WO2023002853A1 - Résine acrylique pour encre - Google Patents

Résine acrylique pour encre Download PDF

Info

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
Authority
WO
WIPO (PCT)
Prior art keywords
meth
parts
mass
acrylate
group
Prior art date
Application number
PCT/JP2022/026943
Other languages
English (en)
Japanese (ja)
Inventor
芳峰 坂元
秀明 安藤
Original Assignee
株式会社日本触媒
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 株式会社日本触媒 filed Critical 株式会社日本触媒
Priority to JP2023536685A priority Critical patent/JPWO2023002853A1/ja
Publication of WO2023002853A1 publication Critical patent/WO2023002853A1/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • 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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Le but de la présente invention est de fournir une résine pour encres qui a une résistance à l'eau et une tenue aux intempéries satisfaisantes dont le rapport de biomasse est élevé. Cette résine pour encres est caractérisée en ce qu'elle est une résine acrylique pour des encres qui a un rapport de biomasse de 10 % ou plus.
PCT/JP2022/026943 2021-07-21 2022-07-07 Résine acrylique pour encre WO2023002853A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2023536685A JPWO2023002853A1 (fr) 2021-07-21 2022-07-07

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2021-120836 2021-07-21
JP2021120836 2021-07-21

Publications (1)

Publication Number Publication Date
WO2023002853A1 true WO2023002853A1 (fr) 2023-01-26

Family

ID=84979172

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2022/026943 WO2023002853A1 (fr) 2021-07-21 2022-07-07 Résine acrylique pour encre

Country Status (2)

Country Link
JP (1) JPWO2023002853A1 (fr)
WO (1) WO2023002853A1 (fr)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008052047A (ja) * 2006-08-24 2008-03-06 Fuji Seal International Inc シュリンクラベル用印刷物およびその印刷のために用いるシュリンクラベル用印刷インキ組成物
JP2008248215A (ja) * 2007-03-29 2008-10-16 Yasuhara Chemical Co Ltd 水添テルペンフェノール（メタ）アクリレート樹脂および樹脂組成物
JP2018070713A (ja) * 2016-10-27 2018-05-10 三菱ケミカル株式会社 インキ組成物及び塗膜
JP2018104708A (ja) * 2012-11-30 2018-07-05 綜研化学株式会社 ペースト組成物、ならびに焼成体およびその製造方法
JP2019131716A (ja) * 2018-01-31 2019-08-08 三菱ケミカル株式会社 非水系印刷インキ用樹脂組成物
JP2021070809A (ja) * 2019-10-30 2021-05-06 株式会社日本触媒 Ｎ−ビニルラクタム系共重合体の製造方法
JP2021098770A (ja) * 2019-12-20 2021-07-01 東洋インキＳｃホールディングス株式会社 活性エネルギー線硬化性インキ組成物およびその印刷物
JP2021155645A (ja) * 2020-03-30 2021-10-07 大成ファインケミカル株式会社 バイオマス（メタ）アクリル共重合体、それを含むコーティング剤及びインク組成物、並びにこれらの製造方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008052047A (ja) * 2006-08-24 2008-03-06 Fuji Seal International Inc シュリンクラベル用印刷物およびその印刷のために用いるシュリンクラベル用印刷インキ組成物
JP2008248215A (ja) * 2007-03-29 2008-10-16 Yasuhara Chemical Co Ltd 水添テルペンフェノール（メタ）アクリレート樹脂および樹脂組成物
JP2018104708A (ja) * 2012-11-30 2018-07-05 綜研化学株式会社 ペースト組成物、ならびに焼成体およびその製造方法
JP2018070713A (ja) * 2016-10-27 2018-05-10 三菱ケミカル株式会社 インキ組成物及び塗膜
JP2019131716A (ja) * 2018-01-31 2019-08-08 三菱ケミカル株式会社 非水系印刷インキ用樹脂組成物
JP2021070809A (ja) * 2019-10-30 2021-05-06 株式会社日本触媒 Ｎ−ビニルラクタム系共重合体の製造方法
JP2021098770A (ja) * 2019-12-20 2021-07-01 東洋インキＳｃホールディングス株式会社 活性エネルギー線硬化性インキ組成物およびその印刷物
JP2021155645A (ja) * 2020-03-30 2021-10-07 大成ファインケミカル株式会社 バイオマス（メタ）アクリル共重合体、それを含むコーティング剤及びインク組成物、並びにこれらの製造方法

Also Published As

Publication number Publication date
JPWO2023002853A1 (fr) 2023-01-26

Similar Documents

Publication Publication Date Title
JP5581815B2 (ja) 水性インクジェットインキ用バインダー樹脂組成物、およびそれを用いたインクジェットインキ
JP6065036B2 (ja) 印刷インキ積層体
JP2010280830A (ja) 水性インクジェットインキ用バインダー樹脂組成物、およびそれを用いたインクジェットインキ
JP7296487B2 (ja) 水性インク用樹脂エマルション
JP2006264312A (ja) 高耐光性記録材料用紫外線吸収性ポリマー
JP7410185B2 (ja) インクジェット用インク
JP6923064B1 (ja) 積層体、及び波長カットフィルター
JP2011094112A (ja) 顔料分散物及びそれを用いたインク組成物
TW201609998A (zh) 包含惰性樹脂之放射線硬化性組成物
JP2019094423A (ja) 水性リキッドインキ、及び該水性リキッドインキを用いた積層体
WO2023002853A1 (fr) Résine acrylique pour encre
JP6258662B2 (ja) 水性インク組成物
JP7340467B2 (ja) 水性インク用樹脂エマルション
JP7356898B2 (ja) 水性インク用樹脂エマルション
JP7446694B2 (ja) 水性インク用エマルション及びそれを含む水性インク用インク組成物
JP2023112803A (ja) 水性分散体ならびに水性インク
JP7393220B2 (ja) インクジェット用インク
JP2023008774A (ja) 重合体含有水性分散体ならびに水性インク
JP2015081322A (ja) 水性インク用改質剤
JP7343655B2 (ja) インクジェット捺染用インク、該インクを用いた印刷物の製造方法および画像固着物品
JP7415802B2 (ja) プライマー及び積層体
JP2024079368A (ja) インク用樹脂エマルション
JP2024054483A (ja) 水性白色インク
WO2022270171A1 (fr) Encre pour impression textile par jet d'encre, procédé de production d'un objet imprimé à l'aide de ladite encre, et article à image fixe
JP2023082767A (ja) 顔料分散体の製造方法

Legal Events

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

Ref document number: 22845787

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2023536685

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE