WO2020121534A1 - Copolymère de styrène-acrylate - Google Patents

Copolymère de styrène-acrylate Download PDF

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Publication number
WO2020121534A1
WO2020121534A1 PCT/JP2018/046190 JP2018046190W WO2020121534A1 WO 2020121534 A1 WO2020121534 A1 WO 2020121534A1 JP 2018046190 W JP2018046190 W JP 2018046190W WO 2020121534 A1 WO2020121534 A1 WO 2020121534A1
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Prior art keywords
acrylate
meth
oxide
styrene
compound
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Ceased
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PCT/JP2018/046190
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English (en)
Japanese (ja)
Inventor
令奈 岩崎
卓也 藤山
井上　聡
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Osaka Soda Co Ltd
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Osaka Soda Co Ltd
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Application filed by Osaka Soda Co Ltd filed Critical Osaka Soda Co Ltd
Priority to JP2019503486A priority Critical patent/JP6537031B1/ja
Priority to CN201880003218.9A priority patent/CN110972480A/zh
Priority to PCT/JP2018/046190 priority patent/WO2020121534A1/fr
Publication of WO2020121534A1 publication Critical patent/WO2020121534A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • 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
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • 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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00

Definitions

  • the present invention relates to a styrene-acrylate copolymer, an active energy ray-curable resin composition containing a styrene-acrylate copolymer, and an ink and a paint containing the resin composition.
  • the weight average molecular weight (Mw) obtained by copolymerizing a monomer component containing styrenes, (meth)acrylic acid alkyl ester and a hydrophilic group-containing vinyl monomer is 5,000 to Active energy ray curable resin having a glass transition temperature (Tg) of 13,000 and an active energy ray curable resin (A) having a glass transition temperature (Tg) of 70 to 100° C. and a reactive diluent (B).
  • Tg glass transition temperature
  • A active energy ray curable resin
  • Tg glass transition temperature
  • B reactive diluent
  • An object of the present invention is to provide a styrene-acrylate copolymer that can obtain excellent physical properties when used in an ink or a paint, and an active energy ray-curable composition containing the copolymer.
  • Item 1 A styrene-acrylate copolymer, The ratio of the structural unit (A) derived from the styrene compound is 10 to 90 mol%, the ratio of the structural unit (B) derived from the acrylate compound is 10 to 90 mol%, and the structural unit derived from the acrylate compound (B) is characterized by containing a structural unit (b-1) derived from a compound having at least three or more acryloyl groups in the molecule.
  • Item 2. Item 2.
  • Item 3 The compound having at least three or more acryloyl groups in the molecule is trimethylolpropane tri(meth)acrylate, trimethyloloctanetri(meth)acrylate, trimethylolpropane polyethoxytri(meth)acrylate, trimethylolpropane polypropoxytril.
  • (Meth)acrylate trimethylolpropane polyethoxypolypropoxytri(meth)acrylate, tris[(meth)acryloyloxyethyl]isocyanurate, pentaerythritol tri(meth)acrylate, pentaerythritol polyethoxytetra(meth)acrylate, pentaerythritol Item 3.
  • the styrene according to Item 1 or 2 which is one kind selected from polypropoxytetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, and dipentaerythritol tetra(meth)acrylate. Acrylate copolymer.
  • Item 4. Item 1. The structural unit (B) derived from an acrylate compound further contains a structural unit (b-2) derived from an aromatic acrylate compound and a structural unit (b-3) derived from an aliphatic acrylate compound. The styrene-acrylate copolymer according to any one of 1. Item 5. Item 5.
  • Item 6. The styrene-acrylate copolymer according to any one of Items 1 to 5, wherein the styrene-acrylate copolymer has an iodine value of 1 to 100.
  • An active energy ray-curable composition comprising the styrene-acrylate copolymer according to any one of items 1 to 6.
  • Item 9. Item 9.
  • An ink comprising the composition according to Item 7 or 8.
  • Item 10. Item 9.
  • a paint comprising the composition according to Item 7 or 8.
  • Item 11. The paint according to Item 10, which is an overprint varnish.
  • an active energy ray-curable composition containing a styrene-acrylate copolymer is used in an ink or paint, whereby an ink or paint excellent in various physical properties (drying property, scratch resistance) can be obtained.
  • Styrene-Acrylate Copolymer The styrene-acrylate copolymer of the present invention will be described below.
  • the styrene-acrylate copolymer of the present invention is a styrene-acrylate copolymer in which the ratio of the structural unit (A) derived from the styrene compound is 10 to 90 mol% and the structural unit derived from the acrylate compound is The ratio of (B) is 10 to 90 mol %, and the structural unit (B) derived from an acrylate compound is a structural unit (b-1) derived from a compound having at least three or more acryloyl groups in the molecule. It is characterized by including.
  • the proportion of the structural unit (A) derived from the styrene compound may be 10 to 90 mol %, preferably 20 to 80 mol %, and 20 to 50 mol %. % Is more preferable. Further, the ratio of the structural unit (B) derived from the acrylate compound may be 10 to 90 mol %, preferably 20 to 80 mol %, and more preferably 50 to 80 mol %.
  • Structural unit (A) derived from styrene compound The structural unit (A) derived from the styrene compound in the styrene-acrylate copolymer of the present invention is not particularly limited, and examples thereof include styrene; methylstyrene, ⁇ -methylstyrene, ⁇ -methylstyrene, p-methylstyrene.
  • Alkyl-substituted styrenes such as tert-butylstyrene; halogen-substituted styrenes such as 4-chlorostyrene, 4-bromostyrene, chloromethylstyrene; p-hydroxystyrene, ⁇ -methyl-p-hydroxystyrene, 2-methyl- Hydroxystyrenes such as 4-hydroxystyrene and 3,4-dihydroxystyrene; vinylbenzyl alcohols; alkoxy-substituted styrenes such as p-methoxystyrene, p-tert-butoxystyrene, m-tert-butoxystyrene; 3-vinyl Vinylbenzoic acids such as benzoic acid and 4-vinylbenzoic acid; 4-vinylbenzyl acetate; 4-acetoxystyrene; amide styrenes such as 2-butylamidost
  • styrene alkyl-substituted styrenes such as methylstyrene, ⁇ -methylstyrene, ⁇ -methylstyrene, p-methylstyrene and tert-butylstyrene; halogen-substituted styrenes such as 4-chlorostyrene, 4-bromostyrene and chloromethylstyrene.
  • hydroxystyrenes such as p-hydroxystyrene, ⁇ -methyl-p-hydroxystyrene, 2-methyl-4-hydroxystyrene and 3,4-dihydroxystyrene, and styrene; methylstyrene, ⁇ -methylstyrene, ⁇ Alkyl-substituted styrenes such as -methylstyrene, p-methylstyrene and tert-butylstyrene are more preferable.
  • Structural unit (B) derived from acrylate compound The constituent unit (B) derived from the acrylate compound in the styrene-acrylate copolymer of the present invention may be a constituent unit (b-1) derived from a compound having at least three or more acryloyl groups in the molecule. Good.
  • an acrylate compound having three acryloyl groups and an acrylate compound having four acryloyl groups may be used. Include trimethylolpropane tri(meth)acrylate, trimethyloloctane tri(meth)acrylate, trimethylolpropane polyethoxytri(meth)acrylate, trimethylolpropane polypropoxytri(meth)acrylate, trimethylolpropane polyethoxypolypropoxy.
  • Tri(meth)acrylate tris[(meth)acryloyloxyethyl]isocyanurate, pentaerythritol tri(meth)acrylate, pentaerythritol polyethoxytetra(meth)acrylate, pentaerythritol polypropoxytetra(meth)acrylate, pentaerythritol tetra( (Meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate are preferable, and trimethylolpropane tri(meth)acrylate is preferable.
  • trimethylolpropane polyethoxytri(meth)acrylate More preferred are trimethylolpropane polyethoxytri(meth)acrylate, trimethylolpropane polypropoxytri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and ditrimethylolpropane tetra(meth)acrylate. ..
  • the structural unit (B) derived from the acrylate compound may further include a structural unit (b-2) derived from the aromatic acrylate compound and a structural unit (b-3) derived from the aliphatic acrylate compound.
  • a structural unit (b-2) derived from the aromatic acrylate compound and a structural unit (b-3) derived from the aliphatic acrylate compound.
  • the aromatic acrylate compound and the aliphatic acrylate compound do not include compounds having at least three or more acryloyl groups in the molecule.
  • a structural unit (b-3) derived from an aliphatic acrylate compound the ratio of each structural unit ((b-1):(b-2):(b-3)) is 1 to 4: It may be in the range of 1 to 5:1 to 4, and is preferably in the range of 1 to 3:1 to 4:1 to 3.
  • the constitutional unit (b-2) derived from an aromatic acrylate compound is an aromatic acrylate compound having one or two acryloyl groups in the molecule (preferably, an aromatic acrylate compound having one acryloyl group in the molecule). ), specifically, benzyl (meth)acrylate, phenyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, biphenyl (meth)acrylate, nonylphenyl (meth)acrylate.
  • Nonylphenoxyethyl (meth)acrylate nonylphenoxypolyethylene glycol (meth)acrylate, cumylphenol (meth)acrylate, cumylphenoxyethyl (meth)acrylate, cumylphenoxypolyethyleneglycol (meth)acrylate, o-phenylphenol ( Examples thereof include (meth)acrylate, ethoxylated o-phenylphenol(meth)acrylate, tribromophenyl(meth)acrylate, and EO-modified tribromophenyl(meth)acrylate. Among them, benzyl (meth)acrylate and phenoxyethyl (meth)acrylate are preferable.
  • an aliphatic acrylate compound having one or two acryloyl groups in the molecule preferably an aliphatic acrylate compound having one acryloyl group in the molecule
  • the structural unit (B) derived from the acrylate compound in the styrene-acrylate copolymer may further include a structural unit (b-4) derived from another acrylate compound.
  • the ratio of the structural unit (b-4) derived from the other acrylate compound in the structural unit (B) derived from the acrylate compound is such that it is derived from a compound having at least three acryloyl groups in the molecule.
  • the structural unit (B) derived from the acrylate compound in the styrene-acrylate copolymer of the present invention further contains a structural unit (b-4) derived from the other acrylate compound
  • the other acrylate compound is as described above.
  • a compound having at least three acryloyl groups in the molecule, an aromatic acrylate compound, and an aliphatic acrylate compound are not included.
  • Examples of other acrylate compounds include compounds having at least three or more acryloyl groups in the molecule described above, aromatic acrylate compounds, monofunctional acrylates other than aliphatic acrylate compounds, and bifunctional acrylates.
  • Examples of the monofunctional acrylate include (meth)acrylate of ethylene oxide adduct, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, tricyclodecane monomethylol (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2- Hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, hydroxypentyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl ( (Meth)acrylate, 2-hydroxy-3-butoxypropyl (meth)acrylate, 2-hydroxy-3-methoxypropyl (meth)acrylate, diethylene glycol mono(meth)acrylate, triethylene glycol mono(meth)acrylate, polyethylene glycol mono( (Meth)acrylate, dipropylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)
  • (meth)acryloylmorpholine is preferable.
  • the structural unit (B) derived from the acrylate compound in the styrene-acrylate copolymer contains the structural unit (b-4) derived from the other acrylate compound
  • the structural unit (b-derived from the other acrylate compound The ratio of 4) may be in the range of 0 mol% to 20 mol% in the entire constitutional unit (B) derived from the acrylate compound, and is preferably in the range of 0 mol% to 10 mol %.
  • the styrene-acrylate copolymer may further contain a structural unit (C) derived from a carboxylic acid.
  • a structural unit (C) derived from a carboxylic acid When the structural unit (C) derived from a carboxylic acid is contained, the ratio of the structural unit (C) derived from a carboxylic acid may be in the range of 0 to 20 mol%, and is in the range of 0 to 10 mol%. Preferably.
  • the carboxylic acid may be any unsaturated aliphatic carboxylic acid, and (meth)acrylic acid, maleic acid, itaconic acid and the like are preferable.
  • the molecular weight distribution (weight average molecular weight (Mw)/number average molecular weight (Mn)) of the styrene-acrylate copolymer may be in the range of 1 to 50, and is preferably in the range of 1 to 40. The range is more preferably.
  • the number average molecular weight (Mn) of the styrene-acrylate copolymer may be 1,000 to 100,000, preferably 1,000 to 50,000, and more preferably 1,000 to 30,000.
  • the weight average molecular weight (Mw) of the styrene-acrylate copolymer is not particularly limited, but may be 1,000 to 500,000, preferably 1,000 to 400,000, and 1,000 to 300,000. More preferable.
  • the “number average molecular weight” and the “weight average molecular weight” are measured at 40° C. by gel permeation chromatography (Prominence-i, LC-2030 manufactured by Shimadzu Corp.) to obtain standard polystyrene. It is obtained using a calibration curve.
  • the iodine value of the styrene-acrylate copolymer may be 1 to 100, preferably 1 to 80, and more preferably 1 to 50.
  • the polymerization reaction for obtaining the styrene-acrylate copolymer can be synthesized by a known method using the above raw materials. Various conditions in this synthesis must be appropriately set according to the raw material used and the amount thereof.
