロール、又は水添シトロネロールと（メタ）アクリル酸とのエステル）などが挙げられる。テルペン由来の環状脂肪族基を有する（メタ）アクリレートとしては、ボルニル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ツヤニル（メタ）アクリレート、１－イソプロル－４－メチルシクロヘキシル（メタ）アクリレート（水添テルピネン－４－オールと（メタ）アクリル酸とのエステル）、１－メチル－４－イソプロピルシクロヘキシル（メタ）アクリレート（水添テルペネオールと（メタ）アクリル酸とのエステル）、２－イソプロピル－５－メチルシクロヘキシル（メタ）アクリレート（水添メントールと（メタ）アクリル酸とのエステル）などが挙げられ、ボルニル（メタ）アクリレート、イソボルニル（メタ）アクリレートなどが好ましい。 (Meth)acrylates having a terpene-derived branched alkyl group include 1-methyl-1-ethyl-5-methylhexyl (meth)acrylate (ester of hydrogenated linalool and (meth)acrylic acid), 2-isopropyl -5-methylhexyl (meth)acrylate (ester of hydrogenated lavandulol and (meth)acrylic acid), 3,7-dimethyloctyl (meth)acrylate (hydrogenated geraniol, hydrogenated nerol, or hydrogenated citronellol) (meth)ester with acrylic acid) and the like. (Meth)acrylates having a terpene-derived cycloaliphatic group include bornyl (meth)acrylate, isobornyl (meth)acrylate, thuyanyl (meth)acrylate, 1-isopropyl-4-methylcyclohexyl (meth)acrylate (hydrogenated terpinene -4-ol and (meth)acrylic acid ester), 1-methyl-4-isopropylcyclohexyl (meth)acrylate (hydrogenated terpeneol and (meth)acrylic acid ester), 2-isopropyl-5-methylcyclohexyl (Meth)acrylates (esters of hydrogenated menthol and (meth)acrylic acid) and the like, preferably bornyl (meth)acrylate, isobornyl (meth)acrylate and the like.
　本開示の好適な単官能モノマーとしては、例えば、アルキル又はアルケニル（メタ）アクリレート（直鎖状アルキル基を有する（メタ）アクリレート、分岐状アルキル基を有する（メタ）アクリレート、又は環状脂肪族基を有する（メタ）アクリレートなど）、水酸基含有（メタ）アクリレート、ピペリジン基含有モノマー、酸基含有モノマー、オキソ基含有モノマー、フッ素原子又は塩素原子含有モノマー、窒素原子含有モノマー、エポキシ基含有モノマー、スチレン系モノマーなどから選ばれる１種以上が挙げられ、直鎖状アルキル基を有する（メタ）アクリレート、分岐状アルキル基を有する（メタ）アクリレート、環状脂肪族基を有する（メタ）アクリレート、水酸基含有（メタ）アクリレート、ピペリジン基含有モノマー、及び酸基含有モノマーなどから選ばれる１種以上を含むことが好ましく、環状脂肪族基を有する（メタ）アクリレート及び水酸基含有（メタ）アクリレートから選ばれる１種以上を含むことがより好ましく、少なくとも環状脂肪族基を有する（メタ）アクリレートを含むことが特に好ましい。これらのモノマーは、それぞれ単独で用いてもよく、２種類以上を併用してもよい。コロナ処理されたＰＥＴやＯＰＰ等への密着性をより向上させる観点から好ましい単官能モノマーを選択することも可能であり、ピペリジン基含有モノマー、窒素原子含有モノマー、付加重合性オキサゾリンなどが好ましく、中でも、ピペリジン基含有モノマー、付加重合性オキサゾリンがより好ましく、４－（メタ）アクリロイルオキシ－２，２，６，６－テトラメチルピペリジン、４－（メタ）アクリロイルオキシ－１，２，２，６，６－ペンタメチルピペリジン、２－イソプロペニル－２－オキサゾリンがさらに好ましい。また、水酸基含有（メタ）アクリレートを単官能モノマーとして含むと、粗大粒子のないエマルション粒子が得られやすく、該エマルション粒子を含むインクの吐出安定性が優れるものとなる観点から、水酸基含有（メタ）アクリレートを含むことが好ましい。 Suitable monofunctional monomers of the present disclosure include, for example, alkyl or alkenyl (meth)acrylates ((meth)acrylates with linear alkyl groups, (meth)acrylates with branched alkyl groups, or cycloaliphatic groups). (Meth)acrylate, etc.), hydroxyl group-containing (meth)acrylate, piperidine group-containing monomer, acid group-containing monomer, oxo group-containing monomer, fluorine atom or chlorine atom-containing monomer, nitrogen atom-containing monomer, epoxy group-containing monomer, styrenic One or more selected from monomers and the like may be mentioned, and (meth)acrylates having a linear alkyl group, (meth)acrylates having a branched alkyl group, (meth)acrylates having a cycloaliphatic group, hydroxyl group-containing (meth) ) It preferably contains one or more selected from acrylates, piperidine group-containing monomers, and acid group-containing monomers, and one or more selected from (meth)acrylates having a cycloaliphatic group and hydroxyl group-containing (meth)acrylates. It is more preferable to contain, and it is particularly preferable to contain at least a (meth)acrylate having a cycloaliphatic group. These monomers may be used alone, respectively, or two or more of them may be used in combination. From the viewpoint of further improving adhesion to corona-treated PET, OPP, etc., preferred monofunctional monomers can be selected, and piperidine group-containing monomers, nitrogen atom-containing monomers, addition-polymerizable oxazolines, etc. are preferred. , piperidine group-containing monomers, addition polymerizable oxazolines are more preferable, 4-(meth)acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-(meth)acryloyloxy-1,2,2,6, More preferred are 6-pentamethylpiperidine and 2-isopropenyl-2-oxazoline. Further, when a hydroxyl group-containing (meth)acrylate is contained as a monofunctional monomer, it is easy to obtain emulsion particles free of coarse particles, and from the viewpoint of excellent ejection stability of the ink containing the emulsion particles, the hydroxyl group-containing (meth)acrylate It preferably contains an acrylate.
　本開示のアクリル系ポリマー１００質量部におけるアクリル系モノマー（特に単官能モノマーとしてのアクリル系モノマー）由来の構造単位の含有量は、５０質量部以上有するポリマーであってよく、６０質量部以上有することが好ましく、７０質量部以上がより好ましく、８０質量部以上がさらに好ましい。本開示のアクリル系ポリマーのバイオマス度は１０％以上であり、２０％以上が好ましく、３０％以上がより好ましく、４０％以上がさらに好ましい。上記範囲を満たすことにより、耐水性、耐候性に優れると共に、環境負荷の観点からも好ましいインクを得ることができる。 The content of structural units derived from acrylic monomers (especially acrylic monomers as monofunctional monomers) in 100 parts by mass of the acrylic polymer of the present disclosure may be 50 parts by mass or more, and should be 60 parts by mass or more. is preferred, 70 parts by mass or more is more preferred, and 80 parts by mass or more is even more preferred. The biomass degree of the acrylic polymer of the present disclosure is 10% or more, preferably 20% or more, more preferably 30% or more, and even more preferably 40% or more. By satisfying the above range, it is possible to obtain an ink that is excellent in water resistance and weather resistance and is also preferable from the viewpoint of environmental load.
　本開示のアクリル系ポリマー１００質量部における酸基含有モノマー（好ましくはアクリル系モノマーとしての酸基含有モノマー）由来の構造単位の含有割合は、０質量部でもよいが、重合安定性、貯蔵安定性、吐出安定性、密着性向上の観点から０．１質量部以上が好ましく、０．５質量部以上がより好ましく、１質量部以上がさらに好ましく、吐出安定性、低粘度化の観点から１０質量部以下が好ましく、８質量部以下がより好ましく、６質量部以下がさらに好ましい（すなわち０～１０質量部が好ましく、０．１～１０質量部がより好ましく、０．５～８質量部がよりさらに好ましく、１～６質量部が特に好ましい）。 The content of structural units derived from an acid group-containing monomer (preferably an acid group-containing monomer as an acrylic monomer) in 100 parts by mass of the acrylic polymer of the present disclosure may be 0 parts by mass, but polymerization stability and storage stability , from the viewpoint of improving ejection stability and adhesion, 0.1 parts by mass or more is preferable, 0.5 parts by mass or more is more preferable, 1 part by mass or more is even more preferable, and from the viewpoint of ejection stability and low viscosity, 10 parts by mass Parts or less is preferable, 8 parts by mass or less is more preferable, and 6 parts by mass or less is more preferable (that is, 0 to 10 parts by mass is preferable, 0.1 to 10 parts by mass is more preferable, and 0.5 to 8 parts by mass is more preferable. More preferably, 1 to 6 parts by mass is particularly preferable).
　本開示のアクリル系ポリマー１００質量部におけるアルキル又はアルケニル（メタ）アクリレート由来の構造単位の含有割合は、耐擦過性、密着性、耐ブロッキング性向上の観点から１０質量部以上が好ましく、１５質量部以上がより好ましく、２０質量部以上がさらに好ましく、４０質量部以上又は６０質量部以上が特に好ましく、耐擦過性、密着性、耐ブロッキング性向上の観点から９５質量部以下又は９０質量部以下が好ましく、８０質量部以下がより好ましく、７５質量部以下がさらに好ましく、７０質量部以下がよりさらに好ましい（すなわち１０～９５質量部が好ましく、１５～９０質量部がより好ましく、２０～８０質量部がよりさらに好ましく、４０～７５質量部が特に好ましく、６０～７０質量部が最も好ましい）。
　本開示のアクリル系ポリマー１００質量部における直鎖状アルキル基を有する（メタ）アクリレート由来の構造単位の含有割合は、０質量部でもよいが、耐擦過性向上の観点から１０質量部以上が好ましく、１５質量部以上がより好ましく、２０質量部以上がさらに好ましく、密着性、耐ブロッキング性向上の観点から７０質量部以下が好ましく、６５質量部以下がより好ましく、６０質量部以下がさらに好ましく、３０質量部以下が特に好ましい（すなわち０～７０質量部が好ましく、１０～６５質量部がより好ましく、１５～６０質量部がさらに好ましく、２０～３０質量部が特に好ましい）。 The content of structural units derived from alkyl or alkenyl (meth)acrylate in 100 parts by mass of the acrylic polymer of the present disclosure is preferably 10 parts by mass or more, and 15 parts by mass from the viewpoint of improving scratch resistance, adhesion, and blocking resistance. more preferably 20 parts by mass or more, particularly preferably 40 parts by mass or more or 60 parts by mass or more, and from the viewpoint of improving scratch resistance, adhesion and blocking resistance, 95 parts by mass or less or 90 parts by mass or less preferably 80 parts by mass or less, more preferably 75 parts by mass or less, and even more preferably 70 parts by mass or less (that is, preferably 10 to 95 parts by mass, more preferably 15 to 90 parts by mass, 20 to 80 parts by mass is more preferred, 40 to 75 parts by weight is particularly preferred, and 60 to 70 parts by weight is most preferred).
The content of structural units derived from (meth)acrylate having a linear alkyl group in 100 parts by mass of the acrylic polymer of the present disclosure may be 0 parts by mass, but is preferably 10 parts by mass or more from the viewpoint of improving scratch resistance. , more preferably 15 parts by mass or more, more preferably 20 parts by mass or more, preferably 70 parts by mass or less from the viewpoint of improving adhesion and blocking resistance, more preferably 65 parts by mass or less, and further preferably 60 parts by mass or less; 30 parts by mass or less is particularly preferable (that is, 0 to 70 parts by mass is preferable, 10 to 65 parts by mass is more preferable, 15 to 60 parts by mass is even more preferable, and 20 to 30 parts by mass is particularly preferable).
　本開示のアクリル系ポリマー１００質量部における分岐状アルキル基を有する（メタ）アクリレート由来の構造単位の含有割合は、０質量部でもよいが、低粘度化、吐出安定性の観点から１０質量部以上が好ましく、１５質量部以上がより好ましく、２０質量部以上がさらに好ましく、密着性、耐ブロッキング性向上の観点から７０質量部以下が好ましく、６５質量部以下がより好ましく、６０質量部以下がさらに好ましく、３０質量部以下が特に好ましい（すなわち０～７０質量部が好ましく、１０～６５質量部がより好ましく、１５～６０質量部がさらに好ましく、２０～３０質量部が特に好ましい）。 The content ratio of the (meth)acrylate-derived structural unit having a branched alkyl group in 100 parts by mass of the acrylic polymer of the present disclosure may be 0 parts by mass, but from the viewpoint of low viscosity and ejection stability, it is 10 parts by mass or more. is preferably 15 parts by mass or more, more preferably 20 parts by mass or more, and from the viewpoint of improving adhesion and blocking resistance, it is preferably 70 parts by mass or less, more preferably 65 parts by mass or less, and further 60 parts by mass or less. 30 parts by weight or less is particularly preferred (that is, 0 to 70 parts by weight is preferred, 10 to 65 parts by weight is more preferred, 15 to 60 parts by weight is even more preferred, and 20 to 30 parts by weight is particularly preferred).
　本開示のアクリル系ポリマー１００質量部における環状脂肪族基を有する（メタ）アクリレート由来の構造単位の含有割合は、密着性向上の観点から３０質量部以上であってよく、３５質量部以上が好ましく、４０質量部以上がより好ましく、４５質量部以上がさらに好ましく、９５質量部以下であってよく、９０質量部以下が好ましく、８５質量部以下がより好ましい（すなわち３０～９５質量部が好ましく、３５～９５質量部がより好ましく、４０～９０質量部がさらに好ましく、４５～８５質量部が特に好ましい）。 The content ratio of the (meth)acrylate-derived structural unit having a cycloaliphatic group in 100 parts by mass of the acrylic polymer of the present disclosure may be 30 parts by mass or more, preferably 35 parts by mass or more, from the viewpoint of improving adhesion. , More preferably 40 parts by mass or more, more preferably 45 parts by mass or more, may be 95 parts by mass or less, preferably 90 parts by mass or less, more preferably 85 parts by mass or less (that is, preferably 30 to 95 parts by mass, 35 to 95 parts by mass is more preferable, 40 to 90 parts by mass is more preferable, and 45 to 85 parts by mass is particularly preferable).
　本開示のアクリル系ポリマーにおいて、アルキル又はアルケニル（メタ）アクリレート由来の構造単位１００質量部における環状脂肪族基を有する（メタ）アクリレート由来の構造単位の含有割合は、密着性向上の観点から３０質量部以上であってよく、３５質量部以上が好ましく、４０質量部以上がより好ましく、４５質量部以上がさらに好ましく、９５質量部以下であってよく、９０質量部以下が好ましく、８５質量部以下がより好ましい（すなわち３０～９５質量部が好ましく、３５～９５質量部がより好ましく、４０～９０質量部がさらに好ましく、４５～８５質量部が特に好ましい）。 In the acrylic polymer of the present disclosure, the content of structural units derived from (meth)acrylate having a cycloaliphatic group in 100 parts by mass of structural units derived from alkyl or alkenyl (meth)acrylate is 30 mass from the viewpoint of improving adhesion. parts or more, preferably 35 parts by mass or more, more preferably 40 parts by mass or more, even more preferably 45 parts by mass or more, may be 95 parts by mass or less, preferably 90 parts by mass or less, and 85 parts by mass or less is more preferred (that is, 30 to 95 parts by weight is preferred, 35 to 95 parts by weight is more preferred, 40 to 90 parts by weight is even more preferred, and 45 to 85 parts by weight is particularly preferred).
　本開示のアクリル系ポリマー１００質量部における水酸基含有（メタ）アクリレート由来の含有割合は、密着性、吐出安定性向上の観点から０．１質量部以上が好ましく、０．５質量部以上がより好ましく、１質量部以上がさらに好ましく、低粘度化、経時安定性の観点から３０質量部以下が好ましく、２５質量部以下がより好ましく、２０質量部以下がさらに好ましい（すなわち０．１～３０質量部が好ましく、０．５～２５質量部がより好ましく、１～２０質量部がさらに好ましい）。 The content ratio derived from hydroxyl group-containing (meth)acrylate in 100 parts by mass of the acrylic polymer of the present disclosure is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, from the viewpoint of improving adhesion and ejection stability. , More preferably 1 part by mass or more, preferably 30 parts by mass or less from the viewpoint of low viscosity and stability over time, more preferably 25 parts by mass or less, further preferably 20 parts by mass or less (that is, 0.1 to 30 parts by mass is preferred, 0.5 to 25 parts by weight is more preferred, and 1 to 20 parts by weight is even more preferred).
　本開示のアクリル系ポリマー１００質量部におけるピペリジン基含有モノマー（好ましくはアクリル系モノマーとしてのピペリジン基含有モノマー）由来の含有割合は、０質量部でもよいが、耐候性および密着性をより向上させる観点から０．１質量部以上が好ましく、０．２質量部以上がより好ましく、０．５質量部以上がさらに好ましく、３質量部以上又は５質量部以上が特に好ましく、耐水性を向上させる観点から３０質量部以下が好ましく、２０質量部以下がより好ましく、１５質量部以下がさらに好ましく、１０質量部以下がよりさらに好ましい（すなわち０～３０質量部が好ましく、０．１～３０質量部がより好ましく、０．２～２０質量部がさらに好ましく、０．５～１５質量部がよりさらに好ましく、３～１０質量部が特に好ましく、５～１０質量部が最も好ましい）。 The content ratio derived from the piperidine group-containing monomer (preferably the piperidine group-containing monomer as the acrylic monomer) in 100 parts by mass of the acrylic polymer of the present disclosure may be 0 parts by mass, but from the viewpoint of further improving weather resistance and adhesion 0.1 parts by mass or more is preferable, 0.2 parts by mass or more is more preferable, 0.5 parts by mass or more is more preferable, and 3 parts by mass or more or 5 parts by mass or more is particularly preferable, from the viewpoint of improving water resistance 30 parts by mass or less is preferable, 20 parts by mass or less is more preferable, 15 parts by mass or less is even more preferable, and 10 parts by mass or less is even more preferable (that is, 0 to 30 parts by mass is preferable, and 0.1 to 30 parts by mass is more preferably 0.2 to 20 parts by mass, even more preferably 0.5 to 15 parts by mass, particularly preferably 3 to 10 parts by mass, and most preferably 5 to 10 parts by mass).
　本開示のアクリル系ポリマー１００質量部におけるスチレン系モノマー由来の含有割合は、０質量部でもよいが、光沢、耐水性向上の観点から１０質量部以上が好ましく、１５質量部以上がより好ましく、２０質量部以上がさらに好ましく、耐光性、耐黄変性の観点から６０質量部以下が好ましく、５５質量部以下がより好ましく、５０質量部以下がさらに好ましい（すなわち０～６０質量部が好ましく、１０～６０質量部がより好ましく、１５～５５質量部がよりさらに好ましく、２０～５０質量部が特に好ましい）。 The content of the styrene-based monomer in 100 parts by mass of the acrylic polymer of the present disclosure may be 0 parts by mass, but is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, from the viewpoint of improving gloss and water resistance. It is more preferably 60 parts by mass or less from the viewpoint of light resistance and yellowing resistance, more preferably 55 parts by mass or less, and even more preferably 50 parts by mass or less (that is, 0 to 60 parts by mass is preferable, and 10 to 60 parts by mass is preferable. 60 parts by mass is more preferable, 15 to 55 parts by mass is even more preferable, and 20 to 50 parts by mass is particularly preferable).
　上記以外のモノマー、すなわち芳香族基を有する（メタ）アクリレート、オキソ基含有モノマー（好ましくはアクリル系モノマーとしてのオキソ基含有モノマー）、フッ素原子又は塩素原子含有モノマー（好ましくはアクリル系モノマーとしてのフッ素原子又は塩素原子含有モノマー）、窒素原子含有モノマー（好ましくはアクリル系モノマーとしての窒素原子含有モノマー）、エポキシ基含有モノマー（好ましくはアクリル系モノマーとしてのエポキシ基含有モノマー）、アルコキシアルキル（メタ）アクリレート、シラン基含有モノマー（好ましくはアクリル系モノマーとしてのシラン基含有モノマー）、カルボニル基含有モノマー（好ましくはアクリル系モノマーとしてのカルボニル基含有モノマー）、アジリジニル基含有モノマー（好ましくはアクリル系モノマーとしてのアジリジニル基含有モノマー）、付加重合性オキサゾリンなどのモノマーに由来する構成単位の割合は、アクリル系ポリマー１００質量部中、それぞれ、例えば、０質量部以上、又は１０質量部以上であって、５０質量部以下、又は３０質量部以下の範囲であってもよい（すなわち０～５０質量部が好ましく、１０～３０質量部がより好ましい）。 Monomers other than the above, that is, (meth)acrylates having aromatic groups, oxo group-containing monomers (preferably oxo group-containing monomers as acrylic monomers), fluorine atom- or chlorine atom-containing monomers (preferably fluorine as acrylic monomers) atom or chlorine atom-containing monomer), nitrogen atom-containing monomer (preferably nitrogen atom-containing monomer as acrylic monomer), epoxy group-containing monomer (preferably epoxy group-containing monomer as acrylic monomer), alkoxyalkyl (meth)acrylate , a silane group-containing monomer (preferably a silane group-containing monomer as an acrylic monomer), a carbonyl group-containing monomer (preferably a carbonyl group-containing monomer as an acrylic monomer), an aziridinyl group-containing monomer (preferably aziridinyl as an acrylic monomer group-containing monomer), the proportion of structural units derived from monomers such as addition-polymerizable oxazoline is, for example, 0 parts by mass or more, or 10 parts by mass or more, and 50 parts by mass in 100 parts by mass of the acrylic polymer. or less, or 30 parts by mass or less (that is, preferably 0 to 50 parts by mass, more preferably 10 to 30 parts by mass).
　＜多官能モノマー＞
　エチレン性二重結合を有するモノマーには多官能モノマーも含まれる。該多官能モノマーは、アクリル系モノマーであってもよく、アクリル系モノマーでなくてもよいが、アクリル系モノマーであることが好ましい。
　本開示アクリル系モノマーとなる多官能モノマーとしては、例えば、エチレングリコールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、１，３－ブタンジオールジ（メタ）アクリレート、１，４－ブタンジオールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、エチレンオキシド変性１，６－ヘキサンジオールジ（メタ）アクリレート、１，９－ノナンジオールジ（メタ）アクリレート、プロピレンオキシド変性ネオペンチルグリコールジ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート、ビスフェノールＡジ（メタ）アクリレートなどの炭素数１～２０（好ましくは炭素数１～１０）の多価アルコールのジ（メタ）アクリレート；エチレンオキシドの付加モル数が２～５０のポリエチレングリコールジ（メタ）アクリレート、プロピレンオキシドの付加モル数が２～５０のポリプロピレングリコールジ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレートなどの炭素数２～４のアルキレンオキシド基の付加モル数が２～５０であるアルキルジ（メタ）アクリレート；エトキシ化グリセリントリ（メタ）アクリレート、プロピレンオキシド変性グリセロールトリ（メタ）アクリレート、エチレンオキシド変性トリメチロールプロパントリ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールモノヒドロキシトリ（メタ）アクリレート、トリメチロールプロパントリエトキシトリ（メタ）アクリレート、トリメチロールプロパントリプロポキシトリ（メタ）アクリレートなどの炭素数１～２０（好ましくは炭素数１～１０）の多価アルコールのトリ（メタ）アクリレート；ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールテトラ（メタ）アクリレート、ジトリメチロールプロパンテトラ（メタ）アクリレートなどの炭素数１～２０（好ましくは炭素数１～１０）の多価アルコールのテトラ（メタ）アクリレート；ペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトール（モノヒドロキシ）ペンタ（メタ）アクリレートなどの炭素数１～２０（好ましくは炭素数１～１０）の多価アルコールのペンタ（メタ）アクリレート；ペンタエリスリトールヘキサ（メタ）アクリレートなどの炭素数１～１０の多価アルコールのヘキサ（メタ）アクリレート；２－（２’－ビニルオキシエトキシエチル）（メタ）アクリレート；ウレタン（メタ）アクリレートなどの多官能（メタ）アクリレートなどが挙げられるが、かかる例示のみに限定されるものではない。これらの多官能モノマーは、それぞれ単独で用いてもよく、２種類以上を併用してもよい。 <Polyfunctional monomer>
Monomers with ethylenic double bonds also include polyfunctional monomers. The polyfunctional monomer may or may not be an acrylic monomer, but is preferably an acrylic monomer.
Examples of polyfunctional monomers to be acrylic monomers of the present disclosure include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, (Meth)acrylate, 1,6-hexanediol di(meth)acrylate, ethylene oxide-modified 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, propylene oxide-modified neopentyl glycol di(meth)acrylate (Meth) acrylate, tripropylene glycol di (meth) acrylate, di (meth) acrylate of polyhydric alcohol having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms) such as bisphenol A di (meth) acrylate; 2 to 4 carbon atoms such as polyethylene glycol di(meth)acrylate with an added mole number of 2 to 50, polypropylene glycol di(meth)acrylate with an added mole number of propylene oxide of 2 to 50, tripropylene glycol di(meth)acrylate, etc. Alkyl di(meth)acrylates having 2 to 50 moles of alkylene oxide groups; ethoxylated glycerin tri(meth)acrylate, propylene oxide-modified glycerol tri(meth)acrylate, ethylene oxide-modified trimethylolpropane tri(meth)acrylate, C1-20 (preferably tri(meth)acrylates of polyhydric alcohols having 1 to 10 carbon atoms; Tetra(meth)acrylate of polyhydric alcohol preferably having 1 to 10 carbon atoms; pentaerythritol penta(meth)acrylate, Number 1-10) polyhydric alcohol penta (meth) acrylate; C 1-10 polyhydric alcohol hexa (meth) acrylate such as pentaerythritol hexa (meth) acrylate Polyfunctional (meth)acrylates such as sa (meth)acrylate; 2-(2'-vinyloxyethoxyethyl) (meth)acrylate; urethane (meth)acrylate, etc., but are not limited to these examples. Absent. Each of these polyfunctional monomers may be used alone, or two or more of them may be used in combination.
　単官能モノマー以外のモノマーが所定のバイオマス度を有していれば、本開示の多官能モノマー（特にアクリル系モノマーとしての多官能モノマー）のバイオマス度は０％であってもよいが、環境負荷の観点からバイオマス度は１％以上が好ましく、５％以上がより好ましい。 If the monomer other than the monofunctional monomer has a predetermined biomass degree, the polyfunctional monomer of the present disclosure (especially the polyfunctional monomer as an acrylic monomer) may have a biomass degree of 0%, but environmental load From the viewpoint of , the biomass degree is preferably 1% or more, more preferably 5% or more.
　本開示のアクリル系ポリマー１００質量部における多官能モノマー（特にアクリル系モノマーとしての多官能モノマー）由来の含有割合は、例えば、０質量部以上又は１質量部以上であり、１０質量部以下又は５質量部以下であってもよい（すなわち０～１０質量部が好ましく、１～５質量部がより好ましい）。 The content ratio derived from a polyfunctional monomer (especially a polyfunctional monomer as an acrylic monomer) in 100 parts by mass of the acrylic polymer of the present disclosure is, for example, 0 parts by mass or more or 1 part by mass or more, and 10 parts by mass or less or 5 It may be less than or equal to parts by mass (that is, preferably 0 to 10 parts by mass, more preferably 1 to 5 parts by mass).
　本開示のアクリル系ポリマーは紫外線吸収性単量体を単量体成分に含有させてもよい。紫外線吸収性単量体としては、例えば、ベンゾトリアゾール系紫外線吸収性単量体、ベンゾフェノン系紫外線吸収性単量体などが挙げられるが、かかる例示のみに限定されるものではない。これらの紫外線吸収性単量体は、それぞれ単独で用いてもよく、２種類以上を併用してもよい。 The acrylic polymer of the present disclosure may contain an ultraviolet absorbing monomer as a monomer component. Examples of ultraviolet absorbing monomers include benzotriazole-based ultraviolet absorbing monomers and benzophenone-based ultraviolet absorbing monomers, but are not limited to these examples. These UV-absorbing monomers may be used alone or in combination of two or more.
　ベンゾトリアゾール系紫外線吸収性単量体としては、例えば、２－［２’－ヒドロキシ－５’－（メタ）アクリロイルオキシメチルフェニル］－２Ｈ－ベンゾトリアゾール、２－［２’－ヒドロキシ－５’－（メタ）アクリロイルオキシエチルフェニル］－２Ｈ－ベンゾトリアゾール、２－［２’－ヒドロキシ－５’－（メタ）アクリロイルオキシメチルフェニル］－５－ｔｅｒｔ－ブチル－２Ｈ－ベンゾトリアゾール、２－［２’－ヒドロキシ－５’－（メタ）アクリロイルアミノメチル－５’－ｔｅｒｔ－オクチルフェニル］－２Ｈ－ベンゾトリアゾール、２－［２’－ヒドロキシ－５’－（メタ）アクリロイルオキシプロピルフェニル］－２Ｈ－ベンゾトリアゾール、２－［２’－ヒドロキシ－５’－（メタ）アクリロイルオキシヘキシルフェニル］－２Ｈ－ベンゾトリアゾール、２－［２’－ヒドロキシ－３’－ｔｅｒｔ－ブチル－５’－（メタ）アクリロイルオキシエチルフェニル］－２Ｈ－ベンゾトリアゾール、２－［２’－ヒドロキシ－３’－ｔｅｒｔ－ブチル－５’－（メタ）アクリロイルオキシエチルフェニル］－５－クロロ－２Ｈ－ベンゾトリアゾール、２－［２’－ヒドロキシ－５’－ｔｅｒｔ－ブチル－３’－（メタ）アクリロイルオキシエチルフェニル］－２Ｈ－ベンゾトリアゾール、２－［２’－ヒドロキシ－５’－（メタ）アクリロイルオキシエチルフェニル］－５－クロロ－２Ｈ－ベンゾトリアゾール、２－［２’－ヒドロキシ－５’－（メタ）アクリロイルオキシエチルフェニル］－５－シアノ－２Ｈ－ベンゾトリアゾール、２－［２’－ヒドロキシ－５’－（メタ）アクリロイルオキシエチルフェニル］－５－ｔｅｒｔ－ブチル－２Ｈ－ベンゾトリアゾール、２－［２’－ヒドロキシ－５’－（β－（メタ）アクリロイルオキシエトキシ）－３’－ｔｅｒｔ－ブチルフェニル］－４－ｔｅｒｔ－ブチル－２Ｈ－ベンゾトリアゾールなどが挙げられるが、かかる例示のみに限定されるものではない。これらのベンゾトリアゾール系紫外線吸収性単量体は、それぞれ単独で用いてもよく、２種類以上を併用してもよい。 Benzotriazole-based UV-absorbing monomers include, for example, 2-[2′-hydroxy-5′-(meth)acryloyloxymethylphenyl]-2H-benzotriazole, 2-[2′-hydroxy-5′- (Meth)acryloyloxyethylphenyl]-2H-benzotriazole, 2-[2′-hydroxy-5′-(meth)acryloyloxymethylphenyl]-5-tert-butyl-2H-benzotriazole, 2-[2′ -hydroxy-5′-(meth)acryloylaminomethyl-5′-tert-octylphenyl]-2H-benzotriazole, 2-[2′-hydroxy-5′-(meth)acryloyloxypropylphenyl]-2H-benzo triazole, 2-[2′-hydroxy-5′-(meth)acryloyloxyhexylphenyl]-2H-benzotriazole, 2-[2′-hydroxy-3′-tert-butyl-5′-(meth)acryloyloxy ethylphenyl]-2H-benzotriazole, 2-[2′-hydroxy-3′-tert-butyl-5′-(meth)acryloyloxyethylphenyl]-5-chloro-2H-benzotriazole, 2-[2′ -hydroxy-5′-tert-butyl-3′-(meth)acryloyloxyethylphenyl]-2H-benzotriazole, 2-[2′-hydroxy-5′-(meth)acryloyloxyethylphenyl]-5-chloro -2H-benzotriazole, 2-[2'-hydroxy-5'-(meth)acryloyloxyethylphenyl]-5-cyano-2H-benzotriazole, 2-[2'-hydroxy-5'-(meth)acryloyl oxyethylphenyl]-5-tert-butyl-2H-benzotriazole, 2-[2′-hydroxy-5′-(β-(meth)acryloyloxyethoxy)-3′-tert-butylphenyl]-4-tert -Butyl-2H-benzotriazole and the like, but are not limited to these examples. Each of these benzotriazole-based UV-absorbing monomers may be used alone, or two or more of them may be used in combination.
　ベンゾフェノン系紫外線吸収性単量体としては、例えば、２－ヒドロキシ－４－（メタ）アクリロイルオキシベンゾフェノン、２－ヒドロキシ－４－［２－ヒドロキシ－３－（メタ）アクリロイルオキシ］プロポキシベンゾフェノン、２－ヒドロキシ－４－［２－（メタ）アクリロイルオキシ］エトキシベンゾフェノン、２－ヒドロキシ－４－［３－（メタ）アクリロイルオキシ－２－ヒドロキシプロポキシ］ベンゾフェノン、２－ヒドロキシ－３－ｔｅｒｔ－ブチル－４－［２－（メタ）アクリロイルオキシ］ブトキシベンゾフェノンなどが挙げられるが、かかる例示のみに限定されるものではない。これらのベンゾフェノン系紫外線吸収性単量体は、それぞれ単独で用いてもよく、２種類以上を併用してもよい。 Benzophenone-based UV-absorbing monomers include, for example, 2-hydroxy-4-(meth)acryloyloxybenzophenone, 2-hydroxy-4-[2-hydroxy-3-(meth)acryloyloxy]propoxybenzophenone, 2- Hydroxy-4-[2-(meth)acryloyloxy]ethoxybenzophenone, 2-hydroxy-4-[3-(meth)acryloyloxy-2-hydroxypropoxy]benzophenone, 2-hydroxy-3-tert-butyl-4- Examples include [2-(meth)acryloyloxy]butoxybenzophenone and the like, but are not limited to these examples. These benzophenone-based UV-absorbing monomers may be used alone or in combination of two or more.
　本開示のアクリル系樹脂はエマルション粒子であることが好ましく、安全性の観点からアクリル系樹脂粒子（樹脂粒子ともいう）を含有する水性分散体であることがより好ましい。本開示の一定のバイオマス度を有し、かつ水性分散体であることにより、環境負荷が少ないインクを得ることが可能となる。 The acrylic resin of the present disclosure is preferably emulsion particles, and more preferably an aqueous dispersion containing acrylic resin particles (also referred to as resin particles) from the viewpoint of safety. By having a certain biomass degree of the present disclosure and being an aqueous dispersion, it is possible to obtain an ink with less environmental impact.
　本開示の樹脂粒子は単層であっても良く、複数層で形成されていてもよい。
　本開示の樹脂粒子が単層で形成されている場合には、前記アクリル系ポリマー記載の組成であって良い。
　本開示の樹脂粒子が複数層で形成されている場合には、ピペリジン基含有モノマー、付加重合性オキサゾリン、および水酸基含有（メタ）アクリレートから選ばれる１種以上は、いずれの層を構成するモノマー成分に含まれていてもよいが、密着性をより向上させる観点から、少なくとも最外層を構成するモノマー成分に含まれていることが好ましい。したがって、本開示の樹脂粒子を構成するモノマー成分には、ピペリジン基含有モノマー、付加重合性オキサゾリン、および水酸基含有（メタ）アクリレートから選ばれる少なくとも１種が含まれていることが好ましい。エマルション粒子が複数層で形成されている場合には、少なくとも最外層を構成するモノマー成分にピペリジン基含有モノマー、付加重合性オキサゾリン、および水酸基含有（メタ）アクリレートから選ばれる少なくとも１種が含まれていることが好ましい。モノマー成分におけるピペリジン基含有モノマー、付加重合性オキサゾリン、および水酸基含有（メタ）アクリレートの含有率がそれぞれ０．１～３０質量％であることがより好ましく、０．２～２０質量％であることがより一層好ましく、０．５～１０質量％であることがさらに好ましい。また、モノマー成分におけるピペリジン基含有モノマー、付加重合性オキサゾリン、および水酸基含有（メタ）アクリレートの合計含有率は、０．２～３０質量％であることが好ましく、０．２～２０質量％であることがより一層好ましい。 The resin particles of the present disclosure may have a single layer, or may be formed with multiple layers.
When the resin particles of the present disclosure are formed of a single layer, it may have the composition described above for the acrylic polymer.
When the resin particles of the present disclosure are formed of multiple layers, one or more selected from piperidine group-containing monomers, addition polymerizable oxazolines, and hydroxyl group-containing (meth)acrylates are monomer components constituting any layer. may be contained in, but from the viewpoint of further improving adhesion, it is preferably contained in at least the monomer component constituting the outermost layer. Therefore, the monomer component constituting the resin particles of the present disclosure preferably contains at least one selected from piperidine group-containing monomers, addition polymerizable oxazolines, and hydroxyl group-containing (meth)acrylates. When the emulsion particles are formed of multiple layers, the monomer component constituting at least the outermost layer contains at least one selected from piperidine group-containing monomers, addition polymerizable oxazolines, and hydroxyl group-containing (meth)acrylates. preferably. The content of the piperidine group-containing monomer, the addition polymerizable oxazoline, and the hydroxyl group-containing (meth)acrylate in the monomer component is more preferably 0.1 to 30% by mass, more preferably 0.2 to 20% by mass. More preferably, it is still more preferably 0.5 to 10% by mass. Further, the total content of the piperidine group-containing monomer, addition polymerizable oxazoline, and hydroxyl group-containing (meth)acrylate in the monomer component is preferably 0.2 to 30% by mass, and is 0.2 to 20% by mass. is even more preferable.
　本開示の樹脂粒子が複数層で形成されている場合には、２層から４層を有することが好ましく、２層または３層であることがより好ましい。多層構造の樹脂層を有するエマルション粒子において、内層は、当該エマルション粒子の最内層（コア）を意味し、外層は最内層を除いたその他層（すなわち最内層以外の層であって、最外層も含む層）を意味し、最外層は最も外側に形成される層を意味する。
　本開示の樹脂粒子が複数層で形成されている場合には、内層（最内層）を形成する単量体成分１００質量部中、環状脂肪族基を有する（メタ）アクリレート由来の構造単位の含有量は３０質量部以上であってよく、３５質量部以上が好ましく、４０質量部以上がより好ましく、４５質量部以上がさらに好ましく、９５質量部以下であってよく、９０質量部以下が好ましく、８５質量部以下がより好ましい（すなわち３０～９５質量部が好ましく、３５～９５質量部がより好ましく、４０～９０質量部がよりさらに好ましく、４５～８５質量部が特に好ましい）。 When the resin particles of the present disclosure are formed of multiple layers, it preferably has 2 to 4 layers, more preferably 2 or 3 layers. In emulsion particles having a multilayer structure resin layer, the inner layer means the innermost layer (core) of the emulsion particle, and the outer layer means the other layers excluding the innermost layer (that is, the layers other than the innermost layer, and the outermost layer and the outermost layer means the layer formed on the outermost side.
When the resin particles of the present disclosure are formed of multiple layers, the content of structural units derived from (meth)acrylate having a cycloaliphatic group in 100 parts by mass of the monomer component forming the inner layer (innermost layer) The amount may be 30 parts by mass or more, preferably 35 parts by mass or more, more preferably 40 parts by mass or more, further preferably 45 parts by mass or more, may be 95 parts by mass or less, preferably 90 parts by mass or less, It is more preferably 85 parts by mass or less (that is, preferably 30 to 95 parts by mass, more preferably 35 to 95 parts by mass, even more preferably 40 to 90 parts by mass, and particularly preferably 45 to 85 parts by mass).
　本開示の樹脂粒子が複数層で形成されている場合には、内層（最内層）を形成する単量体成分１００質量部中、環状脂肪族基を有する（メタ）アクリレート以外の単量体（以下、その他単量体Ａという）由来の構造単位の含有量は２０質量部以上であってよく、２５質量部以上が好ましく、３０質量部以上がより好ましく、３５質量部以上がさらに好ましく、７０質量部以下であってよく、６５質量部以下が好ましく、６０質量部以下がより好ましく、５５質量部以下がさらに好ましい。 When the resin particles of the present disclosure are formed of multiple layers, in 100 parts by mass of the monomer component forming the inner layer (innermost layer), a monomer other than (meth)acrylate having a cycloaliphatic group ( Hereinafter, the content of the structural unit derived from other monomer A) may be 20 parts by mass or more, preferably 25 parts by mass or more, more preferably 30 parts by mass or more, further preferably 35 parts by mass or more, and 70 parts by mass or more. It may be at most parts by mass, preferably at most 65 parts by mass, more preferably at most 60 parts by mass, and even more preferably at most 55 parts by mass.
　本開示の樹脂粒子が複数層で形成されている場合には、内層（最内層）を形成する単量体成分１００質量部中、その他単量体Ａ由来の構造単位としては、酸基含有モノマー（特に（メタ）アクリル酸など）、直鎖状アルキル基又は分岐状アルキル基を有する（メタ）アクリレート（特にメチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔ－ブチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、イソステアリル（メタ）アクリレートなど）、水酸基含有（メタ）アクリレート（特に２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、３－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレートなど）、エポキシ基含有モノマー（特にグリシジル（メタ）アクリレートなど）、スチレン系モノマー（特にスチレンなど）、ピペリジン基含有モノマー（特に４－（メタ）アクリロイルオキシ－２，２，６，６－テトラメチルピペリジン、４－（メタ）アクリロイルオキシ－１，２，２，６，６－ペンタメチルピペリジンなど）が好ましい。 When the resin particles of the present disclosure are formed of a plurality of layers, in 100 parts by mass of the monomer component forming the inner layer (innermost layer), as a structural unit derived from other monomer A, an acid group-containing monomer (especially (meth)acrylic acid, etc.), (meth)acrylates having linear or branched alkyl groups (especially methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate) acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isostearyl (meth)acrylate, etc.), hydroxyl group-containing (meth)acrylate (especially 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc.), epoxy group-containing monomers (particularly glycidyl (meth)acrylate, etc. ), styrenic monomers (especially styrene), piperidine group-containing monomers (especially 4-(meth)acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-(meth)acryloyloxy-1,2,2 , 6,6-pentamethylpiperidine) are preferred.
　本開示の樹脂粒子が複数層で形成されている場合には、外層（最内層以外の層）を形成する単量体成分１００質量部中、環状脂肪族基を有する（メタ）アクリレート由来の構造単位の含有量は３０質量部以上であってよく、３５質量部以上が好ましく、４０質量部以上がより好ましく、４５質量部以上がさらに好ましく、９５質量部以下であってよく、９０質量部以下が好ましく、８５質量部以下がより好ましい（すなわち３０～９５質量部が好ましく、３５～９０質量部がより好ましく、４０～９０質量部がさらに好ましく、４５～８５質量部が特に好ましい）。 When the resin particles of the present disclosure are formed of multiple layers, in 100 parts by mass of the monomer component forming the outer layer (layer other than the innermost layer), a (meth)acrylate-derived structure having a cycloaliphatic group The content of the unit may be 30 parts by mass or more, preferably 35 parts by mass or more, more preferably 40 parts by mass or more, even more preferably 45 parts by mass or more, and may be 95 parts by mass or less and 90 parts by mass or less. is preferred, and 85 parts by weight or less is more preferred (that is, 30 to 95 parts by weight is preferred, 35 to 90 parts by weight is more preferred, 40 to 90 parts by weight is even more preferred, and 45 to 85 parts by weight is particularly preferred).
　本開示の樹脂粒子が複数層で形成されている場合には、外層（最内層以外の層）を形成する単量体成分１００質量部中、環状脂肪族基を有する（メタ）アクリレート以外の単量体（以下、その他単量体Ｂという）由来の構造単位の含有量は２０質量部以上であってよく、２５質量部以上が好ましく、３０質量部以上がより好ましく、３５質量部以上がさらに好ましく、７０質量部以下であってよく、６５質量部以下が好ましく、６０質量部以下がより好ましく、５５質量部以下がさらに好ましい（すなわち、２０～７０質量部が好ましく、２５～６５質量部がより好ましく、３０～６０質量部がさらに好ましく、３５～５５質量部が特に好ましい）。 When the resin particles of the present disclosure are formed of multiple layers, a monomer other than (meth)acrylate having a cycloaliphatic group is included in 100 parts by mass of the monomer component forming the outer layer (layer other than the innermost layer). The content of the structural unit derived from the monomer (hereinafter referred to as other monomer B) may be 20 parts by mass or more, preferably 25 parts by mass or more, more preferably 30 parts by mass or more, and further 35 parts by mass or more. Preferably, it may be 70 parts by mass or less, preferably 65 parts by mass or less, more preferably 60 parts by mass or less, and further preferably 55 parts by mass or less (that is, preferably 20 to 70 parts by mass, and 25 to 65 parts by mass more preferably 30 to 60 parts by mass, and particularly preferably 35 to 55 parts by mass).
　本開示の樹脂粒子が複数層で形成されている場合には、外層（最内層以外の層）を形成する単量体成分１００質量部中、その他単量体Ｂ由来の構造単位としては、酸基含有モノマー（特に（メタ）アクリル酸など）、直鎖状アルキル基又は分岐状アルキル基を有する（特にメタ）アクリレート（特にメチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔ－ブチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、イソステアリル（メタ）アクリレートなど）、水酸基含有（メタ）アクリレート（特に２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、３－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレートなど）、エポキシ基含有モノマー（特にグリシジル（メタ）アクリレートなど）、スチレン系モノマー（特にスチレンなど）、ピペリジン基含有モノマー（特に４－（メタ）アクリロイルオキシ－２，２，６，６－テトラメチルピペリジン、４－（メタ）アクリロイルオキシ－１，２，２，６，６－ペンタメチルピペリジンなど）が好ましい。 When the resin particles of the present disclosure are formed of multiple layers, in 100 parts by mass of the monomer component forming the outer layer (layer other than the innermost layer), as a structural unit derived from other monomer B, acid Group-containing monomers (especially (meth)acrylic acid, etc.), (especially meth)acrylates having linear or branched alkyl groups (especially methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, Butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isostearyl (meth) acrylate, etc.), hydroxyl group-containing (meth) acrylate (especially 2-hydroxyethyl ( meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, etc.), epoxy group-containing monomers (especially glycidyl ( meth) acrylate, etc.), styrenic monomers (especially styrene, etc.), piperidine group-containing monomers (especially 4-(meth)acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-(meth)acryloyloxy-1 , 2,2,6,6-pentamethylpiperidine) are preferred.
　本開示の樹脂粒子が複数層で形成されている場合には、最外層を形成する単量体成分１００質量部中、環状脂肪族基を有する（メタ）アクリレート由来の構造単位の含有量は３０質量部以上であってよく、３５質量部以上が好ましく、４０質量部以上がより好ましく、４５質量部以上がさらに好ましく、９５質量部以下であってよく、９０質量部以下が好ましく、８５質量部以下がより好ましい（すなわち３０～９５質量部が好ましく、３５～９５質量部がより好ましく、４０～９０質量部がさらに好ましく、４５～８５質量部が特に好ましい）。
　本開示の樹脂粒子が複数層で形成されている場合には、最外層を形成する単量体成分１００質量部中、環状脂肪族炭化水素基を有する（メタ）アクリレート以外の単量体（以下、その他単量体Ｃという）由来の構造単位の含有量は２０質量部以上であってよく、２５質量部以上が好ましく、３０質量部以上がより好ましく、３５質量部以上がさらに好ましく、７０質量部以下であってよく、６５質量部以下が好ましく、６０質量部以下がより好ましく、５５質量部以下がさらに好ましい（すなわち２０～７０質量部が好ましく、２５～６５質量部がより好ましく、３０～６０質量部がさらに好ましく、３５～５５質量部が特に好ましい）。 When the resin particles of the present disclosure are formed of multiple layers, the content of structural units derived from (meth)acrylate having a cycloaliphatic group is 30 in 100 parts by mass of the monomer component forming the outermost layer. It may be at least 35 parts by mass, preferably at least 40 parts by mass, even more preferably at least 45 parts by mass, may be at most 95 parts by mass, preferably at most 90 parts by mass, and 85 parts by mass. The following are more preferred (that is, 30 to 95 parts by weight are preferred, 35 to 95 parts by weight are more preferred, 40 to 90 parts by weight are even more preferred, and 45 to 85 parts by weight are particularly preferred).
When the resin particles of the present disclosure are formed of multiple layers, in 100 parts by mass of the monomer component forming the outermost layer, a monomer other than (meth)acrylate having a cycloaliphatic hydrocarbon group (hereinafter , Other monomer C) derived structural unit content may be 20 parts by mass or more, preferably 25 parts by mass or more, more preferably 30 parts by mass or more, further preferably 35 parts by mass or more, and 70 parts by mass parts or less, preferably 65 parts by mass or less, more preferably 60 parts by mass or less, and even more preferably 55 parts by mass or less (that is, preferably 20 to 70 parts by mass, more preferably 25 to 65 parts by mass, 30 to 60 parts by mass is more preferable, and 35 to 55 parts by mass is particularly preferable).
本開示の樹脂粒子が複数層で形成されている場合には、最外層を形成する単量体成分１００質量部中、その他単量体Ｃ由来の構造単位としては、酸基含有モノマー（（メタ）アクリル酸など）、直鎖状アルキル基又は分岐状アルキル基を有する（メタ）アクリレート（特にメチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔ－ブチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、イソステアリル（メタ）アクリレートなど）、水酸基含有（メタ）アクリレート（特に２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、３－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレートなど）、エポキシ基含有モノマー（特にグリシジル（メタ）アクリレートなど）、スチレン系モノマー（特にスチレンなど）、ピペリジン基含有モノマー（特に４－（メタ）アクリロイルオキシ－２，２，６，６－テトラメチルピペリジン、４－（メタ）アクリロイルオキシ－１，２，２，６，６－ペンタメチルピペリジンなど）が好ましい。 When the resin particles of the present disclosure are formed of multiple layers, in 100 parts by mass of the monomer component forming the outermost layer, as structural units derived from other monomer C, an acid group-containing monomer ((meta ) acrylic acid, etc.), (meth)acrylates with linear or branched alkyl groups (especially methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, isobutyl ( meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isostearyl (meth) acrylate, etc.), hydroxyl group-containing (meth) acrylate (especially 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, etc.), epoxy group-containing monomers (especially glycidyl (meth) acrylate, etc.), styrenic Monomers (especially styrene, etc.), piperidine group-containing monomers (especially 4-(meth)acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-(meth)acryloyloxy-1,2,2,6,6 -pentamethylpiperidine, etc.) are preferred.
　本開示の樹脂粒子が複数層で形成されている場合には、本開示の内層（最内層）を構成しているポリマー層と外層（最内層以外の層）を構成しているポリマー層との質量比（内層を構成しているポリマー層／外層を構成しているポリマー層）は、可撓性、耐ブロッキング性、基材に対する密着性および耐引っ掻き傷性を向上させる観点から、好ましくは１０／９０～９０／１０、より好ましくは２０／８０～８０／２０、さらに好ましくは３０／７０～７０／３０、さらに一層好ましくは４０／６０～６０／４０である。 When the resin particles of the present disclosure are formed of multiple layers, the polymer layer constituting the inner layer (innermost layer) of the present disclosure and the polymer layer constituting the outer layer (layer other than the innermost layer) The mass ratio (polymer layer constituting the inner layer/polymer layer constituting the outer layer) is preferably 10 from the viewpoint of improving flexibility, blocking resistance, adhesion to the substrate and scratch resistance. /90 to 90/10, more preferably 20/80 to 80/20, still more preferably 30/70 to 70/30, even more preferably 40/60 to 60/40.
　本開示の内層（最内層）を構成しているポリマー層と最外層を構成しているポリマー層との質量比（内層を構成しているポリマー層／最外層を構成しているポリマー層）は、可撓性、耐ブロッキング性、基材に対する密着性および耐引っ掻き傷性を向上させる観点から、好ましくは１０／９０～９０／１０、より好ましくは２０／８０～８０／２０、さらに好ましくは３０／７０～７０／３０、さらに一層好ましくは４０／６０～６０／４０である。 The mass ratio (polymer layer constituting the inner layer/polymer layer constituting the outermost layer) of the polymer layer constituting the inner layer (innermost layer) and the polymer layer constituting the outermost layer of the present disclosure is , From the viewpoint of improving flexibility, blocking resistance, adhesion to substrates and scratch resistance, preferably 10/90 to 90/10, more preferably 20/80 to 80/20, still more preferably 30 /70 to 70/30, even more preferably 40/60 to 60/40.
　＜アクリル系樹脂の物性＞
　本開示のアクリル系樹脂のガラス転移温度は、耐ブロッキング性、耐擦過性、密着性、耐粘着テープ剥離性向上の観点から－３０℃以上又は－１０℃以上であってよく、０℃以上が好ましく、５℃以上がより好ましく、１０℃以上がさらに好ましく、９０℃以下であってよく、８０℃以下が好ましく、７０℃以下がより好ましく、６０℃以下がさらに好ましい（すなわち、－３０～９０℃であってもよく、－１０～９０℃が好ましく、０～８０℃がより好ましく、５～７０℃がさらに好ましく、１０～６０℃が特に好ましい）。 <Physical properties of acrylic resin>
The glass transition temperature of the acrylic resin of the present disclosure may be −30° C. or higher or −10° C. or higher from the viewpoint of improving blocking resistance, scratch resistance, adhesion, and adhesive tape peeling resistance, and 0° C. or higher is preferably 5° C. or higher, more preferably 10° C. or higher, may be 90° C. or lower, preferably 80° C. or lower, more preferably 70° C. or lower, further preferably 60° C. or lower (that is, −30 to 90 °C, preferably -10 to 90°C, more preferably 0 to 80°C, even more preferably 5 to 70°C, and particularly preferably 10 to 60°C).
　本開示のアクリル系樹脂が樹脂粒子であり、単層のエマルション粒子の場合、アクリル系樹脂を構成するアクリル系ポリマーのガラス転移温度は、上記範囲であることが好ましい。アクリル系ポリマーのガラス転移温度は、アクリル系ポリマーを形成する単量体の種類およびその量を調整することによって調整することができる。 When the acrylic resin of the present disclosure is a resin particle and is a single-layer emulsion particle, the glass transition temperature of the acrylic polymer constituting the acrylic resin is preferably within the above range. The glass transition temperature of the acrylic polymer can be adjusted by adjusting the type and amount of monomers forming the acrylic polymer.
　本開示のアクリル系樹脂が樹脂粒子であり、複数層で形成されている場合には、内層（最内層）を構成するポリマーのガラス転移温度は、密着性、耐スクラッチ性の観点から、－１０℃以上、好ましくは０℃以上であり、当該ガラス転移温度の上限値は、密着性、耐スクラッチ性の観点から、好ましくは１２０℃以下、より好ましくは１００℃以下である（すなわち－１０～１２０℃が好ましく、０～１００℃がより好ましい）。内層（最内層）を形成するポリマーのガラス転移温度は、内層（最内層）を形成する単量体の種類およびその量を調整することによって調整することができる。 When the acrylic resin of the present disclosure is resin particles and is formed of multiple layers, the glass transition temperature of the polymer constituting the inner layer (innermost layer) is -10 from the viewpoint of adhesion and scratch resistance. ° C. or higher, preferably 0 ° C. or higher, and the upper limit of the glass transition temperature is preferably 120 ° C. or lower, more preferably 100 ° C. or lower from the viewpoint of adhesion and scratch resistance (that is, -10 to 120 °C is preferred, and 0 to 100°C is more preferred). The glass transition temperature of the polymer forming the inner layer (innermost layer) can be adjusted by adjusting the type and amount of the monomer forming the inner layer (innermost layer).
　本開示のアクリル系樹脂が樹脂粒子であり、複数層で形成されている場合には、外層（最内層以外の層）を構成するポリマーのガラス転移温度は密着性、耐スクラッチ性、造膜性の観点から、０℃以上、好ましくは１０℃以上であり、当該ガラス転移温度の上限値は、密着性、耐スクラッチ性の観点から、好ましくは１００℃以下、より好ましくは９０℃以下である（すなわち０～１００℃が好ましく、１０～９０℃がより好ましい）。外層（最内層以外の層）を形成するポリマーのガラス転移温度は、外層（最内層以外の層）を形成する単量体の種類およびその量を調整することによって調整することができる。 When the acrylic resin of the present disclosure is a resin particle and is formed of multiple layers, the glass transition temperature of the polymer that constitutes the outer layer (layer other than the innermost layer) has adhesion, scratch resistance, and film-forming properties. From the viewpoint of, the upper limit of the glass transition temperature is preferably 100 ° C. or lower, more preferably 90 ° C. or lower from the viewpoint of adhesion and scratch resistance ( That is, 0 to 100°C is preferable, and 10 to 90°C is more preferable). The glass transition temperature of the polymer forming the outer layer (layer other than the innermost layer) can be adjusted by adjusting the type and amount of the monomer forming the outer layer (layer other than the innermost layer).
　本開示のアクリル系樹脂が樹脂粒子であり、複数層で形成されている場合には、最外層を構成するポリマーのガラス転移温度は密着性、耐スクラッチ性、造膜性の観点から、０℃以上、好ましくは１０℃以上であり、当該ガラス転移温度の上限値は、密着性、耐スクラッチ性の観点から、好ましくは１００℃以下、より好ましくは９０℃以下である（すなわち０～１００℃が好ましく、１０～９０℃がより好ましい）。最外層を形成するポリマーのガラス転移温度は、最外層を形成する単量体の種類およびその量を調整することによって調整することができる。 When the acrylic resin of the present disclosure is resin particles and is formed of multiple layers, the glass transition temperature of the polymer constituting the outermost layer is 0° C. from the viewpoint of adhesion, scratch resistance, and film-forming properties. Above, it is preferably 10° C. or higher, and the upper limit of the glass transition temperature is preferably 100° C. or lower, more preferably 90° C. or lower from the viewpoint of adhesion and scratch resistance (that is, 0 to 100° C. preferably 10 to 90° C.). The glass transition temperature of the polymer forming the outermost layer can be adjusted by adjusting the type and amount of the monomer forming the outermost layer.
　本開示のアクリル系樹脂は酸価を有さなくてもよいが、酸価を有する場合、その値は５０ｍｇＫＯＨ／ｇ以下であってもよく、４０ｍｇＫＯＨ／ｇ以下であることが好ましく、３５ｍｇＫＯＨ／ｇ以下であることがより好ましく、３０ｍｇＫＯＨ／ｇ以下であることがさらに好ましく、１０ｍｇＫＯＨ／ｇ以下であることが特に好ましい。上記範囲を有することにより、インクジェット用インクとして好ましい粘度水性インクが得ることができ、密着性、耐スクラッチ性、耐ブロッキング性、耐粘着テープ剥離性、吐出安定性向上の効果が期待できる。
　本開示のアクリル系樹脂が樹脂粒子であり、複数層で形成されている場合には、内層（最内層）を構成するポリマーは酸価を有さなくてもよいが、酸価を有する場合、その値は、５０ｍｇＫＯＨ／ｇ以下であってもよく、４０ｍｇＫＯＨ／ｇ以下であることが好ましく、３５ｍｇＫＯＨ／ｇ以下であることがより好ましく、３０ｍｇＫＯＨ／ｇ以下であることがさらに好ましく、１０ｍｇＫＯＨ／ｇ以下であることが特に好ましい。樹脂粒子内層（最内層）を構成する重合体の酸価が上記範囲を有することにより、インクジェット用インクとして好ましい粘度水性インクが得ることができ、密着性、耐スクラッチ性、耐ブロッキング性、耐粘着テープ剥離性、吐出安定性向上の効果が期待できる。 The acrylic resin of the present disclosure may not have an acid value, but if it has an acid value, the value may be 50 mgKOH / g or less, preferably 40 mgKOH / g or less, and 35 mgKOH / g It is more preferably 30 mgKOH/g or less, particularly preferably 10 mgKOH/g or less. By having the above range, it is possible to obtain a water-based ink with a preferable viscosity as an inkjet ink, and effects of improving adhesion, scratch resistance, blocking resistance, adhesive tape peeling resistance, and ejection stability can be expected.
When the acrylic resin of the present disclosure is resin particles and is formed of multiple layers, the polymer constituting the inner layer (innermost layer) may not have an acid value, but if it has an acid value, The value may be 50 mgKOH/g or less, preferably 40 mgKOH/g or less, more preferably 35 mgKOH/g or less, further preferably 30 mgKOH/g or less, and 10 mgKOH/g or less. is particularly preferred. When the acid value of the polymer constituting the inner layer of the resin particles (the innermost layer) is within the above range, it is possible to obtain a water-based ink with a viscosity that is preferable as an inkjet ink, and has adhesion, scratch resistance, blocking resistance, and adhesion resistance. Effects of improving tape releasability and ejection stability can be expected.
　本開示のアクリル系樹脂が樹脂粒子であり、複数層で形成されている場合には、外層（最内層以外の層）を構成する重合体の酸価を有さなくてもよいが、５０ｍｇＫＯＨ／ｇ以下であってもよく、４０ｍｇＫＯＨ／ｇ以下であることが好ましく、３５ｍｇＫＯＨ／ｇ以下であることがより好ましく、３０ｍｇＫＯＨ／ｇ以下であることがさらに好ましく、１０ｍｇＫＯＨ／ｇ以下であることが特に好ましい。樹脂粒子の外層（最内層以外の層）の酸価が上記範囲を有することにより、インクジェット用インクとして好ましい粘度水性インクが得ることができ、密着性、耐スクラッチ性、耐ブロッキング性、耐粘着テープ剥離性、吐出安定性向上の効果が期待できる。 When the acrylic resin of the present disclosure is a resin particle and is formed of multiple layers, the polymer constituting the outer layer (layer other than the innermost layer) may not have an acid value of 50 mg KOH/ g or less, preferably 40 mgKOH/g or less, more preferably 35 mgKOH/g or less, even more preferably 30 mgKOH/g or less, and particularly preferably 10 mgKOH/g or less. . By having the acid value of the outer layer (layer other than the innermost layer) of the resin particles within the above range, it is possible to obtain a viscosity water-based ink that is preferable as an inkjet ink, and has adhesion, scratch resistance, blocking resistance, and adhesive tape resistance. The effect of improving releasability and ejection stability can be expected.
　本開示のアクリル系樹脂が樹脂粒子であり、複数層で形成されている場合には、最外層を構成する重合体は酸価を有さなくてもよいが、酸価を有する場合、その値は、５０ｍｇＫＯＨ／ｇ以下であってもよく、４０ｍｇＫＯＨ／ｇ以下であることが好ましく、３５ｍｇＫＯＨ／ｇ以下であることがより好ましく、３０ｍｇＫＯＨ／ｇ以下であることがさらに好ましく、１０ｍｇＫＯＨ／ｇ以下であることが特に好ましい。樹脂粒子の最外層の酸価が上記範囲を有することにより、インクジェット用インクとして好ましい粘度水性インクが得ることができ、密着性、耐スクラッチ性、耐ブロッキング性、耐粘着テープ剥離性、吐出安定性向上の効果が期待できる。 When the acrylic resin of the present disclosure is a resin particle and is formed of multiple layers, the polymer constituting the outermost layer may not have an acid value, but if it has an acid value, the value may be 50 mgKOH/g or less, preferably 40 mgKOH/g or less, more preferably 35 mgKOH/g or less, even more preferably 30 mgKOH/g or less, and 10 mgKOH/g or less. is particularly preferred. By having the acid value of the outermost layer of the resin particles within the above range, it is possible to obtain a water-based ink with a viscosity that is preferable as an inkjet ink, and it has excellent adhesion, scratch resistance, blocking resistance, adhesive tape releasability, and ejection stability. An improvement effect can be expected.
　本開示のアクリル系樹脂の重合平均分子量は、密着性、造膜性、レベリング性向上の観点から好ましくは１０万以上、より好ましくは３０万以上、さらに好ましくは４０万以上、さらに一層好ましくは５０万以上である。当該樹脂の重量平均分子量の上限値は、架橋構造を有する場合、その重量平均分子量を測定することが困難なため、特に限定されないが、架橋構造を有しない場合には、画像均一性、基材に対する密着性、耐ブロッキング性、粘度変化安定性および連続吐出安定性に総合的に優れた水性インクを得る観点から、４００万以下であることが好ましい。
　本発明においてアクリル系樹脂の重量平均分子量は、ＲＩ検出器を装備したゲルパーミエイションクロマトグラフィー〔東ソー（株）製、品番：ＨＬＣ－８１２０ＧＰＣ、カラム：ＴＳＫｇｅｌ　Ｇ－５０００ＨＸＬとＴＳＫｇｅｌＧＭＨＸＬ－Ｌとを直列に使用、展開溶媒：テトラヒドロフラン（ＴＨＦ）〕を用いて作成されるゲルパーミエイションクロマトグラフィーのチャートと、東ソー（株）製の標準ポリスチレンＦ－４５０、Ａ－５０００、Ａ－１０００およびＡ－３００を用いて作成される校正曲線から求められた重量平均分子量（ポリスチレン換算）を意味する。 The polymerization average molecular weight of the acrylic resin of the present disclosure is preferably 100,000 or more, more preferably 300,000 or more, still more preferably 400,000 or more, and even more preferably 50,000 from the viewpoint of improving adhesion, film-forming properties, and leveling properties. more than 10,000. The upper limit of the weight average molecular weight of the resin is not particularly limited because it is difficult to measure the weight average molecular weight when it has a crosslinked structure. It is preferably 4,000,000 or less from the viewpoint of obtaining a water-based ink that is comprehensively excellent in adhesion to liquid, blocking resistance, viscosity change stability, and continuous ejection stability.
In the present invention, the weight average molecular weight of the acrylic resin is determined by gel permeation chromatography equipped with an RI detector [manufactured by Tosoh Corporation, product number: HLC-8120GPC, column: TSKgel G-5000HXL and TSKgelGMHXL-L are connected in series. used, developing solvent: tetrahydrofuran (THF)] and standard polystyrene F-450, A-5000, A-1000 and A-300 manufactured by Tosoh Corporation. Means the weight average molecular weight (polystyrene conversion) obtained from the calibration curve created using.
　＜アクリル系樹脂の製造方法＞
　本開示のアクリル系樹脂の製造方法としては、塊状重合、懸濁重合、溶液重合、沈殿重合、乳化重合等の既存の方法を適用することができる。これらの中でも、環境負荷低減の観点から乳化重合が好ましく、中でも安全性の観点から溶媒に水などの水性媒体を用いることがより好ましい。 <Method for producing acrylic resin>
Existing methods such as bulk polymerization, suspension polymerization, solution polymerization, precipitation polymerization, and emulsion polymerization can be applied as the method for producing the acrylic resin of the present disclosure. Among these, emulsion polymerization is preferable from the viewpoint of reducing environmental load, and it is more preferable to use an aqueous medium such as water as a solvent from the viewpoint of safety.
　本開示のアクリル系樹脂を製造するにあたり、モノマー成分を乳化重合させる方法としては、例えば、メタノールなどの低級アルコールなどの水溶性有機溶媒と水とを含む水性媒体、水などの媒体中に乳化剤を溶解させ、撹拌下でモノマー成分および重合開始剤を滴下させる方法、乳化剤および水を用いてあらかじめ乳化させておいたモノマー成分を水または水性媒体中に滴下させる方法などが挙げられるが、かかる方法のみに限定されるものではない。なお、媒体の量は、得られるエマルションに含まれる不揮発分量を考慮して適宜設定すればよい。媒体は、あらかじめ反応容器に仕込んでおいてもよく、あるいはプレエマルションとして使用してもよい。また、媒体は、必要により、モノマー成分を乳化重合させ、エマルションを製造しているときに用いてもよい。 In producing the acrylic resin of the present disclosure, the method of emulsion polymerization of the monomer component includes, for example, an aqueous medium containing a water-soluble organic solvent such as a lower alcohol such as methanol and water, or an emulsifier in a medium such as water. Examples include a method of dissolving and dropping the monomer component and the polymerization initiator under stirring, and a method of dropping the monomer component previously emulsified using an emulsifier and water into water or an aqueous medium, but only such a method. is not limited to In addition, the amount of the medium may be appropriately set in consideration of the amount of non-volatile matter contained in the obtained emulsion. The medium may be charged into the reaction vessel in advance, or may be used as a pre-emulsion. In addition, the medium may be used, if necessary, during emulsion polymerization of the monomer components to produce an emulsion.
　モノマー成分を乳化重合させる際には、モノマー成分、乳化剤および媒体を混合した後に乳化重合を行なってもよく、モノマー成分、乳化剤および媒体を撹拌することによって乳化させ、プレエマルションを調製した後に乳化重合を行なってもよく、あるいはモノマー成分、乳化剤および媒体のうちの少なくとも１種類とその残部のプレエマルションとを混合して乳化重合を行なってもよい。モノマー成分、乳化剤および媒体は、それぞれ一括添加してもよく、分割添加してもよく、あるいは連続滴下してもよい。 When the monomer component is emulsion polymerized, the emulsion polymerization may be performed after mixing the monomer component, the emulsifier and the medium. Alternatively, emulsion polymerization may be carried out by mixing at least one of the monomer components, emulsifier and medium with the rest of the pre-emulsion. The monomer component, emulsifier and medium may be added all at once, added in portions, or added dropwise continuously.
　上記で得られたエマルションに含まれているエマルション粒子上に外層用ポリマー成分からなる外層を形成させる場合には、上記エマルション中で上記と同様にして単量体成分を乳化重合させることにより、上記エマルション粒子上に外層を形成させることができる。また、上記外層（中間層）が形成されたエマルション粒子上にさらに外層を形成させる場合には、上記と同様にしてエマルション中で単量体成分を乳化重合させることにより、上記エマルション粒子上にさらに他の外層用ポリマー成分からなる外層を形成させることができる。このように多段乳化重合法により、多層構造を有するエマルション粒子（コアシェルエマルション粒子）を調製することができる。 In the case of forming an outer layer composed of the outer layer polymer component on the emulsion particles contained in the emulsion obtained above, the monomer component is emulsion-polymerized in the emulsion in the same manner as described above to obtain the above An outer layer can be formed on the emulsion particles. Further, in the case of forming an outer layer on the emulsion particles on which the outer layer (intermediate layer) is formed, the monomer component is emulsion-polymerized in the emulsion in the same manner as described above to form an additional layer on the emulsion particles. An outer layer comprising other outer layer polymer components can be formed. Thus, emulsion particles having a multilayer structure (core-shell emulsion particles) can be prepared by the multistage emulsion polymerization method.
　なお、コアシェルエマルション粒子を調製する際、先に内層用ポリマー成分からなる内層を形成する乳化重合を行なう前に１段または複数段の乳化重合を行なってもよく、上記内層を形成する乳化重合と上記中間層を形成する乳化重合との間に１段または複数段の乳化重合を行なってもよい。また、上記中間層を形成する乳化重合と上記外層を形成する乳化重合との間に１段または複数段の乳化重合を行なってもよい。さらに、上記外層を形成する乳化重合の後に１段または複数段の乳化重合を行なってもよい。
　乳化剤としては、アニオン性乳化剤、ノニオン性乳化剤、カチオン性乳化剤、両性乳化剤、高分子乳化剤などが挙げられ、これらの乳化剤は、それぞれ単独で用いてもよく、２種類以上を併用してもよい。 When preparing the core-shell emulsion particles, one-stage or multiple-stage emulsion polymerization may be carried out prior to the emulsion polymerization for forming the inner layer composed of the polymer component for the inner layer. One or more stages of emulsion polymerization may be carried out between the emulsion polymerization for forming the intermediate layer. Further, between the emulsion polymerization for forming the intermediate layer and the emulsion polymerization for forming the outer layer, one or more stages of emulsion polymerization may be performed. Further, one-stage or multiple-stage emulsion polymerization may be carried out after the emulsion polymerization for forming the outer layer.
Examples of emulsifiers include anionic emulsifiers, nonionic emulsifiers, cationic emulsifiers, amphoteric emulsifiers, polymer emulsifiers, etc. These emulsifiers may be used alone or in combination of two or more.
　本開示の乳化剤のバイオマス度は、環境負荷の観点から１０％以上であることが好ましく、２０％以上がより好ましく、３０％以上がさらに好ましく、４０％以上が特に好ましい。 The biomass degree of the emulsifier of the present disclosure is preferably 10% or more, more preferably 20% or more, even more preferably 30% or more, and particularly preferably 40% or more, from the viewpoint of environmental load.
　アニオン性乳化剤としては、例えば、アンモニウムドデシルサルフェート、ナトリウムドデシルサルフェートなどのアルキルサルフェート塩；アンモニウムドデシルスルホネート、ナトリウムドデシルスルホネート、ナトリウムアルキルジフェニルエーテルジスルホネートなどのアルキルスルホネート塩；アンモニウムドデシルベンゼンスルホネート、ナトリウムドデシルナフタレンスルホネートなどのアルキルアリールスルホネート塩；ポリオキシエチレンアルキルスルホネート塩；ポリオキシエチレンアルキルサルフェート塩；ポリオキシエチレンアルキルアリールサルフェート塩；ジアルキルスルホコハク酸塩；アリールスルホン酸－ホルマリン縮合物；アンモニウムラウリレート、ナトリウムステアリレートなどの脂肪酸塩；ビス（ポリオキシエチレン多環フェニルエーテル）メタクリレートスルホネート塩、プロペニル－アルキルスルホコハク酸エステル塩、（メタ）アクリル酸ポリオキシエチレンスルホネート塩、（メタ）アクリル酸ポリオキシエチレンホスフォネート塩、アリルオキシメチルアルキルオキシポリオキシエチレンのスルホネート塩などのアリル基を有する硫酸エステルまたはその塩；アリルオキシメチルアルコキシエチルポリオキシエチレンの硫酸エステル塩、ポリオキシアルキレンアルケニルエーテル硫酸アンモニウム塩などが挙げられるが、かかる例示のみに限定されるものではない。 Examples of anionic emulsifiers include alkylsulfate salts such as ammonium dodecylsulfate and sodium dodecylsulfate; alkylsulfonate salts such as ammonium dodecylsulfonate, sodium dodecylsulfonate and sodium alkyldiphenylether disulfonate; ammonium dodecylbenzenesulfonate, sodium dodecylnaphthalenesulfonate and the like. polyoxyethylene alkylsulfonate salts; polyoxyethylene alkylsulfate salts; polyoxyethylene alkylarylsulfate salts; dialkylsulfosuccinates; arylsulfonic acid-formalin condensates; Fatty acid salt; bis(polyoxyethylene polycyclic phenyl ether) methacrylate sulfonate salt, propenyl-alkyl sulfosuccinate ester salt, (meth)acrylic acid polyoxyethylene sulfonate salt, (meth)acrylic acid polyoxyethylene phosphonate salt, allyl allyl group-containing sulfate esters such as oxymethylalkyloxypolyoxyethylene sulfonate salts or salts thereof; allyloxymethylalkoxyethylpolyoxyethylene sulfate ester salts; is not limited to only
　ノニオン性乳化剤としては、例えば、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルアリールエーテル、ポリエチレングリコールとポリプロピレングリコールとの縮合物、ソルビタン脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル、脂肪酸モノグリセライド、エチレンオキサイドと脂肪族アミンとの縮合生成物、アリルオキシメチルアルコキシエチルヒドロキシポリオキシエチレン、ポリオキシアルキレンアルケニルエーテルなどが挙げられるが、かかる例示のみに限定されるものではない。 Examples of nonionic emulsifiers include polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, condensates of polyethylene glycol and polypropylene glycol, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, fatty acid monoglycerides, ethylene oxide and aliphatic Condensation products with amines, allyloxymethylalkoxyethylhydroxypolyoxyethylenes, polyoxyalkylene alkenyl ethers, etc., but not limited to these examples.
　カチオン性乳化剤としては、例えば、ドデシルアンモニウムクロライドなどのアルキルアンモニウム塩などが挙げられるが、かかる例示のみに限定されるものではない。
　両性乳化剤としては、例えば、ベタインエステル型乳化剤などが挙げられるが、かかる例示のみに限定されるものではない。
　高分子乳化剤としては、例えば、ポリアクリル酸ナトリウムなどのポリ（メタ）アクリル酸塩；ポリビニルアルコール；ポリビニルピロリドン；ポリヒドロキシエチルアクリレートなどのポリヒドロキシアルキル（メタ）アクリレート；これらの重合体を構成する単量体のうちの１種類以上を共重合成分とする共重合体などが挙げられるが、かかる例示のみに限定されるものではない。 Cationic emulsifiers include, for example, alkylammonium salts such as dodecylammonium chloride, but are not limited to these examples.
Examples of amphoteric emulsifiers include betaine ester emulsifiers, but are not limited to these examples.
Polymeric emulsifiers include, for example, poly(meth)acrylates such as sodium polyacrylate; polyvinyl alcohol; polyvinylpyrrolidone; polyhydroxyalkyl(meth)acrylates such as polyhydroxyethyl acrylate; Examples thereof include copolymers containing one or more of the monomers as a copolymer component, but are not limited to these examples.
　また、上記乳化剤として、耐水性と画像均一性をより向上させる観点から、重合性基を有する乳化剤、すなわち、いわゆる反応性乳化剤が好ましく、環境保護の観点から、非ノニルフェニル型の乳化剤が好ましい。 As the emulsifier, an emulsifier having a polymerizable group, that is, a so-called reactive emulsifier is preferable from the viewpoint of further improving water resistance and image uniformity, and a non-nonylphenyl emulsifier is preferable from the viewpoint of environmental protection.
　反応性乳化剤としては、例えば、プロペニル－アルキルスルホコハク酸エステル塩、（メタ）アクリル酸ポリオキシエチレンスルホネート塩、（メタ）アクリル酸ポリオキシエチレンホスフォネート塩〔例えば、三洋化成工業（株）製、商品名：エレミノールＲＳ－３０など〕、ポリオキシエチレンアルキルプロペニルフェニルエーテルスルホネート塩〔例えば、第一工業製薬（株）製、商品名：アクアロンＨＳ－１０など〕、アリルオキシメチルアルキルオキシポリオキシエチレンのスルホネート塩〔例えば、第一工業製薬（株）製、商品名：アクアロンＫＨ－１０など〕、アリルオキシメチルノニルフェノキシエチルヒドロキシポリオキシエチレンのスルホネート塩〔例えば、（株）ＡＤＥＫＡ製、商品名：アデカリアソープＳＥ－１０など〕、アリルオキシメチルアルコキシエチルヒドロキシポリオキシエチレン硫酸エステル塩〔例えば、（株）ＡＤＥＫＡ製、商品名：アデカリアソープＳＲ－１０、ＳＲ－２０、ＳＲ－３０など〕、ビス（ポリオキシエチレン多環フェニルエーテル）メタクリレート化スルホネート塩〔例えば、日本乳化剤（株）製、商品名：アントックスＭＳ－６０など〕、アリルオキシメチルアルコキシエチルヒドロキシポリオキシエチレン〔例えば、（株）ＡＤＥＫＡ製、商品名：アデカリアソープＥＲ－１０、ＥＲ－２０、ＥＲ－３０など〕、ポリオキシエチレンアルキルプロペニルフェニルエーテル〔例えば、第一工業製薬（株）製、商品名：アクアロンＲＮ－２０など〕、アリルオキシメチルノニルフェノキシエチルヒドロキシポリオキシエチレン〔例えば、（株）ＡＤＥＫＡ製、商品名：アデカリアソープＮＥ－１０など）などが挙げられるが、かかる例示のみに限定されるものではない。 Examples of reactive emulsifiers include propenyl-alkylsulfosuccinate ester salts, (meth)acrylic acid polyoxyethylene sulfonate salts, (meth)acrylic acid polyoxyethylene phosphonate salts [for example, manufactured by Sanyo Chemical Industries, Ltd., Product name: Eleminol RS-30, etc.], polyoxyethylene alkylpropenyl phenyl ether sulfonate salt [for example, Daiichi Kogyo Seiyaku Co., Ltd., product name: Aqualon HS-10, etc.], allyloxymethylalkyloxypolyoxyethylene Sulfonate salts [for example, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon KH-10, etc.], sulfonate salts of allyloxymethyl nonylphenoxyethyl hydroxypolyoxyethylene [for example, manufactured by ADEKA Co., Ltd., trade name: ADEKA rear soap SE-10, etc.], allyloxymethylalkoxyethyl hydroxypolyoxyethylene sulfate ester salt [for example, manufactured by ADEKA Corporation, trade names: Adeka rear soap SR-10, SR-20, SR-30, etc.], bis (Polyoxyethylene polycyclic phenyl ether) methacrylated sulfonate salt [for example, manufactured by Nippon Nyukazai Co., Ltd., trade name: Antox MS-60, etc.], allyloxymethylalkoxyethyl hydroxypolyoxyethylene [for example, ADEKA Corporation] manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: Adekari Soap ER-10, ER-20, ER-30, etc.], polyoxyethylene alkylpropenyl phenyl ether [for example, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon RN-20, etc.] , allyloxymethyl nonylphenoxyethyl hydroxypolyoxyethylene [eg, manufactured by ADEKA Co., Ltd., trade name: Adekari Soap NE-10, etc.], etc., but are not limited to these examples.
　単量体成分１００質量部あたりの乳化剤の量は、重合安定性を向上させる観点から、好ましくは０．５質量部以上、より好ましくは１質量部以上、さらに好ましくは２質量部以上、特に好ましくは３質量部以上であり、耐水性を向上させる観点から、好ましくは１０質量部以下、より好ましくは６質量部以下である。 The amount of the emulsifier per 100 parts by mass of the monomer component is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, still more preferably 2 parts by mass or more, and particularly preferably, from the viewpoint of improving polymerization stability. is 3 parts by mass or more, preferably 10 parts by mass or less, more preferably 6 parts by mass or less from the viewpoint of improving water resistance.
　重合開始剤としては、例えば、アゾビスイソブチロニトリル、２，２－アゾビス（２－メチルブチロニトリル）、２，２－アゾビス（２，４－ジメチルバレロニトリル）、２，２－アゾビス（２―ジアミノプロパン）ハイドロクロライド、４，４－アゾビス（４－シアノ吉草酸）、２，２－アゾビス（２－メチルプロピオンアミジン）などのアゾ化合物；過硫酸アンモニウム、過硫酸カリウムなどの過硫酸塩；過酸化水素、ベンゾイルパーオキサイド、パラクロロベンゾイルパーオキサイド、ラウロイルパーオキサイド、過酸化アンモニウムなどの過酸化物などが挙げられるが、かかる例示のみに限定されるものではない。これらの重合開始剤は、それぞれ単独で用いてもよく、２種類以上を併用してもよい。 Examples of polymerization initiators include azobisisobutyronitrile, 2,2-azobis(2-methylbutyronitrile), 2,2-azobis(2,4-dimethylvaleronitrile), 2,2-azobis ( 2-diaminopropane) hydrochloride, 4,4-azobis (4-cyanovaleric acid), azo compounds such as 2,2-azobis (2-methylpropionamidine); persulfates such as ammonium persulfate and potassium persulfate; Hydrogen peroxide, benzoyl peroxide, parachlorobenzoyl peroxide, lauroyl peroxide, and peroxides such as ammonium peroxide are included, but are not limited to these examples. These polymerization initiators may be used alone or in combination of two or more.
　単量体成分１００質量部あたりの重合開始剤の量は、重合速度を高め、未反応の単量体成分の残存量を低減させる観点から、好ましくは０．０５質量部以上、より好ましくは０．１質量部以上であり、耐水性を向上させる観点から、好ましくは１質量部以下、より好ましくは０．５質量部以下である（すなわち０．０５～１質量部が好ましく、０．１～０．５質量部がより好ましい）。 The amount of the polymerization initiator per 100 parts by mass of the monomer component is preferably 0.05 parts by mass or more, more preferably 0, from the viewpoint of increasing the polymerization rate and reducing the residual amount of unreacted monomer components. .1 parts by mass or more, preferably 1 part by mass or less, more preferably 0.5 parts by mass or less from the viewpoint of improving water resistance (that is, 0.05 to 1 part by mass is preferable, 0.1 to 0.5 parts by mass is more preferable).
　重合開始剤の添加方法は、特に限定されない。その添加方法としては、例えば、一括仕込み、分割仕込み、連続滴下などが挙げられる。また、重合反応の終了時期を早める観点から、単量体成分を反応系内に添加する終了前またはその終了後に、重合開始剤の一部を添加してもよい。 The method of adding the polymerization initiator is not particularly limited. Examples of the method of addition include batch charging, divided charging, and continuous dropwise addition. Moreover, from the viewpoint of advancing the completion time of the polymerization reaction, part of the polymerization initiator may be added before or after the completion of adding the monomer components to the reaction system.
　なお、重合開始剤の分解を促進するために、例えば、亜硫酸水素ナトリウムなどの還元剤、硫酸第一鉄などの遷移金属塩などの重合開始剤の分解剤を反応系内に適量で添加してもよい。
　また、エマルション粒子の重量平均分子量を調整するために、連鎖移動剤を用いることができる。連鎖移動剤としては、例えば、チオグリコール酸２－エチルヘキシル、ｔｅｒｔ－ドデシルメルカプタン、ｎ－オクチルメルカプタン、ｎ－ドデシルメルカプタン、メルカプト酢酸、メルカプトプロピオン酸、２－メルカプトエタノール、α－メチルスチレン、α－メチルスチレンダイマーなどが挙げられるが、かかる例示のみに限定されるものではない。これらの連鎖移動剤は、それぞれ単独で用いてもよく、２種類以上を併用してもよい。単量体成分１００質量部あたりの連鎖移動剤の量は、エマルション粒子の重量平均分子量を適切に調整する観点から、０．０１～１０質量部であることが好ましい。 In order to accelerate the decomposition of the polymerization initiator, for example, a reducing agent such as sodium bisulfite and a decomposing agent for the polymerization initiator such as a transition metal salt such as ferrous sulfate are added to the reaction system in an appropriate amount. good too.
A chain transfer agent can also be used to adjust the weight average molecular weight of the emulsion particles. Examples of chain transfer agents include 2-ethylhexyl thioglycolate, tert-dodecylmercaptan, n-octylmercaptan, n-dodecylmercaptan, mercaptoacetic acid, mercaptopropionic acid, 2-mercaptoethanol, α-methylstyrene, α-methyl Examples include styrene dimer and the like, but are not limited to these examples. These chain transfer agents may be used alone or in combination of two or more. The amount of the chain transfer agent per 100 parts by weight of the monomer component is preferably 0.01 to 10 parts by weight from the viewpoint of appropriately adjusting the weight average molecular weight of the emulsion particles.
　また、反応系内には、必要により、ｐＨ緩衝剤、キレート剤、造膜助剤などの添加剤を添加してもよい。添加剤の量は、その種類によって異なるので一概には決定することができない。通常、単量体成分１００質量部あたりの添加剤の量は、好ましくは０．０１～５質量部程度、より好ましくは０．１～３質量部程度である。
　単量体成分を乳化重合させる際の雰囲気は、特に限定されないが、重合開始剤の効率を高める観点から、窒素ガスなどの不活性ガスであることが好ましい。
　単量体成分を乳化重合させる際の重合温度は、特に限定がないが、通常、好ましくは５０～１００℃、より好ましくは６０～９５℃である。重合温度は、一定であってもよく、重合反応の途中で変化させてもよい。 Additives such as a pH buffer, a chelating agent, and a film-forming aid may be added to the reaction system, if necessary. The amount of the additive varies depending on its type and cannot be determined unconditionally. Generally, the amount of the additive per 100 parts by weight of the monomer component is preferably about 0.01 to 5 parts by weight, more preferably about 0.1 to 3 parts by weight.
The atmosphere in which the monomer components are emulsion-polymerized is not particularly limited, but from the viewpoint of increasing the efficiency of the polymerization initiator, an inert gas such as nitrogen gas is preferable.
The polymerization temperature for emulsion polymerization of the monomer components is not particularly limited, but is generally preferably 50 to 100°C, more preferably 60 to 95°C. The polymerization temperature may be constant or may be changed during the polymerization reaction.
　単量体成分を乳化重合させる重合時間は、特に限定がなく、重合反応の進行状況に応じて適宜設定すればよいが、通常、２～９時間程度である。
　なお、単量体成分を乳化重合させるとき、得られるポリマー成分が有する酸性基の一部または全部が中和剤で中和されるようにしてもよい。中和剤は、最終段で単量体成分を添加した後に使用してもよく、例えば、１段目の重合反応と２段目の重合反応との間に使用してもよく、初期の乳化重合反応の終了時に使用してもよい。
　中和剤としては、例えば、水酸化ナトリウムなどのアルカリ金属やアルカリ土類金属の水酸化物；炭酸水素ナトリウム、炭酸カルシウムなどのアルカリ金属またはアルカリ土類金属の炭酸化物；アンモニア、モノメチルアミン、ジメチルアミノエタノールなどの有機アミンなどのアルカリ性物質が挙げられるが、かかる例示のみに限定されるものではない。これらの中和剤のなかでは、耐水性を向上させる観点から、アンモニアなどの揮発性を有するアルカリ性物質が好ましく、エマルション粒子の貯蔵安定性を向上させる観点から、炭酸水素ナトリウムが好ましい。中和剤は、例えば、水溶液として用いることができる。 The polymerization time for emulsion polymerization of the monomer components is not particularly limited, and may be appropriately set according to the progress of the polymerization reaction, but is usually about 2 to 9 hours.
In addition, when the monomer component is emulsion-polymerized, part or all of the acidic groups possessed by the obtained polymer component may be neutralized with a neutralizing agent. The neutralizing agent may be used after adding the monomer component in the final stage, for example, may be used between the first-stage polymerization reaction and the second-stage polymerization reaction, and may be used during the initial emulsification. It may be used at the end of the polymerization reaction.
Neutralizing agents include, for example, hydroxides of alkali metals and alkaline earth metals such as sodium hydroxide; carbonates of alkali metals and alkaline earth metals such as sodium hydrogen carbonate and calcium carbonate; ammonia, monomethylamine, dimethyl Examples include, but are not limited to, alkaline substances such as organic amines such as aminoethanol. Among these neutralizing agents, a volatile alkaline substance such as ammonia is preferable from the viewpoint of improving water resistance, and sodium hydrogen carbonate is preferable from the viewpoint of improving the storage stability of emulsion particles. Neutralizing agents can be used, for example, as aqueous solutions.
　また、単量体成分を乳化重合させるとき、耐水性を向上させる観点から、シランカップリング剤を適量で用いてもよい。シランカップリング剤としては、例えば、（メタ）アクリロイル基、ビニル基、アリル基、プロペニル基などの重合性不飽和結合を有するシランカップリング剤などが挙げられるが、かかる例示のみに限定されるものではない。以上のようにして単量体成分を乳化重合させることにより、エマルション粒子を含むエマルションが得られる。
　上記で得られたエマルション粒子上に外層を形成させる場合には、上記エマルション粒子を製造する際の重合反応率が９０％以上、好ましくは９５％以上に到達した後に外層を構成する単量体成分を乳化重合させることが、エマルション粒子内で層分離構造を形成させる観点から好ましい。 Moreover, when emulsion-polymerizing a monomer component, you may use an appropriate amount of silane coupling agents from a viewpoint of improving water resistance. Silane coupling agents include, for example, (meth)acryloyl groups, vinyl groups, allyl groups, silane coupling agents having polymerizable unsaturated bonds such as propenyl groups, etc., but are limited only to such examples. is not. An emulsion containing emulsion particles is obtained by subjecting the monomer component to emulsion polymerization as described above.
When the outer layer is formed on the emulsion particles obtained above, the monomer component constituting the outer layer after the polymerization reaction rate in producing the emulsion particles reaches 90% or more, preferably 95% or more. is preferably emulsion-polymerized from the viewpoint of forming a layer-separated structure in the emulsion particles.
　なお、エマルション粒子の内層を形成させた後、外層を形成させる前に、本発明の目的が阻害されない範囲内で、必要により、他のポリマー成分からなる層が形成されていてもよい。したがって、本開示の水性インク用エマルションに含まれるエマルション粒子を製造する際には、エマルション粒子の内層を形成させた後、外層を形成させる前に、本発明の目的が阻害されない範囲内で、必要により、他のポリマー成分からなる層を形成させてもよい。 After forming the inner layer of the emulsion particles and before forming the outer layer, a layer made of other polymer components may be formed, if necessary, as long as the object of the present invention is not hindered. Therefore, when producing the emulsion particles contained in the emulsion for water-based ink of the present disclosure, after forming the inner layer of the emulsion particles and before forming the outer layer, the required may form a layer composed of other polymer components.
　外層を構成するために用いられる単量体成分は、上記エマルション粒子の内層の原料として用いられる単量体成分と同様とすることができる。また、外層を形成させる際の乳化重合の方法および重合条件は、上記エマルション粒子の内層を製造する際の方法および重合条件と同様とすることができる。
　以上のようにして内層および外層を有するエマルション粒子を得ることができる。なお、外層の表面上には、本発明の目的が阻害されない範囲内で、必要により、他のポリマー成分からなる表面層がさらに形成されていてもよい。
　以上のようにしてエマルション粒子の内層を調製した後、当該内層上に外層を形成させることにより、内層および外層を有するエマルション粒子が得られる。
　上記エマルションには、さらに架橋剤を含有させることにより、架橋性を付与することができる。架橋剤としては、常温で架橋反応を開始するものであってもよく、熱により架橋反応を開始するものであってもよい。本開示の水性インク用エマルションでは、上記エマルション粒子に架橋剤を含有させることにより、耐ブロッキング性および密着性をより向上させることができる。
　好適な架橋剤としては、例えば、オキサゾリン基含有化合物、イソシアネート基含有化合物、アミノプラスト樹脂などが挙げられる。これらの架橋剤は、それぞれ単独で用いてもよく、２種類以上を併用してもよい。これらの架橋剤のなかでは、本開示の水性インク用エマルションの保存安定性を向上させる観点から、オキサゾリン基含有化合物が好ましい。 The monomer component used for forming the outer layer may be the same as the monomer component used as the starting material for the inner layer of the emulsion particles. The emulsion polymerization method and polymerization conditions for forming the outer layer can be the same as the method and polymerization conditions for producing the inner layer of the emulsion particles.
Emulsion particles having an inner layer and an outer layer can be obtained as described above. If necessary, a surface layer made of other polymer components may be further formed on the surface of the outer layer as long as the object of the present invention is not hindered.
After the inner layer of the emulsion particle is prepared as described above, an outer layer is formed on the inner layer to obtain an emulsion particle having an inner layer and an outer layer.
Crosslinkability can be imparted to the above emulsion by further containing a crosslinking agent. The cross-linking agent may be one that initiates the cross-linking reaction at room temperature, or one that initiates the cross-linking reaction by heat. In the aqueous ink emulsion of the present disclosure, blocking resistance and adhesion can be further improved by incorporating a cross-linking agent into the emulsion particles.
Suitable cross-linking agents include, for example, oxazoline group-containing compounds, isocyanate group-containing compounds, aminoplast resins, and the like. These cross-linking agents may be used alone or in combination of two or more. Among these cross-linking agents, oxazoline group-containing compounds are preferable from the viewpoint of improving the storage stability of the aqueous ink emulsion of the present disclosure.
　＜アクリル系樹脂粒子を含有する水性分散体＞
　本開示の水性分散体１００質量部におけるアクリル系ポリマーの含有量は、低粘度化、吐出安定性の観点から２０質量部以上であってよく、２５質量部以上が好ましく、３０質量部以上がより好ましく、３５質量部以上がさらに好ましく、７０質量部以下であってよく、６５質量部以下が好ましく、６０質量部以下がより好ましく、５５質量部以下がさらに好ましい（すなわち２０～７０質量部が好ましく、２５～６５質量部がより好ましく、３０～６０質量部がさらに好ましく、３５～５５質量部が特に好ましい）。
　本開示の水性分散体の不揮発分１００質量部におけるアクリル系ポリマーの含有量は、低粘度化、吐出安定性の観点から８０質量部以上であってよく、８２質量部以上が好ましく、８５質量部以上がより好ましく、１００質量部以下であってよく、９８質量部以下が好ましく、９５質量部以下がより好ましい（すなわち８０～１００質量部が好ましく、８２～９８質量部がより好ましく、８５～９５質量部がさらに好ましい）。
　本開示の水性分散体の不揮発分は、水性分散体全質量から、樹脂及び各種添加剤に含まれる揮発成分質量を除く質量として算出してもよいし、水性分散体１ｇを秤量し、熱風乾燥機で１１０℃の温度で１時間乾燥させ、得られた残渣を不揮発分とし、式：
〔水系樹脂分散体における不揮発分量（質量％）〕
＝（〔残渣の質量〕÷〔水系樹脂分散体１ｇ〕）×１００
に基づいて求めてもよい。 <Aqueous Dispersion Containing Acrylic Resin Particles>
The content of the acrylic polymer in 100 parts by mass of the aqueous dispersion of the present disclosure may be 20 parts by mass or more, preferably 25 parts by mass or more, and more preferably 30 parts by mass or more from the viewpoint of low viscosity and ejection stability. It is preferably 35 parts by mass or more, more preferably 70 parts by mass or less, preferably 65 parts by mass or less, more preferably 60 parts by mass or less, and further preferably 55 parts by mass or less (that is, preferably 20 to 70 parts by mass , more preferably 25 to 65 parts by mass, still more preferably 30 to 60 parts by mass, and particularly preferably 35 to 55 parts by mass).
The content of the acrylic polymer in 100 parts by mass of the non-volatile content of the aqueous dispersion of the present disclosure may be 80 parts by mass or more, preferably 82 parts by mass or more, and 85 parts by mass from the viewpoint of low viscosity and ejection stability. More preferably, it may be 100 parts by mass or less, preferably 98 parts by mass or less, more preferably 95 parts by mass or less (that is, preferably 80 to 100 parts by mass, more preferably 82 to 98 parts by mass, 85 to 95 parts by mass Parts by weight are more preferred).
The non-volatile content of the aqueous dispersion of the present disclosure may be calculated as a mass excluding the mass of volatile components contained in the resin and various additives from the total mass of the aqueous dispersion, and 1 g of the aqueous dispersion is weighed and dried with hot air. Machine dried at a temperature of 110 ° C. for 1 hour, the resulting residue is the non-volatile matter, the formula:
[Non-volatile content (mass%) in aqueous resin dispersion]
= ([mass of residue] ÷ [water-based resin dispersion 1 g]) × 100
can be determined based on
　また、本開示の水性分散体には、本発明の目的が阻害されない範囲内で、例えば、界面活性剤、成膜助剤、紫外線吸収剤、紫外線防止剤、充填剤、レベリング剤、分散剤、増粘剤、湿潤剤、可塑剤、安定剤、酸化防止剤、高分子ワックスなどの添加剤が適量で含まれていてもよい。
　本開示の高分子ワックスとしては、天然ワックス、合成ワックスを挙げることができる。 In addition, the aqueous dispersion of the present disclosure contains, for example, surfactants, film-forming aids, UV absorbers, UV inhibitors, fillers, leveling agents, dispersants, Additives such as thickeners, wetting agents, plasticizers, stabilizers, antioxidants, polymeric waxes and the like may be included in appropriate amounts.
Polymeric waxes of the present disclosure may include natural waxes and synthetic waxes.
　天然ワックスとしては、石油系ワックス、植物系ワックス、動植物系ワックスなどを挙げることができる。石油系ワックスとしては、パラフィン系ワックス、マイクロクリスタリンワックス、ペトロラタムなどを挙げることができる。植物系ワックスとしては、カルナバワックス、キャンデリラワックス、ライスワックス、木ロウなどを挙げることができる。動植物系ワックスとしては、ラノリン、みつろうなどを挙げることができる。 Examples of natural waxes include petroleum-based waxes, plant-based waxes, and animal and plant-based waxes. Examples of petroleum wax include paraffin wax, microcrystalline wax, petrolatum, and the like. Plant-based waxes include carnauba wax, candelilla wax, rice wax, Japan wax, and the like. Examples of animal and plant waxes include lanolin and beeswax.
　合成ワックスとしては、合成炭化水素系ワックス、変性ワックスなどを挙げることができる。合成炭化水素系ワックスとしては、ポリオレフィン系ワックス、（メタ）アクリル系ワックス、フィッシャー・トロプシュワックスなどを挙げることができる。変性ワックスとしては、パラフィンワックス誘導体、モンタンワックス誘導体、マイクロクリスタリンワックス誘導体などを挙げることができる。密着性、耐スクラッチ性向上の観点から、ポリオレフィン系ワックス、（メタ）アクリル系ワックスが好ましい。 Synthetic waxes include synthetic hydrocarbon waxes and modified waxes. Synthetic hydrocarbon waxes include polyolefin waxes, (meth)acrylic waxes, Fischer-Tropsch waxes, and the like. Modified waxes include paraffin wax derivatives, montan wax derivatives, microcrystalline wax derivatives and the like. Polyolefin waxes and (meth)acrylic waxes are preferred from the viewpoint of improving adhesion and scratch resistance.
　（メタ）アクリル系ワックスとしては特に限定されるものではなく、例えば、炭素数１０以上のアルキル基を有するモノマーを用いて製造されたものであってよく炭素数１０以上のアルキル基を有する（メタ）アクリル系モノマーとして（メタ）アクリル酸ラウリル、（メタ）アクリル酸トリデシル、（メタ）アクリル酸セチル、（メタ）アクリル酸ステアリル、（メタ）アクリル酸ベヘニル、またはその誘導体から製造されたポリマー等が挙げられる。 The (meth)acrylic wax is not particularly limited. ) As acrylic monomers, polymers produced from lauryl (meth)acrylate, tridecyl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, behenyl (meth)acrylate, or derivatives thereof, etc. mentioned.
　（メタ）アクリル系ワックスとしては、市販品を用いることもできる。好ましい市販品としては、日本触媒社製のＳＴ１００、ＳＴ２００等が挙げられる。 A commercially available product can also be used as the (meth)acrylic wax. Preferred commercially available products include ST100 and ST200 manufactured by Nippon Shokubai Co., Ltd.
　ポリオレフィン系ワックスとしては、特に限定されるものではなく、例えば、エチレン、プロピレン、ブチレン等のオレフィンまたはその誘導体から製造されたワックスおよびそのコポリマー、具体的には、ポリエチレン系ワックス、ポリプロピレン系ワックス、ポリブチレン系ワックス、エチレンとメタクリル酸あるいはアクリル酸等のカルボン酸基を有するモノマーからなる共重合体ワックス、酸化ポリエチレンワックス等が挙げられる。これらの中でも、密着性、耐スクラッチ性向上の観点から、ポリエチレン系ワックス、ポリプロピレン系ワックス、エチレンとメタクリル酸あるいはアクリル酸等のカルボン酸基を有するモノマーからなる共重合体ワックス、酸化ポリエチレンワックスが好ましい。 The polyolefin wax is not particularly limited, and examples thereof include waxes produced from olefins such as ethylene, propylene and butylene or derivatives thereof, and copolymers thereof, specifically polyethylene waxes, polypropylene waxes and polybutylene. wax, a copolymer wax composed of ethylene and a monomer having a carboxylic acid group such as methacrylic acid or acrylic acid, and an oxidized polyethylene wax. Among these, polyethylene waxes, polypropylene waxes, copolymer waxes composed of ethylene and a monomer having a carboxylic acid group such as methacrylic acid or acrylic acid, and oxidized polyethylene waxes are preferred from the viewpoint of improving adhesion and scratch resistance. .
　本開示の酸化ポリエチレンワックスは、ポリエチレンワックスを酸化処理したものであり、ポリエチレン由来の骨格（ポリエチレン骨格）を有している。ポリエチレン骨格は、主として、エチレンに由来する構造単位を有している。ポリエチレン骨格は、ホモポリエチレン（エチレンの単独重合体）骨格であってよく、ブロックポリエチレン（エチレンと他のオレフィンとのブロック共重合体）骨格であってもよく、ランダムポリエチレン（エチレンと他のオレフィンとのランダム共重合体）骨格であってもよい。他のオレフィンとしては、例えばプロピレン、イソブチレン、１－ブテン、１－ペンテン、１－ヘキセン等のアルケンが挙げられる。これらの成分は、直鎖状であっても分岐状であってもよい。他のオレフィン成分の炭素数は、例えば、２～６である。 The oxidized polyethylene wax of the present disclosure is obtained by oxidizing polyethylene wax, and has a skeleton derived from polyethylene (polyethylene skeleton). The polyethylene skeleton mainly has structural units derived from ethylene. The polyethylene skeleton may be a homopolyethylene (ethylene homopolymer) skeleton, a block polyethylene (a block copolymer of ethylene and another olefin) skeleton, or a random polyethylene (ethylene and another olefin random copolymer) skeleton. Other olefins include alkenes such as propylene, isobutylene, 1-butene, 1-pentene and 1-hexene. These components may be linear or branched. Other olefin components have, for example, 2 to 6 carbon atoms.
　ポリエチレン骨格におけるエチレン成分の含有量（エチレンに由来する構造単位の含有量）は、例えば６０モル％以上であり、７０モル％以上であってもよい。ポリエチレン骨格がブロックポリエチレン骨格又はランダムポリエチレン骨格である場合、ポリエチレン骨格におけるエチレン成分の含有量（エチレンに由来する構造単位の含有量）は、例えば９５モル％以下であり、９０モル％以下であってもよい（すなわち前記含有量は、６０～９５モル％が好ましく、７０～９０モル％がより好ましい）。 The content of the ethylene component in the polyethylene skeleton (content of structural units derived from ethylene) is, for example, 60 mol% or more, and may be 70 mol% or more. When the polyethylene skeleton is a block polyethylene skeleton or a random polyethylene skeleton, the content of the ethylene component in the polyethylene skeleton (the content of structural units derived from ethylene) is, for example, 95 mol% or less, and 90 mol% or less. (that is, the content is preferably 60 to 95 mol %, more preferably 70 to 90 mol %).
　酸化ポリエチレンワックスは、より優れた密着性、耐スクラッチ性が得られる観点から、好ましくは高密度酸化ポリエチレンワックスを含む。 The oxidized polyethylene wax preferably contains high-density oxidized polyethylene wax from the viewpoint of obtaining better adhesion and scratch resistance.
　酸化ポリエチレンワックスとしては、市販品を用いることもできる。好ましい市販品としては、ＢＹＫ社製のＡＱＵＡＣＥＲ４９７、ＡＱＵＡＣＥＲ５１５、ＡＱＵＡＣＥＲ４５３１、ＡＱＵＡＣＥＲ１５４７等、が挙げられる。 A commercially available product can also be used as the oxidized polyethylene wax. Preferred commercially available products include BYK AQUACER497, AQUACER515, AQUACER4531, AQUACER1547, and the like.
　高分子ワックスは、１種単独または２種以上組み合わせて用いることができる。 The polymer wax can be used singly or in combination of two or more.
　本開示の高分子ワックスは固体ワックス粒子を溶媒中に溶解又は分散した状態のものを用いることが好ましく、溶媒中に分散したエマルションの状態のものを用いることがより好ましい。上記溶媒は、水性媒体であることが好ましく、水性インク組成物の溶媒に用いられる水性媒体と同じ水性媒体であることがより好ましい。 The polymer wax of the present disclosure is preferably in a state in which solid wax particles are dissolved or dispersed in a solvent, and more preferably in an emulsion state in which solid wax particles are dispersed in a solvent. The solvent is preferably an aqueous medium, more preferably the same aqueous medium as the aqueous medium used for the solvent of the aqueous ink composition.
　本開示の高分子ワックスの含有量（固形分基準）は、密着性、耐スクラッチ性、耐ブロッキング性、耐粘着テープ剥離性向上の観点から、アクリル系樹脂１００質量部に対して、０．１～１００質量部であることが好ましく、１～５０質量部であることがより好ましく、３～２０質量部であることがよりさらに好ましい。 The content (based on solid content) of the polymer wax of the present disclosure is 0.1 per 100 parts by mass of the acrylic resin from the viewpoint of improving adhesion, scratch resistance, blocking resistance, and adhesive tape peeling resistance. It is preferably from 1 to 100 parts by mass, more preferably from 1 to 50 parts by mass, and even more preferably from 3 to 20 parts by mass.
　本開示の水性分散体に用いる各種添加剤のバイオマス度は、環境負荷の観点から１０％以上であることが好ましく、２０％以上がより好ましく、３０％以上がさらに好ましく、４０％以上が特に好ましい。 The biomass degree of various additives used in the aqueous dispersion of the present disclosure is preferably 10% or more, more preferably 20% or more, even more preferably 30% or more, and particularly preferably 40% or more, from the viewpoint of environmental load. .
　本開示の水性分散体の最低造膜温度は、耐スクラッチ性、密着性、耐粘着テープ剥離性を向上させる観点から、好ましくは１００℃以下、より好ましくは９０℃以下、よりさらに好ましくは７０℃以下である。また本開示の水性分散体の最低造膜温度の下限値は、耐水性、耐候性、耐スクラッチ性、密着性、耐粘着テープ剥離性および耐ブロッキング性をより向上させる観点から、好ましくは０℃以上、より好ましくは１０℃以上、さらに好ましくは３０℃以上である（すなわち最低造膜温度は、０～１００℃が好ましく、１０～９０℃がより好ましく、３０～７０℃がさらに好ましい）。 The minimum film-forming temperature of the aqueous dispersion of the present disclosure is preferably 100° C. or lower, more preferably 90° C. or lower, and even more preferably 70° C., from the viewpoint of improving scratch resistance, adhesion, and adhesive tape peeling resistance. It is below. In addition, the lower limit of the lowest film-forming temperature of the aqueous dispersion of the present disclosure is preferably 0° C. from the viewpoint of further improving water resistance, weather resistance, scratch resistance, adhesion, adhesive tape peeling resistance and blocking resistance. Above, more preferably 10° C. or higher, still more preferably 30° C. or higher (that is, the minimum film-forming temperature is preferably 0 to 100° C., more preferably 10 to 90° C., and still more preferably 30 to 70° C.).
　なお、本明細書において、水性分散体の最低造膜温度は、水性分散体を乾燥させたとき、き裂のない均一皮膜が形成される最低温度のことを意味し、ＪＩＳＫ６８２８－２：２００３に準拠して測定される。 In the present specification, the minimum film-forming temperature of the aqueous dispersion means the minimum temperature at which a crack-free uniform film is formed when the aqueous dispersion is dried, and is defined in JIS K6828-2: 2003. Measured in compliance.
　水性分散体中のアクリル系樹脂はエマルション粒子として存在していることが好ましい。アクリル系樹脂粒子の平均粒子径は、粒子自体の機械的安定性を向上させる観点から、好ましくは５０ｎｍ以上、より好ましくは１００ｎｍ以上である。平均粒子径の上限は、耐スクラッチ性、密着性などを向上させ、また耐水性、耐候性などをより良好にする観点から、好ましくは３００ｎｍ以下、より好ましくは２００ｎｍ以下である（すなわち平均粒子径は、５０～３００ｎｍが好ましく、１００～２００ｎｍがより好ましい）。 The acrylic resin in the aqueous dispersion preferably exists as emulsion particles. From the viewpoint of improving the mechanical stability of the particles themselves, the average particle size of the acrylic resin particles is preferably 50 nm or more, more preferably 100 nm or more. The upper limit of the average particle size is preferably 300 nm or less, more preferably 200 nm or less, from the viewpoint of improving scratch resistance, adhesion, etc., and improving water resistance, weather resistance, etc. (i.e., average particle size is preferably 50 to 300 nm, more preferably 100 to 200 nm).
　なお、本明細書において、水性分散体中のアクリル系樹脂粒子の平均粒子径は、動的光散乱法による粒子径測定装置である多検体ナノ粒子径測定システム〔大塚電子（株）製、商品名：ｎａｎｏＳＡＱＬＡ〕を用い、光子相関法で自己相関関数を求め、キュムラント解析することによって求まる値（流体力学的径）である。 In this specification, the average particle size of the acrylic resin particles in the aqueous dispersion is a multi-sample nanoparticle size measurement system [manufactured by Otsuka Electronics Co., Ltd., product name: nanoSAQLA], the autocorrelation function is obtained by the photon correlation method, and the value (hydrodynamic diameter) is obtained by cumulant analysis.
　＜用途＞
　本開示のアクリル系樹脂又はアクリル系樹脂を含む水性分散体はインクに好適に用いることができ、特に水系溶媒を含む水性インクとして用いることが好ましい。
　本開示の水性インク１００質量部におけるアクリル系樹脂の含有量は白色インクに用いる場合は、吐出安定性、貯蔵安定性、分散安定性の観点から１質量部以上であってよく、３質量部以上が好ましく、５質量部以上がより好ましく、５０質量部以下であってよく、４０質量部以下が好ましく、３０質量部以下がより好ましく、２０質量部以下がさらに好ましい（すなわち、１～５０質量部が好ましく、３～４０質量部がより好ましく、５～３０がさらに好ましく、５～２０質量部が特に好ましい）。一方、白色インクを除くカラーインクに用いる場合は、吐出安定性、貯蔵安定性の観点から１質量部以上であってよく、３質量部以上が好ましく、５質量部以上がより好ましく、４０質量部以下であってよく、３０質量部以下が好ましく、２５質量部以下がより好ましく、２０質量部以下がさらに好ましい（すなわち１～４０質量部が好ましく、１～３０質量部がより好ましく、３～２５質量部がさらに好ましく、５～２０質量部が特に好ましい）。
　本開示の水性インクは着色剤を含有する。着色剤の色相としては、例えば、ホワイト、ブラック、グレーなどの無彩色およびイエロー、マゼンタ、シアン、ブルー、レッド、オレンジ、グリーンなどの有彩色が挙げられるが、本開示の水性インクは、かかる例示のみに限定されるものではない。 <Application>
The acrylic resin or the aqueous dispersion containing the acrylic resin of the present disclosure can be suitably used for ink, and is particularly preferably used as an aqueous ink containing an aqueous solvent.
The content of the acrylic resin in 100 parts by mass of the water-based ink of the present disclosure may be 1 part by mass or more from the viewpoint of ejection stability, storage stability, and dispersion stability when used for white ink, and may be 3 parts by mass or more. is preferable, 5 parts by mass or more is more preferable, it may be 50 parts by mass or less, preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and even more preferably 20 parts by mass or less (i.e., 1 to 50 parts by mass is preferred, 3 to 40 parts by weight is more preferred, 5 to 30 parts by weight is even more preferred, and 5 to 20 parts by weight is particularly preferred). On the other hand, when used for color inks other than white ink, from the viewpoint of ejection stability and storage stability, the amount may be 1 part by mass or more, preferably 3 parts by mass or more, more preferably 5 parts by mass or more, and 40 parts by mass. or less, preferably 30 parts by mass or less, more preferably 25 parts by mass or less, more preferably 20 parts by mass or less (that is, preferably 1 to 40 parts by mass, more preferably 1 to 30 parts by mass, 3 to 25 parts by mass Parts by weight are more preferred, and 5 to 20 parts by weight are particularly preferred).
Aqueous inks of the present disclosure contain a colorant. Colorant hues include, for example, achromatic colors such as white, black, and gray, and chromatic colors such as yellow, magenta, cyan, blue, red, orange, and green. is not limited to only
　本開示の着色剤としては、顔料および染料が挙げられる。これらのなかでは、耐候性に優れていることから、顔料が好ましい。顔料を用いる場合、当該顔料は、例えば、ペーストなどの顔料分散液の形態で用いてもよい。顔料としては、有機顔料および無機顔料が挙げられ、これらは、それぞれ単独で用いてもよく、併用してもよい。
　本開示の水性インクに用いる着色剤は、白色顔料、イエロー、マゼンタ、シアン、ブラック、レッド、ブルー及びグリーンから選ばれるいずれか一種の着色剤であることが好ましい。 Colorants of the present disclosure include pigments and dyes. Among these, pigments are preferred because of their excellent weather resistance. When a pigment is used, the pigment may be used in the form of a pigment dispersion such as a paste. Examples of pigments include organic pigments and inorganic pigments, and these may be used alone or in combination.
The colorant used in the water-based ink of the present disclosure is preferably any one colorant selected from white pigments, yellow, magenta, cyan, black, red, blue and green.
　白色顔料としては、特に限定はなく公知の無機白色顔料を使用できる。例えば、アルカリ土類金属の硫酸塩、または炭酸塩；微粉ケイ酸、合成珪酸塩等のシリカ類；ケイ酸カルシウム、アルミナ、アルミナ水和物、酸化チタン、酸化亜鉛、タルク、クレイ等があげられる。また、前記無機白色顔料が各種表面処理方法で表面処理されていてもよい。中でも、表面処理された酸化チタンが、水性媒体中において比較的良好な分散性を示すことから好ましい。例えば光触媒性による影響を避けるために、無機物で表面処理された酸化チタンが好ましく、シリカとアルミナで表面処理された酸化チタンが好ましい。更に、該シリカとアルミナで表面処理後、更にシランカップリング剤によって表面処理した酸化チタンを使用することもできなお好ましい。シリカとアルミナで表面処理された酸化チタンにおいて、酸化チタンとしては、公知のルチル型・アナターゼ型の二酸化チタンが使用でき、より好ましくはルチル型二酸化チタンである。 The white pigment is not particularly limited, and any known inorganic white pigment can be used. Examples thereof include alkaline earth metal sulfates or carbonates; silicas such as fine powder silicic acid and synthetic silicate; calcium silicate, alumina, alumina hydrate, titanium oxide, zinc oxide, talc, clay and the like. . Moreover, the inorganic white pigment may be surface-treated by various surface treatment methods. Among them, surface-treated titanium oxide is preferable because it exhibits relatively good dispersibility in an aqueous medium. For example, in order to avoid photocatalytic effects, titanium oxide surface-treated with an inorganic substance is preferred, and titanium oxide surface-treated with silica and alumina is preferred. Furthermore, it is also possible to use titanium oxide which has been surface-treated with the silica and alumina and then further surface-treated with a silane coupling agent. In titanium oxide surface-treated with silica and alumina, known rutile-type or anatase-type titanium dioxide can be used as titanium oxide, and rutile-type titanium dioxide is more preferable.
　また前記酸化チタンの平均粒径としては、１００～５００ｎｍのものを使用することが好ましく、１５０～４００ｎｍのものを使用することがより好ましい。平均粒径が１００ｎｍ以下であると水性媒体中の非沈降性や分散安定性はより実現し易くなるものの、白色度や隠蔽性が劣ってしまい本来の白色インキとしての実用性が低下するおそれがあり、一方平均粒径が５００ｎｍ以上になると白色度や隠蔽性の点では問題ないが、吐出安定性が不十分となる傾向にある。粒径について実用的には２００～３００ｎｍが更により好ましい。なお原料としての酸化チタンの平均粒径は電子顕微鏡写真により２０個の粒径測定を行って平均をとったものとする。
　なお、本発明において、水性分散体、水性分散体を用いた水性インクに含まれる酸化チタンの平均粒子径は特に限定されないが動的光散乱法、レーザー回折／散乱法、コールターカウンター、顕微鏡法等によって測定する事が出来る。
　より具体的には、前記平均粒子径は、動的光散乱法による粒子径測定装置である多検体ナノ粒子径測定システム〔大塚電子（株）製、商品名：ｎａｎｏＳＡＱＬＡ〕を用い、光子相関法で自己相関関数を求め、キュムラント解析によって求めた平均粒子径（流体力学的径）であることが好ましい。 The average particle size of the titanium oxide is preferably 100-500 nm, more preferably 150-400 nm. When the average particle size is 100 nm or less, non-settling property and dispersion stability in an aqueous medium are more likely to be achieved, but the whiteness and opacity are inferior, and there is a possibility that the practicality as an original white ink is reduced. On the other hand, if the average particle diameter is 500 nm or more, there is no problem in terms of whiteness and hiding power, but ejection stability tends to be insufficient. Practically, the particle size is more preferably 200 to 300 nm. The average particle diameter of titanium oxide used as a raw material is obtained by measuring the particle diameters of 20 particles using an electron micrograph and taking the average.
In the present invention, the average particle size of the titanium oxide contained in the aqueous dispersion or the aqueous ink using the aqueous dispersion is not particularly limited, but the dynamic light scattering method, laser diffraction/scattering method, coulter counter, microscopic method, etc. can be measured by
More specifically, the average particle size is measured by a photon correlation method using a multi-sample nanoparticle size measuring system [manufactured by Otsuka Electronics Co., Ltd., trade name: nanoSAQLA], which is a particle size measuring device using a dynamic light scattering method. It is preferable that the average particle diameter (hydrodynamic diameter) is obtained by obtaining the autocorrelation function in and by cumulant analysis.
　イエロー用の有機顔料としては、Ｃ．Ｉ．ピグメントイエロー１(ハンザイエローＧ)，２，３(ハンザイエロー１０Ｇ)，４，５（ハンザイエロー５Ｇ），６，７，１０，１１，１２（ジスアゾイエローＡＡＡ），１３，１４，１６，１７，２４(フラバントロンイエロー)，５５（ジスアゾイエローＡＡＰＴ），６１，６１：１，６５，７３，７４（ファストイエロー５ＧＸ），７５，８１，８３（ジスアゾイエローＨＲ），９３（縮合アゾイエロー３Ｇ），９４（縮合アゾイエロー６Ｇ），９５（縮合アゾイエローＧＲ），９７（ファストイエローＦＧＬ），９８，９９（アントラキノン），１００，１０８(アントラピリミジンイエロー)，１０９（イソインドリノンイエロー２ＧＬＴ），１１０（イソインドリノンイエロー３ＲＬＴ），１１３，１１７，１２０（ベンズイミダゾロンイエローＨ２Ｇ），１２３（アントラキノンイエロー），１２４，１２８（縮合アゾイエロー８Ｇ），１２９，１３３，１３８(キノフタロンイエロー)，１３９(イソインドリノンイエロー)，１４７，１５１（ベンズイミダゾロンイエローＨ４Ｇ），１５３(ニッケルニトロソイエロー)，１５４（ベンズイミダゾロンイエローＨ３Ｇ），１５５，１５６（ベンズイミダゾロンイエローＨＬＲ），１６７，１６８，１７２，１７３（イソインドリノンイエロー６ＧＬ）,１８０（ベンズイミダゾロンイエロー）等を挙げることができる。
　マゼンタ水性インク用の有機顔料としては、Ｃ．Ｉ．ピグメントレッド１（パラレッド），２，３（トルイジンレッド），４，５（ｌＴＲ　Ｒｅｄ），６，７，８，９，１０，１１，１２，１４，１５，１６，１７，１８，１９，２１，２２，２３，３０，３１，３２，３７，３８（ピラゾロンレッドＢ），４０，４１，４２，８８（チオインジゴボルドー），１１２（ナフトールレッドＦＧＲ），１１４（ブリリアントカーミンＢＳ），１２２（ジメチルキナクリドン），１２３（ペリレンバーミリオン），１４４，１４６，１４９（ペリレンスカーレッド），１５０，１６６，１６８（アントアントロンオレンジ），１７０（ナフトールレッドＦ３ＲＫ），１７１（ベンズイミダゾロンマルーンＨＦＭ），１７５（ベンズイミダゾロンレッドＨＦＴ），１７６（ベンズイミダゾロンカーミンＨＦ３Ｃ），１７７，１７８（ペリレンレッド），１７９（ペリレンマルーン），１８５（ベンズイミダゾロンカーミンＨＦ４Ｃ），１８７，１８８，１８９（ペリレンレッド），１９０（ペリレンレッド），１９４（ペリノンレッド），２０２（キナクリドンマゼンタ），２０９（ジクロロキナクリドンレッド），２１４（縮合アゾレッド），２１６，２１９，２２０（縮合アゾ），２２４（ペリレンレッド），２４２（縮合アゾスカーレット），２４５（ナフトールレッド），又は、Ｃ．Ｉ．ピグメントバイオレット１９（キナクリドン），２３（ジオキサジンバイオレット），３１，３２，３３，３６，３８，４３，５０等を挙げることができる。 Organic pigments for yellow include C.I. I. Pigment Yellow 1 (Hansa Yellow G), 2, 3 (Hansa Yellow 10G), 4, 5 (Hansa Yellow 5G), 6, 7, 10, 11, 12 (Disazo Yellow AAA), 13, 14, 16, 17, 24 (flavanthrone yellow), 55 (disazo yellow AAPT), 61, 61: 1, 65, 73, 74 (fast yellow 5GX), 75, 81, 83 (disazo yellow HR), 93 (condensed azo yellow 3G), 94 (condensed azo yellow 6G), 95 (condensed azo yellow GR), 97 (fast yellow FGL), 98, 99 (anthraquinone), 100, 108 (anthrapyrimidine yellow), 109 (isoindolinone yellow 2GLT), 110 ( isoindolinone yellow 3RLT), 113, 117, 120 (benzimidazolone yellow H2G), 123 (anthraquinone yellow), 124, 128 (condensed azo yellow 8G), 129, 133, 138 (quinophthalone yellow), 139 (isoind Linon Yellow), 147, 151 (Benzimidazolone Yellow H4G), 153 (Nickel Nitroso Yellow), 154 (Benzimidazolone Yellow H3G), 155, 156 (Benzimidazolone Yellow HLR), 167, 168, 172, 173 ( isoindolinone yellow 6GL), 180 (benzimidazolone yellow) and the like.
Organic pigments for magenta water-based ink include C.I. I. Pigment Red 1 (Para Red), 2, 3 (Toluidine Red), 4, 5 (lTR Red), 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21 , 22, 23, 30, 31, 32, 37, 38 (pyrazolone red B), 40, 41, 42, 88 (thioindigo Bordeaux), 112 (naphthol red FGR), 114 (brilliant carmine BS), 122 (dimethyl quinacridone), 123 (perylene vermillion), 144, 146, 149 (perylene scarred), 150, 166, 168 (anthanthrone orange), 170 (naphthol red F3RK), 171 (benzimidazolone maroon HFM), 175 ( benzimidazolone red HFT), 176 (benzimidazolone carmine HF3C), 177, 178 (perylene red), 179 (perylene maroon), 185 (benzimidazolone carmine HF4C), 187, 188, 189 (perylene red), 190 (perylene red), 194 (perinone red), 202 (quinacridone magenta), 209 (dichloroquinacridone red), 214 (condensed azo red), 216, 219, 220 (condensed azo), 224 (perylene red), 242 (condensed azo scarlet) ), 245 (naphthol red), or C.I. I. Pigment Violet 19 (quinacridone), 23 (dioxazine violet), 31, 32, 33, 36, 38, 43, 50 and the like.
　シアン用の有機顔料としては、Ｃ．Ｉ．ピグメントブルー１５，１５：１，１５：２，１５：３，１５：４，１５：６（以上いずれもフタロシアニンブルー），１６（無金属フタロシアニンブルー），１７：１，１８（アルカリブルートナー），１９，２１，２２，２５，５６，６０（スレンブルー），６４（ジクロロインダントロンブルー），６５（ビオラントロン），６６（インジゴ）等を挙げることができる。
　ブラック用の有機顔料としては、アニリンブラック（Ｃ．Ｉ．ピグメントブラック１）等の黒色有機顔料を用いることができる。 Organic pigments for cyan include C.I. I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6 (all of these are phthalocyanine blue), 16 (metal-free phthalocyanine blue), 17:1, 18 (alkali blue toner), 19, 21, 22, 25, 56, 60 (thren blue), 64 (dichloroindanthrone blue), 65 (violanthrone), 66 (indigo) and the like.
As the organic pigment for black, a black organic pigment such as aniline black (C.I. Pigment Black 1) can be used.
　白色顔料、イエロー、シアン、又はマゼンタ水性インク以外のカラー水性インクに用いる有機顔料としては、Ｃ．Ｉ．ピグメントオレンジ１，２，５，７，１３，１４，１５，１６（バルカンオレンジ），２４，３１（縮合アゾオレンジ４Ｒ），３４，３６（ベンズイミダゾロンオレンジＨＬ），３８，４０（ピラントロンオレンジ），４２（イソインドリノンオレンジＲＬＴ），４３，５１，６０（ベンズイミダゾロン系不溶性モノアゾ顔料），６２（ベンズイミダゾロン系不溶性モノアゾ顔料），６３；Ｃ．Ｉ．ピグメントグリーン７（フタロシアニングリーン），１０（グリーンゴールド），３６（塩臭素化フタロシアニングリーン），３７，４７（ビオラントロングリーン）；あるいはＣ．Ｉ．ピグメントブラウン１，２，３，５，２３（縮合アゾブラウン５Ｒ），２５（ベンズイミダゾロンブラウンＨＦＲ），２６（ペリレンボルドー），３２（ベンズイミダゾロンブラウンＨＦＬ）等を挙げることができる。
　本開示の水性インクに用いられる水性インク用樹脂エマルションの不揮発分１００質量部あたりの着色剤の量は、水性インクで形成された印字または画像を十分に着色させる観点から、好ましくは３０質量部以上、より好ましくは５０質量部以上であり、均一な塗膜を形成させる観点から、好ましくは３００質量部以下、より好ましくは２００質量部以下である（すなわち３０～３００質量部が好ましく、５０～２００質量部がより好ましい）。 Organic pigments used in color water-based inks other than white pigments, yellow, cyan, or magenta water-based inks include C.I. I. Pigment Orange 1, 2, 5, 7, 13, 14, 15, 16 (Vulcan Orange), 24, 31 (Condensed Azo Orange 4R), 34, 36 (Benzimidazolone Orange HL), 38, 40 (Pyrantrone Orange ), 42 (isoindolinone orange RLT), 43, 51, 60 (benzimidazolone-based insoluble monoazo pigment), 62 (benzimidazolone-based insoluble monoazo pigment), 63; I. Pigment Green 7 (phthalocyanine green), 10 (green gold), 36 (chlorobrominated phthalocyanine green), 37, 47 (violanthrone green); or C.I. I. Pigment Brown 1, 2, 3, 5, 23 (Condensed Azo Brown 5R), 25 (Benzimidazolone Brown HFR), 26 (Perylene Bordeaux), 32 (Benzimidazolone Brown HFL) and the like.
The amount of the coloring agent per 100 parts by mass of the non-volatile content of the resin emulsion for aqueous ink used in the aqueous ink of the present disclosure is preferably 30 parts by mass or more from the viewpoint of sufficiently coloring the print or image formed with the aqueous ink. , More preferably 50 parts by mass or more, preferably 300 parts by mass or less, more preferably 200 parts by mass or less from the viewpoint of forming a uniform coating film (that is, 30 to 300 parts by mass is preferable, 50 to 200 parts by mass parts by weight are more preferred).
　白色顔料を用いる場合、水性インク用樹脂エマルションの不揮発分１００質量部あたり白色顔料の量は、水性インクで形成された印字または画像を十分に着色させ、カラーの発色を向上させる観点から、好ましくは５０質量部以上、より好ましくは６０質量部以上であり、均一な塗膜を形成させる観点および／または光沢を向上させる観点から、好ましくは５００質量部以下、より好ましくは４００質量部以下である（すなわち５０～５００質量部が好ましく、６０～４００質量部がより好ましい）。 When a white pigment is used, the amount of the white pigment per 100 parts by mass of the non-volatile matter of the resin emulsion for water-based ink is preferably from the viewpoint of sufficiently coloring the print or image formed with the water-based ink and improving the color development. 50 parts by mass or more, more preferably 60 parts by mass or more, and from the viewpoint of forming a uniform coating film and/or improving gloss, preferably 500 parts by mass or less, more preferably 400 parts by mass or less ( That is, 50 to 500 parts by mass is preferable, and 60 to 400 parts by mass is more preferable).
　水性インクにおけるインク粘度、印刷する記録媒体への濡れ広がりの制御、画質向上、吐出安定性の観点から、当該水性インクには、水をはじめ水溶性有機溶媒を含有させてもよい。 The water-based ink may contain water and other water-soluble organic solvents from the viewpoints of the ink viscosity of the water-based ink, the control of wetting and spreading on the recording medium to be printed, the improvement of the image quality, and the ejection stability.
　有機溶剤としては、例えば、プロピレングリコール、１，３－プロパンジオール、グリセリン、ジプロピレングリコール、トリプロピレングリコール、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール等のグリコール；モノエチレングリコールモノメチルエーテル、モノエチレングリコールモノエチルエーテル、モノエチレングリコールモノプロピルエーテル、モノエチレングリコールモノイソプロピルエーテル、モノエチレングリコールモノブチルエーテル、モノエチレングリコールモノイソブチルエーテル等のモノエチレングリコールのエーテル；モノプロピレングリコールモノメチルエーテル、モノプロピレングリコールモノエチルエーテル、モノプロピレングリコールモノプロピルエーテル、モノプロピレングリコールモノイソプロピルエーテル、モノプロピレングリコールモノブチルエーテル、モノプロピレングリコールモノイソブチルエーテル等のモノプロピレングリコールのエーテル；ジエチレングリコールモノメチルエーテルなどのポリエチレングリコール（ＥＯ付加モル数＝２～１０、好ましくは２～４）のモノメチルエーテル、ジエチレングリコールモノエチルエーテルなどのポリエチレングリコール（ＥＯ付加モル数＝２～１０、好ましくは２～４）のモノエチルエーテル、ジエチレングリコールモノプロピルエーテルなどのポリエチレングリコール（ＥＯ付加モル数＝２～１０、好ましくは２～４）のモノプロピルエーテル、ジエチレングリコールモノイソプロピルエーテルなどのポリエチレングリコール（ＥＯ付加モル数＝２～１０、好ましくは２～４）のモノイソプロピルエーテル、ジエチレングリコールモノブチルエーテルなどのポリエチレングリコール（ＥＯ付加モル数＝２～１０、好ましくは２～４）のモノブチルエーテル、ジエチレングリコールモノイソブチルエーテルなどのポリエチレングリコール（ＥＯ付加モル数＝２～１０、好ましくは２～４）のモノイソブチルエーテル等のポリエチレングリコールのエーテル；ポリプロピレングリコール（ＥＯ付加モル数＝２～１０、好ましくは２～４）のモノメチルエーテル、ポリプロピレングリコール（ＥＯ付加モル数＝２～１０、好ましくは２～４）のモノエチルエーテル、ポリプロピレングリコール（ＥＯ付加モル数＝２～１０、好ましくは２～４）のモノプロピルエーテル、ポリプロピレングリコール（ＥＯ付加モル数＝２～１０、好ましくは２～４）のモノイソプロピルエーテル、ポリプロピレングリコール（ＥＯ付加モル数＝２～１０、好ましくは２～４）のモノブチルエーテル、ポリプロピレングリコール（ＥＯ付加モル数＝２～１０、好ましくは２～４）のモノイソブチルエーテル等のポリプロピレングリコールのエーテル；等が挙げられる。これらの中でも、プロピレングリコール、ジエチレングリコール、トリエチレングリコール、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノイソプロピルエーテル、ジエチレングリコールモノブチルエーテル、ジエチレングリコールモノイソブチルエーテル、トリプロピレングリコールモノメチルエーテル、モノエチレングリコールモノイソプロピルエーテル、モノプロピレングリコールモノプロピルエーテルが好ましい。これらの有機溶剤は、それぞれ単独で用いてもよく、２種類以上を併用してもよい。 Examples of organic solvents include glycols such as propylene glycol, 1,3-propanediol, glycerin, dipropylene glycol, tripropylene glycol, diethylene glycol, triethylene glycol and tetraethylene glycol; monoethylene glycol monomethyl ether, monoethylene glycol mono Ethers of monoethylene glycol such as ethyl ether, monoethylene glycol monopropyl ether, monoethylene glycol monoisopropyl ether, monoethylene glycol monobutyl ether, monoethylene glycol monoisobutyl ether; monopropylene glycol monomethyl ether, monopropylene glycol monoethyl ether, Ethers of monopropylene glycol such as monopropylene glycol monopropyl ether, monopropylene glycol monoisopropyl ether, monopropylene glycol monobutyl ether, monopropylene glycol monoisobutyl ether; polyethylene glycols such as diethylene glycol monomethyl ether (EO addition moles = 2 to 10 , preferably 2 to 4) monomethyl ethers, polyethylene glycols such as diethylene glycol monoethyl ether (EO addition moles = 2 to 10, preferably 2 to 4) monoethyl ethers, diethylene glycol monopropyl ethers and other polyethylene glycols (EO Polyethylene glycol (EO addition mole number = 2 to 10, preferably 2 to 4) monoisopropyl ether, diethylene glycol monopropyl ether, diethylene glycol monoisopropyl ether, etc. (addition mole number = 2 to 10, preferably 2 to 4) Monobutyl ether of polyethylene glycol such as butyl ether (number of EO addition moles = 2 to 10, preferably 2 to 4), polyethylene glycol such as diethylene glycol monoisobutyl ether (number of EO addition moles = 2 to 10, preferably 2 to 4) Ether of polyethylene glycol such as monoisobutyl ether; monomethyl ether of polypropylene glycol (number of EO addition moles = 2 to 10, preferably 2 to 4), polypropylene glycol (number of EO addition moles = 2 to 10, preferably 2 to 4) Monoethyl ether of, polypropylene glycol (EO addition mole number = 2 to 10, preferably 2 to 4) monopropyl ether, polypropylene glycol (EO addition moles = 2 to 10, preferably 2 to 4), monoisopropyl ether of polypropylene glycol (EO addition moles = 2 to 10, preferably 2 to 4), polypropylene glycol (EO addition moles = 2 to 10, preferably 2 to 4) Ethers of polypropylene glycol such as monoisobutyl ether having a molarity of 2 to 10, preferably 2 to 4); Among these, propylene glycol, diethylene glycol, triethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether, tripropylene glycol monomethyl ether, monoethylene glycol monoisopropyl ether, mono Propylene glycol monopropyl ether is preferred. These organic solvents may be used alone or in combination of two or more.
　水溶性有機溶媒の量は、水性インクに含まれる着色剤の種類およびその量などによって異なるので一概には決定することができないことから、水性インクに含まれる着色剤の種類およびその量などに応じて適宜決定することが好ましい。 Since the amount of the water-soluble organic solvent varies depending on the type and amount of the colorant contained in the water-based ink, it cannot be determined unconditionally. It is preferable to determine it as appropriate.
　例えば着色剤に白色顔料を含む場合であれば、水性インク１００質量中の有機溶剤の量は、印刷する記録媒体への濡れ広がりの制御と画質を向上させる観点から５質量部以上であってよく、８質量部以上が好ましく、１０質量部以上がより好ましく、５０質量部以下であってよく、４５質量部以下が好ましく、４０質量部以下がより好ましい（すなわち５～５０質量部が好ましく、８～４５質量部がより好ましく、１０～４０質量部がさらに好ましい）。 For example, if the colorant contains a white pigment, the amount of the organic solvent in 100 mass of the water-based ink may be 5 parts by mass or more from the viewpoint of controlling the wetting and spreading on the recording medium to be printed and improving the image quality. , preferably 8 parts by mass or more, more preferably 10 parts by mass or more, may be 50 parts by mass or less, preferably 45 parts by mass or less, more preferably 40 parts by mass or less (that is, preferably 5 to 50 parts by mass, 8 ~45 parts by mass is more preferable, and 10 to 40 parts by mass is even more preferable).
　本開示の水性インクは、前記水性インク用樹脂エマルションおよび着色剤を含有するものであるが、本発明の目的が阻害されない範囲内で、前記水性インク用樹脂エマルション以外の樹脂エマルション、水溶性樹脂、水分散性樹脂などの樹脂が含まれていてもよい。また、本発明の水性インクには、本発明の目的が阻害されない範囲内で、例えば、界面活性剤、成膜助剤、紫外線吸収剤、紫外線防止剤、充填剤、レベリング剤、分散剤、増粘剤、湿潤剤、可塑剤、安定剤、酸化防止剤などの添加剤が適量で含まれていてもよい。 The water-based ink of the present disclosure contains the resin emulsion for water-based ink and a colorant. A resin such as a water-dispersible resin may also be included. The water-based ink of the present invention may contain, for example, surfactants, film-forming aids, UV absorbers, UV inhibitors, fillers, leveling agents, dispersants, and thickening agents, as long as the objects of the present invention are not hindered. Additives such as thickeners, wetting agents, plasticizers, stabilizers and antioxidants may be included in appropriate amounts.
　本開示の水性インクの固形分は、耐水性、耐候性、環境負荷の観点からバイオマス度が３％以上であり、５％以上が好ましく、１０％以上がより好ましい。またバイオマス度の上限は特に限定されないが、例えば５０％以下であり、３０％以下でもよい。すなわち固形分のバイオマス度は、３～５０％が好ましく、５～５０％がより好ましく、１０～３０％がさらに好ましい。 The solid content of the water-based ink of the present disclosure has a biomass degree of 3% or more, preferably 5% or more, more preferably 10% or more, from the viewpoint of water resistance, weather resistance, and environmental load. Although the upper limit of the biomass degree is not particularly limited, it is, for example, 50% or less, and may be 30% or less. That is, the biomass degree of the solid content is preferably 3 to 50%, more preferably 5 to 50%, even more preferably 10 to 30%.
　以上のようにして得られる本開示の水性インクは、密着性に優れると共に、耐引っ掻き傷性に優れているので、例えば、インクジェット用水性インク、フレキソ印刷用インク、オフセット印刷用インク、リソグラフ印刷用インク、グラビア印刷用インク、スクリーン印刷用インクなどのインク、なかでも特にインクジェット用水性インクとして好適に使用することができる。 The water-based ink of the present disclosure obtained as described above has excellent adhesion and excellent scratch resistance. It can be suitably used as an ink such as an ink, gravure printing ink, or screen printing ink, especially as an aqueous inkjet ink.
　本開示のインク組成物または水性インクは、印刷基材上に塗布する工程を含むことにより積層体を製造することができる。例えば、インクジェット記録装置などを用いて水性インクを印刷基材上に所定のパターンで吐出することにより、所定のパターンを有する印字または画像を形成することができる。 A laminate can be produced by including a step of applying the ink composition or water-based ink of the present disclosure onto a printing substrate. For example, printing or an image having a predetermined pattern can be formed by ejecting water-based ink onto a printing base material in a predetermined pattern using an inkjet recording apparatus or the like.
　印刷基材としては、例えば、紙をはじめ、ポリエチレン、ポリプロピレン、ポリスチレンなどの樹脂フィルムが積層された紙（コート紙など）、アルミニウム、亜鉛、銅などの金属板、セルロース、ポリエチレンテレフタレート、ポリスチレン、オレフィン系樹脂、ポリカーボネート、ポリビニルアセタール、ポリ塩化ビニル、ポリアミド、ナイロン、アクリル樹脂などの樹脂フィルム、金属被膜を有する紙、金属被膜を有する樹脂フィルムなどが挙げられる。本開示の水性インクを印字する印刷基材としては樹脂フィルムが好ましく、中でもポリエチレンテレフタレート、オレフィン系樹脂への適用が好ましい。
　オレフィン系樹脂としては、ポリエチレン、ポリプロピレンが挙げられ、特に二軸延伸ポリプロピレンフィルム（ＯＰＰ）、無延伸ポリプロピレンフィルム（ＣＰＰ）等のポリプロピレンへの適用が好ましい。 Examples of printing substrates include paper, paper laminated with resin films such as polyethylene, polypropylene, and polystyrene (coated paper, etc.), metal plates such as aluminum, zinc, and copper, cellulose, polyethylene terephthalate, polystyrene, and olefin. base resins, polycarbonate, polyvinyl acetal, polyvinyl chloride, polyamide, nylon, resin films such as acrylic resins, paper having a metal coating, resin films having a metal coating, and the like. A resin film is preferable as a printing substrate for printing the water-based ink of the present disclosure, and application to polyethylene terephthalate and olefin-based resin is particularly preferable.
Examples of olefinic resins include polyethylene and polypropylene, and application to polypropylene such as biaxially oriented polypropylene film (OPP) and non-oriented polypropylene film (CPP) is particularly preferred.
　本開示の水性インクは、樹脂フィルム上に形成されることが好ましく、その態様は樹脂フィルムの水性インクから形成された印刷層を有する積層体である。
　本開示の積層体は、樹脂フィルムと印刷層の間にプライマー層を有してもよいし、有さなくてもよいが、生産性の観点から有さないことが好ましく、樹脂フィルムに直接印刷層を形成することが好ましい。本開示の積層体は樹脂フィルム、印刷層の順に積層され、印刷層上に保護膜（ラミネート層）を有してもよいし、有さなくてもよいが、生産性の観点から有さないことが好ましく、本開示の水性インクを用いることにより、プライマー層や保護膜（ラミネート層）を有さなくても基材への密着性に優れると共に耐引っ掻き傷性も良好な積層体が得られることが期待できる。
　本開示の積層体は各種印刷物に好適に使用することができる。 The water-based ink of the present disclosure is preferably formed on a resin film, and its embodiment is a laminate having a printed layer formed from the water-based ink on the resin film.
The laminate of the present disclosure may or may not have a primer layer between the resin film and the printed layer, but it is preferable not to have it from the viewpoint of productivity, and printing is performed directly on the resin film. Layer formation is preferred. The laminate of the present disclosure is laminated in the order of a resin film and a printed layer, and may or may not have a protective film (laminate layer) on the printed layer, but does not have it from the viewpoint of productivity. By using the water-based ink of the present disclosure, it is possible to obtain a laminate that has excellent adhesion to a substrate and good scratch resistance even without a primer layer or a protective film (laminate layer). can be expected.
The laminate of the present disclosure can be suitably used for various printed matter.
　本願は、２０２１年７月２１日に出願された日本国特許出願第２０２１－１２０８３６号に基づく優先権の利益を主張するものである。２０２１年７月２１日に出願された日本国特許出願第２０２１－１２０８３６号の明細書の全内容が、本願に参考のため援用される。 This application claims the benefit of priority based on Japanese Patent Application No. 2021-120836 filed on July 21, 2021. The entire contents of the specification of Japanese Patent Application No. 2021-120836 filed on July 21, 2021 are incorporated herein by reference.
　次に本発明を実施例に基づいてさらに詳細に説明するが、本発明は、かかる実施例のみに限定されるものではない。なお、以下の実施例において、特に断りがない限り、「部」は「質量部」を意味し、「％」は「質量％」を意味する。 Next, the present invention will be described in more detail based on examples, but the present invention is not limited only to such examples. In the following examples, "parts" means "parts by mass" and "%" means "% by mass" unless otherwise specified.
　＜ポリマー成分のガラス転移温度＞
　ポリマー成分のガラス転移温度（Ｔｇ）は、当該ポリマー成分を構成する単量体成分に使用されている単量体の単独重合体のガラス転移温度を用いて、式：
　　　１／Ｔｇ＝Σ（Ｗｍ／Ｔｇｍ）／１００
〔式中、Ｗｍはポリマー成分を構成する単量体成分における単量体ｍの含有率（質量％）、Ｔｇｍは単量体ｍの単独重合体のガラス転移温度（絶対温度：Ｋ）を示す〕
で表されるフォックス（Ｆｏｘ）の式に基づいて計算から求めた。 <Glass transition temperature of polymer component>
The glass transition temperature (Tg) of the polymer component is expressed by the formula:
1/Tg=Σ(Wm/Tgm)/100
[Wherein, Wm is the content (% by mass) of the monomer m in the monomer component constituting the polymer component, and Tgm is the glass transition temperature (absolute temperature: K) of the homopolymer of the monomer m. ]
It was obtained by calculation based on the Fox equation represented by:
　＜樹脂エマルション粒子のカルボキシル基由来の酸価＞
　樹脂エマルション粒子のカルボキシル基由来の酸価は、粒子の製造に用いた単量体成分１ｇ中に存在するカルボキシル基を中和するために必要な水酸化カリウムのｍｇ数を意味する。 <Acid value derived from carboxyl group of resin emulsion particles>
The acid value derived from the carboxyl groups of the resin emulsion particles means the number of mg of potassium hydroxide required to neutralize the carboxyl groups present in 1 g of the monomer component used in the production of the particles.
　＜不揮発分測定＞
　樹脂エマルション１ｇを秤量し、熱風乾燥機で１１０℃の温度で１時間乾燥させ、得られた残渣を、下記式を用いて不揮発分として算出した。
〔樹脂エマルションにおける不揮発分量（質量％）〕
＝（〔残渣の質量〕÷〔樹脂エマルション１ｇ〕）×１００ <Measurement of non-volatile content>
1 g of the resin emulsion was weighed and dried in a hot air dryer at a temperature of 110° C. for 1 hour, and the resulting residue was calculated as a non-volatile content using the following formula.
[Non-volatile content (mass%) in resin emulsion]
= ([mass of residue] ÷ [1 g of resin emulsion]) x 100
　＜最低造膜温度＞
　樹脂エマルションの最低造膜温度は、ＪＩＳＫ６８２８－２：２００３に準拠して、測定した。 <Minimum film-forming temperature>
The minimum film-forming temperature of the resin emulsion was measured according to JISK6828-2:2003.
　＜平均粒子径＞
　測定温度２５±０．５℃、動的光散乱法による粒子径測定装置である多検体ナノ粒子径測定システム〔大塚電子（株）製、商品名：ｎａｎｏＳＡＱＬＡ〕を用い、光子相関法で自己相関関数を求め、キュムラント解析によって平均粒子径（流体力学的径）を求めた。 <Average particle size>
Measurement temperature 25 ± 0.5 ° C., using a multi-sample nanoparticle size measurement system [manufactured by Otsuka Electronics Co., Ltd., product name: nanoSAQLA], which is a particle size measurement device by the dynamic light scattering method, autocorrelation by the photon correlation method A function was determined, and the average particle size (hydrodynamic size) was determined by cumulant analysis.
　なお、各表に記載の略号は、以下のことを意味する。
ＩＢＯＡ　　　：イソボルニルアクリレート
ＥＡ　　　　　：エチルアクリレート
ＣＨＭＡ　　　：シクロヘキシルメタクリレート
Ｓｔ　　　　　：スチレン
２ＥＨＡ　　　：２－エチルヘキシルアクリレート
ＡＡ　　　　　：アクリル酸
ＨＥＭＡ　　　：ヒドロキシエチルメタクリレート
ＬＡ－８７　　：４－メタクリロイルオキシ－２，２，６，６－テトラメチルピペリジン
ＬＡ－８２　　：４－メタクリロイルオキシ－１，２，２，６，６－ペンタメチルピペリジン
ＢＹＫ－１９０：ビックケミージャパン社製、分散剤（酸価１０ｍｇＫＯＨ／ｇ）
ＰＧ　　　　　：ＡＤＥＫＡ社製、プロピレングリコール
ＣＲ－９５　　：石原産業社製、酸化チタン（ルチル型）
ＳＴ－２００　：日本触媒社製、（メタ）アクリル系ＷＡＸエマルション
ＢＤＧ　　　　：日本乳化剤社製、ジエチレングリコールモノブチルエーテル
ＫＦ－６０１１：信越化学工業社製、ＰＥＧ－１１メチルエーテルジメチコン（ポリエーテル変性シリコーン界面活性剤）
ＰＥＴ　　　　：フタムラ化学社製、商品名：太閤ポリエステルフィルムＦＥ２００１
ＯＰＰ　　　　：フタムラ化学社製、商品名：ＦＯＲ－ＡＱ The abbreviations in each table mean the following.
IBOA: isobornyl acrylate EA: ethyl acrylate CHMA: cyclohexyl methacrylate St: styrene 2EHA: 2-ethylhexyl acrylate AA: acrylic acid HEMA: hydroxyethyl methacrylate LA-87: 4-methacryloyloxy-2,2,6,6-tetra Methylpiperidine LA-82: 4-methacryloyloxy-1,2,2,6,6-pentamethylpiperidine BYK-190: manufactured by BYK Chemie Japan, dispersant (acid value 10mgKOH/g)
PG: Propylene glycol CR-95 manufactured by ADEKA Co., Ltd. Titanium oxide (rutile type) manufactured by Ishihara Sangyo Co., Ltd.
ST-200: Nippon Shokubai Co., Ltd., (meth)acrylic WAX emulsion BDG: Nippon Nyukazai Co., Ltd., diethylene glycol monobutyl ether KF-6011: Shin-Etsu Chemical Co., Ltd., PEG-11 methyl ether dimethicone (polyether-modified silicone surfactant )
PET: manufactured by Futamura Chemical Co., Ltd., trade name: Taiko polyester film FE2001
OPP: manufactured by Futamura Chemical Co., Ltd., product name: FOR-AQ
　＜樹脂エマルション＞
　　＜コアシェルエマルション＞
　［製造例１］
　滴下ロート、撹拌機、窒素ガス導入管、温度計および還流冷却管を備えたフラスコ内に、脱イオン水５２０部を仕込んだ。滴下ロートに、脱イオン水１６３部、乳化剤［（株）ＡＤＥＫＡ製、商品名：アデカリアソーブＳＲ－１０］の２５％水溶液８０部、イソボルニルアクリレート（ＩＢＯＡ）（バイオマス度７３％）３２２部、２－エチルヘキシルアクリレート（２ＥＨＡ）１０３部、２－ヒドロキシエチルメタクリレート（ＨＥＭＡ）７５部からなる１段目滴下用プレエマルションを調製し、そのうち全単量体成分の総量の５％にあたる７４部をフラスコ内に添加し、ゆるやかに窒素ガスを吹き込みながら７０℃まで昇温し、５％過硫酸アンモニウム水溶液３０部を添加し、重合を開始した。その後、滴下用プレエマルションの残部を１２０分間にわたりフラスコ内に均一に滴下した。
　滴下終了後、フラスコの内容物を７０℃で６０分間維持し、引き続いて、脱イオン水１６３部、乳化剤［（株）ＡＤＥＫＡ製、商品名：アデカリアソーブＳＲ－１０］の２５％水溶液８０部、イソボルニルアクリレート（ＩＢＯＡ）（バイオマス度７３％）３１０部、２－エチルヘキシルアクリレート（２ＥＨＡ）１０５部、２－ヒドロキシエチルメタクリレート（ＨＥＭＡ）７５部および４－（メタ）アクリロイルオキシ－１，２，２，６，６－ペンタメチルピペリジン〔（株）ＡＤＥＫＡ製、商品名：アデカスタブＬＡ－８２〕１０部からなる２段目滴下用プレエマルションと５％過硫酸アンモニウム水溶液３０部を１２０分間にわたって均一にフラスコ内に滴下した。
　滴下終了後、フラスコの内容物を７０℃で６０分間維持し、２５％アンモニア水を添加することによってｐＨを８に調整し、重合を終了した。得られた反応液を室温まで冷却した後、３００メッシュの金網で濾過することにより、樹脂エマルションを調製した。この樹脂エマルションにおける不揮発分の含有率は５０％であり、樹脂エマルション粒子のカルボキシル基由来の酸価は０ｍｇＫＯＨ／ｇ、樹脂エマルションに含まれている粒子（樹脂エマルション粒子）を構成している内層の樹脂のガラス転移温度は３８℃であり、外層樹脂のガラス転移温度は３８℃であった。最低増膜温度は５０℃であり、平均粒子径は１５０ｎｍ、不揮発分中のバイオマス度４６％であった。 <Resin emulsion>
<Core shell emulsion>
[Production Example 1]
A flask equipped with a dropping funnel, a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser was charged with 520 parts of deionized water. In a dropping funnel, 163 parts of deionized water, 80 parts of a 25% aqueous solution of emulsifier [manufactured by ADEKA Co., Ltd., trade name: Adekari Sorb SR-10], isobornyl acrylate (IBOA) (biomass degree 73%) 322 parts, 2 - Prepare a pre-emulsion for the first stage dropwise addition consisting of 103 parts of ethylhexyl acrylate (2EHA) and 75 parts of 2-hydroxyethyl methacrylate (HEMA), of which 74 parts corresponding to 5% of the total amount of all monomer components are placed in a flask. The temperature was raised to 70° C. while gently blowing nitrogen gas, and 30 parts of a 5% aqueous ammonium persulfate solution was added to initiate polymerization. Thereafter, the remainder of the pre-emulsion for dropping was uniformly dropped into the flask over 120 minutes.
After the dropwise addition was completed, the contents of the flask were maintained at 70° C. for 60 minutes, followed by 163 parts of deionized water, 80 parts of a 25% aqueous solution of an emulsifier [manufactured by ADEKA Co., Ltd., trade name: Adekari Sorb SR-10], iso Bornyl acrylate (IBOA) (73% biomass) 310 parts, 2-ethylhexyl acrylate (2EHA) 105 parts, 2-hydroxyethyl methacrylate (HEMA) 75 parts and 4-(meth)acryloyloxy-1,2,2, 6,6-Pentamethylpiperidine [manufactured by ADEKA Co., Ltd., trade name: ADEKA STAB LA-82] pre-emulsion for second stage dropping consisting of 10 parts and 30 parts of 5% ammonium persulfate aqueous solution were uniformly added to the flask over 120 minutes. Dripped.
After the dropwise addition was completed, the contents of the flask were maintained at 70° C. for 60 minutes, and the pH was adjusted to 8 by adding 25% aqueous ammonia to complete the polymerization. After cooling the resulting reaction solution to room temperature, it was filtered through a wire mesh of 300 mesh to prepare a resin emulsion. The content of non-volatile matter in this resin emulsion is 50%, the acid value derived from the carboxyl groups of the resin emulsion particles is 0 mgKOH/g, and the inner layer constituting the particles contained in the resin emulsion (resin emulsion particles) The glass transition temperature of the resin was 38°C, and the glass transition temperature of the outer layer resin was 38°C. The minimum film growth temperature was 50° C., the average particle size was 150 nm, and the biomass content in the non-volatile matter was 46%.
　［製造例５］
　製造例５において、表１に示す単量体成分を用いて重合させたことを除き、製造例１と同様にして重合体を調製し、製造例５の樹脂エマルションを得た。得られた樹脂エマルションの特性を表１に示す。 [Production Example 5]
In Production Example 5, a polymer was prepared in the same manner as in Production Example 1, except that the monomer components shown in Table 1 were used for polymerization, and a resin emulsion of Production Example 5 was obtained. Table 1 shows the properties of the obtained resin emulsion.
　　＜シングルエマルション＞
　［製造例２］
　滴下ロート、撹拌機、窒素ガス導入管、温度計および還流冷却管を備えたフラスコ内に、脱イオン水５３６部を仕込んだ。滴下ロートに、脱イオン水３２６部、乳化剤［（株）ＡＤＥＫＡ製、商品名：アデカリアソーブＳＲ－１０］の２５％水溶液１６０部、イソボルニルアクリレート（ＩＢＯＡ）（バイオマス度７３％）６３２部、２－エチルヘキシルアクリレート（２ＥＨＡ）２０８部、２－ヒドロキシエチルメタクリレート（ＨＥＭＡ）１５０部、４－（メタ）アクリロイルオキシ－２，２，６，６－テトラメチルピペリジン〔（株）ＡＤＥＫＡ製、商品名：アデカスタブＬＡ－８７〕１０部からなる１段目滴下用プレエマルションを調製し、そのうち全単量体成分の総量の５％にあたる７４部をフラスコ内に添加し、ゆるやかに窒素ガスを吹き込みながら７０℃まで昇温し、５％過硫酸アンモニウム水溶液３０部を添加し、重合を開始した。その後、滴下用プレエマルションの残部と５％過硫酸アンモニウム水溶液３０部を１８０分間にわたりフラスコ内に均一に滴下した。
　滴下終了後、フラスコの内容物を７０℃で６０分間維持し、２５％アンモニア水を添加することによってｐＨを８に調整し、重合を終了した。得られた反応液を室温まで冷却した後、３００メッシュの金網で濾過することにより、樹脂エマルションを調製した。この樹脂エマルションにおける不揮発分の含有率は５０％であり、樹脂エマルション粒子のカルボキシル基由来の酸価は０ｍｇＫＯＨ／ｇ、樹脂エマルションに含まれている粒子（樹脂エマルション粒子）を構成している樹脂のガラス転移温度は３８℃であった。最低増膜温度は４０℃であり、平均粒子径は１５０ｎｍ、不揮発分中のバイオマス度４６％であった。 <Single emulsion>
[Production Example 2]
A flask equipped with a dropping funnel, a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser was charged with 536 parts of deionized water. In a dropping funnel, 326 parts of deionized water, 160 parts of a 25% aqueous solution of emulsifier [manufactured by ADEKA Co., Ltd., trade name: Adekari Sorb SR-10], isobornyl acrylate (IBOA) (biomass degree 73%) 632 parts, 2 -Ethylhexyl acrylate (2EHA) 208 parts, 2-hydroxyethyl methacrylate (HEMA) 150 parts, 4-(meth)acryloyloxy-2,2,6,6-tetramethylpiperidine [manufactured by ADEKA Corporation, trade name: Adekastab LA-87] 10 parts of a pre-emulsion for the first stage dropping was prepared, of which 74 parts corresponding to 5% of the total amount of all monomer components was added to the flask, and the mixture was heated to 70°C while slowly blowing nitrogen gas. The temperature was raised, and 30 parts of a 5% aqueous ammonium persulfate solution was added to initiate polymerization. Thereafter, the remainder of the pre-emulsion for dropping and 30 parts of a 5% aqueous ammonium persulfate solution were uniformly dropped into the flask over 180 minutes.
After the dropwise addition was completed, the contents of the flask were maintained at 70° C. for 60 minutes, and the pH was adjusted to 8 by adding 25% aqueous ammonia to complete the polymerization. After cooling the resulting reaction solution to room temperature, it was filtered through a wire mesh of 300 mesh to prepare a resin emulsion. The content of non-volatile matter in this resin emulsion is 50%, the acid value derived from the carboxyl groups of the resin emulsion particles is 0 mgKOH/g, and the resin constituting the particles (resin emulsion particles) contained in the resin emulsion is The glass transition temperature was 38°C. The minimum film growth temperature was 40° C., the average particle size was 150 nm, and the biomass content in the non-volatile matter was 46%.
　［製造例３、４］
　製造例３、４において、表１に示す単量体成分を用いて重合させたことを除き、製造例２と同様にして重合体を調製し、製造例３、４の樹脂エマルションを得た。得られた樹脂エマルションの特性を表１に示す。 [Production Examples 3 and 4]
Polymers were prepared in the same manner as in Production Example 2, except that in Production Examples 3 and 4, the monomer components shown in Table 1 were used for polymerization, and resin emulsions of Production Examples 3 and 4 were obtained. Table 1 shows the properties of the obtained resin emulsion.
　［製造例６－９］
　製造例６－９において、表２に示す単量体成分を用いて重合させたことを除き、製造例２と同様にして重合体を調製し、製造例６－９の樹脂エマルションを得た。得られた樹脂エマルションの特性を表２に示す。 [Production Example 6-9]
A polymer was prepared in the same manner as in Production Example 2, except that in Production Example 6-9, the monomer components shown in Table 2 were used for polymerization to obtain a resin emulsion of Production Example 6-9. Table 2 shows the properties of the obtained resin emulsion.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表１および表２に示された各種バイオマスモノマーのバイオマス度は以下の通りである。
ＩＢＯＡ：イソボルニルアクリレート　バイオマス度７３％
ＥＡ　　：エチルアクリレート　バイオマス度４６％ The biomass degrees of various biomass monomers shown in Tables 1 and 2 are as follows.
IBOA: isobornyl acrylate biomass content 73%
EA: Ethyl acrylate Biomass content 46%
　［製造例１０］
　特開２０１９－１７２９７７号公報の実施例１と同様の方法にて、樹脂溶液を調製した。すなわち、多官能カルボン酸成分として植物由来成分からなるダイマー酸（ダイマー純度９８％）／植物由来成分からなるコハク酸＝９０／１０（モル比）を用い、多官能アルコール成分として、植物由来成分からなる１，３－プロパンジオールを用いた。そして、これらの成分を、目的の分子量となる適宜な量で用いて重合して、水酸基価が３７．３ｍｇＫＯＨ／ｇ、酸価が０．３ｍｇＫＯＨ／ｇ、数平均分子量が３０００である、１００％植物由来成分からなるポリエステルジオールＰＥ１を得た。
　次に、反応容器に、上記で得たポリエステルジオールＰＥ１を５００部と、有機ジイソシアネートであるイソホロンジイソシアネート６６．４部を仕込み、窒素気流下、１００℃で５時間反応させて、ＮＣＯ基含有率１．８７％のウレタンプレポリマーを得た。得られたウレタンプレポリマーを希釈用有機溶剤である酢酸エチル１８８．８部に溶解して、不揮発分７５％のウレタンプレポリマー溶液とした。
　次いで、ポリアミンであるイソホロンジアミン２３．６部と、酢酸エチル９８１．４部と、イソプロピルアルコール２０６．５部の混合物（ジアミン溶液）を配合し、撹拌しながら、先に得たウレタンプレポリマー溶液を７５５．２部滴下して、４０℃で１時間反応した。その結果、不揮発分（固形分）３０％、粘度１１５０ｍＰａ・ｓ（２５℃）の、末端のアミノ基濃度が樹脂固形分１ｇ当たり４２．８μｇ当量で、樹脂固形分中に植物由来成分を８４．７％（バイオマス度８４．７％）有するポリウレタン樹脂エマルションＰＵ１を得た。 [Production Example 10]
A resin solution was prepared in the same manner as in Example 1 of JP-A-2019-172977. That is, using dimer acid (dimer purity 98%) composed of plant-derived components / succinic acid composed of plant-derived components = 90/10 (molar ratio) as a polyfunctional carboxylic acid component, and as a polyfunctional alcohol component, plant-derived components 1,3-propanediol was used. Then, these components are polymerized using appropriate amounts to achieve the desired molecular weight, and the hydroxyl value is 37.3 mgKOH / g, the acid value is 0.3 mgKOH / g, and the number average molecular weight is 3000. 100% A polyester diol PE1 composed of a plant-derived component was obtained.
Next, 500 parts of the polyester diol PE1 obtained above and 66.4 parts of isophorone diisocyanate, which is an organic diisocyanate, were charged into a reaction vessel and reacted at 100° C. for 5 hours under a nitrogen stream to obtain an NCO group content of 1. A 0.87% urethane prepolymer was obtained. The resulting urethane prepolymer was dissolved in 188.8 parts of ethyl acetate, which is an organic solvent for dilution, to obtain a urethane prepolymer solution having a non-volatile content of 75%.
Next, a mixture (diamine solution) of 23.6 parts of polyamine isophoronediamine, 981.4 parts of ethyl acetate, and 206.5 parts of isopropyl alcohol was blended, and the previously obtained urethane prepolymer solution was added while stirring. 755.2 parts were added dropwise and reacted at 40° C. for 1 hour. As a result, it was found that the non-volatile content (solid content) was 30%, the viscosity was 1150 mPa·s (25°C), the terminal amino group concentration was 42.8 μg equivalent per 1 g of resin solid content, and the plant-derived component was 84.5 μg equivalent per 1 g of resin solid content. A polyurethane resin emulsion PU1 having a biomass content of 7% (84.7% biomass content) was obtained.
　＜白色ペースト＞
　脱イオン水４１１部、分散剤［ビックケミージャパン株式会社製、ＢＹＫ－１９０］９７部、プロピレングリコール６０部、酸化チタン［石原産業株式会社製、ＣＲ－９５］１０００部およびガラスビーズ（直径１ｍｍ）２００部をディスパーで回転速度３０００ｍｉｎ－１にて１２０分間分散させた後、３００メッシュの金網で濾過することにより白色ペーストを調製した。白色ペーストの組成を表３に記載する。 <White paste>
411 parts of deionized water, dispersant [BYK-190 manufactured by BYK Chemie Japan Co., Ltd.] 97 parts, propylene glycol 60 parts, titanium oxide [CR-95 manufactured by Ishihara Sangyo Co., Ltd.] 1000 parts and glass beads (diameter 1 mm) A white paste was prepared by dispersing 200 parts with a disper at a rotation speed of 3000 min −1 for 120 minutes and then filtering through a 300-mesh wire mesh. The composition of the white paste is given in Table 3.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　［実施例１］
　製造例１にて得られた樹脂エマルション１９．８部にＷＡＸエマルションとしてＳＴ２００（日本触媒製）２．８部を加え、ホモディスパーで回転速度１０００ｍｉｎ－１にて撹拌しながら、白色ペースト３０部、プロピレングリコール（ＰＧ）２０部、ジエチレングリコールモノブチルエーテル（ＢＤＧ、ＳＰ値９．５）１０部、界面活性剤［信越化学工業株式会社製、ＫＦ－６０１１］０．４部、および全体で１００部となるようにイオン交換水を加え、更に３０分間撹拌した後、３μｍのフィルター［アドバンテック社製、ＭＣＰ－３－Ｃ１０Ｓ］で濾過することで水性インクを調製した。 [Example 1]
To 19.8 parts of the resin emulsion obtained in Production Example 1, 2.8 parts of ST200 (manufactured by Nippon Shokubai Co., Ltd.) as a WAX emulsion was added, and while stirring with a homodisper at a rotation speed of 1000 min -1 , 30 parts of a white paste, 20 parts of propylene glycol (PG), 10 parts of diethylene glycol monobutyl ether (BDG, SP value 9.5), 0.4 parts of surfactant [KF-6011 manufactured by Shin-Etsu Chemical Co., Ltd.], and 100 parts in total Ion-exchanged water was added in the manner described above, and the mixture was further stirred for 30 minutes, followed by filtration through a 3 μm filter [MCP-3-C10S, manufactured by Advantech] to prepare an aqueous ink.
　［実施例２～１２、比較例１～２］
　表４～５に示す組成にする以外は実施例１と同様にして、実施例２～１２、及び比較例１～２の水性インクを得た。 [Examples 2-12, Comparative Examples 1-2]
Water-based inks of Examples 2-12 and Comparative Examples 1-2 were obtained in the same manner as in Example 1 except that the compositions shown in Tables 4-5 were used.
　＜インクジェット印刷物の作製１（試験用シート（ＰＥＴ））＞
　温度２５±１℃および相対湿度３０±５％の空気中でインクジェットプリントヘッド〔京セラ（株）製、品番：ＫＪ４Ｂ－ＹＨ０６ＷＳＴ－ＳＴＤＶ〕を装備した印字評価装置〔（株）ジェネシス製〕に水性インクを充填した。
　次に、印字評価装置において、ヘッド電圧を２６Ｖに、周波数を４ｋＨｚに、吐出液滴量を１２ｐＬ（ピコリットル）に、ヘッド温度を３２℃に、解像度を６００ｄｐｉに、負圧を－４．０ｋＰａに設定した。記録媒体としてコロナ処理ポリエステルフィルム（ＰＥＴ）〔フタムラ化学（株）製、商品名：太閤ポリエステルフィルムＦＥ２００１〕を用い、当該コロナ処理ポリエステルフィルムの長手方向と搬送方向とが同一方向となるようにして搬送台に固定した。印字命令を前記印字評価装置に転送し、水性インクをインクジェット記録方式でコロナ処理ポリエステルフィルム上に打ち込み量１００％（１２ｐＬ、６００×６００ｄｐｉ）でベタ画像を印刷し、その直後に１００℃の乾燥機で当該コロナ処理ポリエステルフィルムを１０秒間乾燥させることにより、試験用シート（ＰＥＴ）を得た。 <Preparation of Inkjet Printed Material 1 (Test Sheet (PET))>
Water-based ink is applied to a print evaluation device [manufactured by Genesis Co., Ltd.] equipped with an inkjet print head [manufactured by Kyocera Corporation, product number: KJ4B-YH06WST-STDV] in air at a temperature of 25 ± 1 ° C and a relative humidity of 30 ± 5%. was filled.
Next, in the print evaluation device, the head voltage was set to 26 V, the frequency was set to 4 kHz, the ejected droplet volume was set to 12 pL (picoliters), the head temperature was set to 32° C., the resolution was set to 600 dpi, and the negative pressure was set to −4.0 kPa. set to A corona-treated polyester film (PET) [manufactured by Futamura Chemical Co., Ltd., trade name: Taiko polyester film FE2001] was used as a recording medium, and the corona-treated polyester film was conveyed so that the longitudinal direction and the conveying direction were the same. fixed to the table. A print command is transferred to the print evaluation device, and a solid image is printed on a corona-treated polyester film with an ink-jet recording method at a printing amount of 100% (12 pL, 600 x 600 dpi). A test sheet (PET) was obtained by drying the corona-treated polyester film at for 10 seconds.
　＜インクジェット印刷物の作製２（試験用シート（ＯＰＰ））＞
　記録媒体をコロナ処理ポリエステルフィルム（ＰＥＴ）〔フタムラ化学（株）製、商品名：太閤ポリエステルフィルムＦＥ２００１〕からコロナ処理ＯＰＰフィルム［フタムラ化学（株）製、商品名：ＦＯＲ－ＡＱ］に変える以外はインクジェット印刷物の作製１（試験用シート（ＰＥＴ））と同様にして試験用シート（ＯＰＰ）を得た。 <Production of inkjet printed matter 2 (test sheet (OPP))>
Except for changing the recording medium from corona-treated polyester film (PET) [manufactured by Futamura Chemical Co., Ltd., trade name: Taiko Polyester Film FE2001] to corona-treated OPP film [manufactured by Futamura Chemical Co., Ltd., trade name: FOR-AQ]. A test sheet (OPP) was obtained in the same manner as in Preparation 1 of inkjet printed matter (test sheet (PET)).
　－評価方法－
　＜耐スクラッチ性＞
　試験用シート（ＰＥＴ）の印刷画像をナイロン製不織布で擦り、以下の評価基準に基づいて基材に対する密着性を評価した。各実施例、比較例の評価結果を表４～５に示す。
〔評価基準〕
５：印刷画像を擦っても画像がまったく剥がれない。
４：印刷画像を擦ると画像がごく僅かだけ剥がれる。
３：印刷画像を擦ると画像が僅かに剥がれる。
２：印刷画像を擦ると画像が少しだけ剥がれる。
１：印刷画像を擦ると画像が明確に剥がれる。
０：印刷画像を擦ると画像が容易に剥がれる。 -Evaluation method-
<Scratch resistance>
The printed image on the test sheet (PET) was rubbed with a nylon nonwoven fabric, and the adhesion to the substrate was evaluated based on the following evaluation criteria. Tables 4 and 5 show the evaluation results of each example and comparative example.
〔Evaluation criteria〕
5: Even if the printed image is rubbed, the image is not peeled off at all.
4: The image peels off only slightly when the printed image is rubbed.
3: The image is slightly peeled off when the printed image is rubbed.
2: When the printed image is rubbed, the image is slightly peeled off.
1: When the printed image is rubbed, the image is clearly peeled off.
0: The image is easily peeled off when the printed image is rubbed.
　＜密着性（ＰＥＴ）＞
　試験用シート（ＰＥＴ）の印刷画像を手指の爪で擦り、以下の評価基準に基づいて基材に対する密着性を評価した。各実施例、比較例の評価結果を表４～５に示す。
〔評価基準〕
５：印刷画像を手指の爪で擦っても画像がまったく剥がれない。
４：印刷画像を手指の爪で擦ると画像がごく僅かだけ剥がれる。
３：印刷画像を手指の爪で擦ると画像が僅かに剥がれる。
２：印刷画像を手指の爪で擦ると画像が少しだけ剥がれる。
１：印刷画像を手指の爪で擦ると画像が明確に剥がれる。
０：印刷画像を手指の爪で擦ると画像が容易に剥がれる。 <Adhesion (PET)>
The printed image on the test sheet (PET) was rubbed with a fingernail, and the adhesion to the substrate was evaluated based on the following evaluation criteria. Tables 4 and 5 show the evaluation results of each example and comparative example.
〔Evaluation criteria〕
5: Even if the printed image is rubbed with a fingernail, the image is not peeled off at all.
4: When the printed image is rubbed with a fingernail, the image is very slightly peeled off.
3: The image is slightly peeled off when the printed image is rubbed with a fingernail.
2: When the printed image is rubbed with a fingernail, the image is slightly peeled off.
1: When the printed image is rubbed with a fingernail, the image is clearly peeled off.
0: The image is easily peeled off when the printed image is rubbed with a fingernail.
　＜密着性（ＯＰＰ）＞
　試験用シート（ＰＥＴ）に変えて試験用シート（ＯＰＰ）とした以外は＜密着性（ＰＥＴ）＞と同条件で評価した。各実施例、比較例の評価結果を表４～５に示す。 <Adhesion (OPP)>
Evaluation was performed under the same conditions as <Adhesion (PET)> except that the test sheet (PET) was replaced with the test sheet (OPP). Tables 4 and 5 show the evaluation results of each example and comparative example.
　＜耐ブロッキング性＞
　試験用シート（ＰＥＴ）の印刷面にコロナ処理が施されていないポリエステルフィルムを重ね合わせ、当該ポリエステルフィルムの上に２５℃の空気中で２Ｎ／ｃｍ２の荷重を１時間加えた後、当該ポリエステルフィルムを素早く引き剥がし、そのときの抵抗感を観察し、以下の評価基準に基づいて耐ブロッキング性を評価した。各実施例、比較例の評価結果を表４～５に示す。
〔評価基準〕
５：ポリエステルフィルムを引き剥がすときに抵抗がまったく感じられない。
４：ポリエステルフィルムを引き剥がすときに抵抗がごく僅かだけ感じられる。
３：ポリエステルフィルムを引き剥がすときに抵抗が少しだけ感じられる。
２：ポリエステルフィルムを引き剥がすときに抵抗が明らかに感じられる。
１：ポリエステルフィルムを引き剥がすときに抵抗が強く感じられる。
０：ポリエステルフィルムを引き剥がすときに抵抗が非常に強く感じられる。 <Blocking resistance>
A polyester film not subjected to corona treatment was superimposed on the printed surface of the test sheet (PET), and a load of 2 N/cm 2 was applied on the polyester film in the air at 25 ° C. for 1 hour. The film was quickly peeled off, resistance was observed at that time, and blocking resistance was evaluated based on the following evaluation criteria. Tables 4 and 5 show the evaluation results of each example and comparative example.
〔Evaluation criteria〕
5: No resistance is felt when the polyester film is peeled off.
4: Very little resistance is felt when the polyester film is peeled off.
3: Only a little resistance is felt when the polyester film is peeled off.
2: Resistance is clearly felt when the polyester film is peeled off.
1: Strong resistance is felt when the polyester film is peeled off.
0: Very strong resistance is felt when the polyester film is peeled off.
　＜耐粘着テープ剥離性＞
　試験用シート（ＯＰＰ）の印刷面に対し粘着テープ（ニチバン（株）製、セロテープ（登録商標）Ｎｏ．４０５、２４ｍｍ幅）を常温環境下で貼付け、１分間静置した。その後、１８０°方向に引き剥がし以下の評価基準に基づいて耐粘着テープ剥離性を評価した。各実施例、比較例の評価結果を表４～５に示す。
〔評価基準〕
５：印刷画像が全く剥れない。
４：印刷画像が１～２０％剥れる。
３：印刷画像が２１～５０％剥れる。
２：印刷画像が５１～７５％剥れる。
１：印刷画像が７６～１００％剥れる。 <Removability of adhesive tape>
An adhesive tape (Cellotape (registered trademark) No. 405, 24 mm width, manufactured by Nichiban Co., Ltd.) was attached to the printed surface of the test sheet (OPP) in a normal temperature environment, and left to stand for 1 minute. After that, it was peeled off in the direction of 180°, and the adhesive tape peel resistance was evaluated based on the following evaluation criteria. Tables 4 and 5 show the evaluation results of each example and comparative example.
〔Evaluation criteria〕
5: The printed image is not peeled off at all.
4: 1 to 20% of the printed image is peeled off.
3: 21 to 50% of the printed image is peeled off.
2: 51 to 75% of the printed image is peeled off.
1: 76 to 100% of the printed image is peeled off.
　＜バイオマス度＞
　製造例１～９の樹脂エマルションの不揮発分中におけるバイオマス度、及び実施例及び比較例の水性インキの不揮発分中（インク固形分中）におけるバイオマス度は、バイオマス成分の含有量（質量％）から算出して求めた。
　製造例１におけるバイオマス度の算出は以下の通りである。
｛バイオマスモノマーＩＢＯＡ（３２２＋３１０）部×バイオマス度７３％／１０００部｝×１００（％）
＝４６％
　各製造例における樹脂エマルションの不揮発分中のバイオマス度は表１～２に示した。
　実施例１におけるバイオマス度の算出は以下の通りである。
｛樹脂エマルション１９．８部×不揮発分（５０％）×バイオマス度（４６％）／不揮発分（３１．３部）｝×１００
＝４．６／３１．３×１００（％）＝１５％
　各実施例、比較例における水性インクのインク固形分中のバイオマス度は表４～５に示した。 <Biomass degree>
The biomass degree in the non-volatile content of the resin emulsions of Production Examples 1 to 9 and the biomass degree in the non-volatile content (ink solid content) of the water-based inks of Examples and Comparative Examples were calculated from the biomass component content (% by mass). Calculated and obtained.
The calculation of the biomass degree in Production Example 1 is as follows.
{Biomass monomer IBOA (322 + 310) parts x biomass degree 73% / 1000 parts} x 100 (%)
= 46%
Tables 1 and 2 show the biomass content in the nonvolatile matter of the resin emulsion in each production example.
The calculation of the biomass degree in Example 1 is as follows.
{Resin emulsion 19.8 parts x non-volatile content (50%) x biomass degree (46%) / non-volatile content (31.3 parts)} x 100
= 4.6/31.3 x 100 (%) = 15%
Tables 4 and 5 show the biomass content in the ink solid content of the water-based inks in each example and comparative example.
　＜耐水性＞
　耐水性は、以下の耐水性浸漬前後の試験用シート（ＰＥＴ）の６０°鏡面光沢を光沢計〔日本電色工業（株）製、品番：ＶＧ-７０００〕で測定することによって決定した。
　具体的には、４０℃温水に試験用シート（ＰＥＴ）を２４時間浸漬させ（耐水性試験）、十分に水を拭き取り前記光沢計で当該試験用シート（ＰＥＴ）の光沢を測定し、
式：［光沢保持率（％）］＝〔［耐水性試験後の光沢］÷［耐水性試験前の光沢］〕×１００
に基づいて光沢保持率を求めた。この光沢保持率の値から、以下の評価基準に基づいて耐水性を評価した。
５：光沢保持率が８０％以上
３：光沢保持率が７０以上８０％未満
１：光沢保持率が７０％未満 <Water resistance>
The water resistance was determined by measuring the 60° specular gloss of the test sheet (PET) before and after immersion in water resistance with a gloss meter (manufactured by Nippon Denshoku Industries Co., Ltd., product number: VG-7000).
Specifically, the test sheet (PET) is immersed in hot water at 40 ° C. for 24 hours (water resistance test), the water is wiped off sufficiently, and the gloss of the test sheet (PET) is measured with the gloss meter.
Formula: [gloss retention (%)] = [[gloss after water resistance test] ÷ [gloss before water resistance test]] × 100
The gloss retention rate was determined based on. Based on the value of this gloss retention rate, the water resistance was evaluated based on the following evaluation criteria.
5: Gloss retention rate is 80% or more 3: Gloss retention rate is 70 or more and less than 80% 1: Gloss retention rate is less than 70%
　＜耐候性＞
　耐候性は、以下の耐候性試験前後の試験用シート（ＰＥＴ）の６０°鏡面光沢を光沢計〔日本電色工業（株）製、品番：ＶＧ-７０００〕で測定することによって決定した。
　耐候性試験条件
　設置条件：南面３０度、直接暴露（暴露地：大阪府吹田市／（株）日本触媒敷地内）
　試験期間：２ヵ月
　光沢保持率算出式
式：［光沢保持率（％）］＝〔［耐候性試験後の光沢］÷［耐候性試験前の光沢］〕×１００
　耐候性評価基準
５：光沢保持率が８０％以上
３：光沢保持率が７０以上８０％未満
１：光沢保持率が７０％未満 <Weather resistance>
The weather resistance was determined by measuring the 60° specular gloss of the test sheet (PET) before and after the following weather resistance test with a gloss meter (manufactured by Nippon Denshoku Industries Co., Ltd., product number: VG-7000).
Weather resistance test conditions Installation conditions: South facing 30 degrees, direct exposure (Exposure site: Suita City, Osaka / Nippon Shokubai Co., Ltd. premises)
Test period: 2 months Gloss retention rate formula: [gloss retention rate (%)] = [[gloss after weather resistance test] ÷ [gloss before weather resistance test]] × 100
Weather resistance evaluation criteria 5: Gloss retention rate is 80% or more 3: Gloss retention rate is 70 or more and less than 80% 1: Gloss retention rate is less than 70%
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
　本発明のインク用アクリル系樹脂は、インクジェット用インク、フレキソ印刷用インク、オフセット印刷用インク、リソグラフ印刷用インク、グラビア印刷用インク、スクリーン印刷用インクなどのインクに含有させる樹脂として好適に使用することができる。 The acrylic resin for ink of the present invention is suitably used as a resin to be contained in ink such as inkjet ink, flexographic printing ink, offset printing ink, lithographic printing ink, gravure printing ink, and screen printing ink. be able to.

Claims (11)

  1. 　バイオマス度１０％以上のインク用アクリル系樹脂。 　Acrylic resin for ink with a biomass content of 10% or more.
  2. 　環状脂肪族基を有する（メタ）アクリレート由来の構造単位を有する請求項１に記載のインク用アクリル系樹脂。 The acrylic resin for ink according to claim 1, which has a structural unit derived from a (meth)acrylate having a cycloaliphatic group.
  3. 　前記環状脂肪族基を有する（メタ）アクリレートが、１つの水酸基を有する環状脂肪族炭化水素と（メタ）アクリル酸とのエステルである請求項２に記載のインク用アクリル系樹脂。 The acrylic resin for ink according to claim 2, wherein the (meth)acrylate having a cycloaliphatic group is an ester of a cycloaliphatic hydrocarbon having one hydroxyl group and (meth)acrylic acid.
  4. 　ポリマー１００質量部に対する環状脂肪族基を有する（メタ）アクリレート由来の構造単位の割合が３０質量部以上８０質量部以下である請求項２又は３に記載のインク用アクリル系樹脂。 The acrylic resin for ink according to claim 2 or 3, wherein the ratio of the (meth)acrylate-derived structural unit having a cycloaliphatic group to 100 parts by mass of the polymer is 30 parts by mass or more and 80 parts by mass or less.
  5. 　前記環状脂肪族基がテルペン由来の基である請求項２又は３に記載のインク用アクリル系樹脂。 The acrylic resin for ink according to claim 2 or 3, wherein the cycloaliphatic group is a terpene-derived group.
  6. 　酸価が２０ｍｇＫＯＨ／ｇ以下である請求項１～３のいずれかに記載のインク用アクリル系樹脂。 The acrylic resin for ink according to any one of claims 1 to 3, which has an acid value of 20 mgKOH/g or less.
  7. 　請求項１に記載のインク用アクリル系樹脂を含む水性分散体。 An aqueous dispersion containing the acrylic resin for ink according to claim 1.
  8. 　請求項１～３のいずれかに記載のアクリル系樹脂、または請求項７に記載の水性分散体を含むインク組成物。 An ink composition comprising the acrylic resin according to any one of claims 1 to 3 or the aqueous dispersion according to claim 7.
  9. 　さらに高分子ワックスを含む請求項８に記載のインク組成物。 The ink composition according to claim 8, further comprising polymeric wax.
  10. 　印刷用基材上に請求項１～３のいずれかに記載のインク用アクリル系樹脂を含む層を有する積層体。 A laminate having a layer containing the acrylic resin for ink according to any one of claims 1 to 3 on a substrate for printing.
  11. 　請求項８に記載のインク組成物を印刷基材上に塗布する工程を含む積層体の製造方法。
          A method for producing a laminate, comprising the step of applying the ink composition according to claim 8 onto a printing substrate.
PCT/JP2022/026943 2021-07-21 2022-07-07 Acrylic resin for ink WO2023002853A1 (en)

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