  • a catalyst can be used if necessary.
  • the catalyst include azobisisobutyronitrile, azo initiators such as dimethyl 2,2'-azobisisobutyrate, ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides.
  • Peroxyesters and other peroxide initiators 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 1-hydroxycyclohexylphenyl ketone and other acetophenone-based compounds
  • catalysts include benzoin-based compounds such as benzoin and benzoin ethyl ether, benzophenone-based compounds such as benzophenone, phosphorus-based compounds such as acylphosphine oxide, and sulfur-based compounds such as thioxanthone.
  • ketone peroxides include methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, acetylacetone peroxide, cyclohexanone peroxide, and methylcyclohexanone peroxide.
  • hydroperoxides include, for example, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, tert-butyl hydroperoxide, p-menthane hydroperoxide, and diisopropylbenzene hydroperoxide.
  • hydroperoxides include, for example, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, tert-butyl hydroperoxide, p-menthane hydroperoxide, and diisopropylbenzene hydroperoxide.
  • peroxides include, for example, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, tert-butyl hydroperoxide, p-menthane hydroperoxide, and diisopropylbenzene hydroperoxide.
  • peroxides include, for example, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydro
  • diacyl peroxides include, for example, diisobutyryl peroxide, bis-3,5,5-trimethylhexanol peroxide, dilauroyl peroxide, dibenzoyl peroxide, m-toluylbenzoyl peroxide, and succinic acid.
  • examples include peroxides.
  • dialkyl peroxides include dicumyl peroxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, 1,3-bis(tert-butylperoxyisopropyl)hexane, Mention may be made of tert-butyl cumyl peroxide, di-tert-butyl peroxide, di-tert-hexyl peroxide, and 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexyne-3.
  • peroxyketals include, for example, 1,1-bis(tert-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-hexylperoxy)cyclohexane, 1, 1-bis(tert-butylperoxy)-2-methylcyclohexane, 1,1-bis(tert-butylperoxy)cyclohexane, 2,2-bis(tert-butylperoxy)butane, and 4,4-bis Examples thereof include butyl (tert-butylperoxy)pentanoate and 1,1-di(tert-hexylperoxy)cyclohexane.
  • alkyl peresters include, for example, 1,1,3,3-tetramethylbutyl peroxy neodecanoate, ⁇ -cumylperoxy neodecanoate, and tert-butyl perester.
  • the order of adding the raw materials used for the reaction of the styrene-acrylate copolymer of the present invention may be such that after all the raw materials used for the reaction are added to the reaction vessel, the polymerization reaction may be started by heating, and a part of the reaction may be performed first. The polymerization reaction may be carried out while adding it to the vessel and heating and then dropping the rest.After adding the solvent to the reaction vessel and heating, the polymerization reaction is carried out while dropping the mixture of the raw materials used in the reaction. May be.
  • the amount of the catalyst used for the reaction of the styrene-acrylate copolymer of the present invention may be appropriately adjusted, and may be 10.0 parts by weight or less based on 100 parts by weight of the components used for the polymerization reaction. It is preferably not more than 0.0 parts by weight. Further, it is more preferably 0.001 to 8.0 parts by weight.
  • a solvent may be used if necessary.
  • a solvent it is preferably used within the range of 80% by weight or less based on the total amount of the reaction solution.
  • the solvent examples include alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol and n-butyl alcohol, acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl isopropyl ketone, methyl-n-butyl ketone, Methyl isobutyl ketone, methyl-n-amyl ketone, methyl isoamyl ketone, diethyl ketone, ethyl-n-propyl ketone, ethyl isopropyl ketone, ethyl-n-butyl ketone, ethyl isobutyl ketone, di-n-propyl ketone, diisobutyl ketone, cyclohexanone, Ketones such as methylcyclohexanone and isophorone, esters such as methyl acetate, e
  • Cyclic unsaturated hydrocarbons such as nitrogen-containing heterocycles, cyclohexene, cycloheptene, cyclooctene, 1,1,3,5,7-cyclooctatetraene and cyclododecene, aromatic carbonization such as benzene, toluene, xylene and mesitylene Examples thereof include hydrogens. These organic solvents may be used alone or in combination of two or more.
  • the reaction atmosphere is preferably an inert gas atmosphere such as nitrogen or argon.
  • the reaction pressure may be either atmospheric pressure or increased pressure, but it is preferably atmospheric pressure in view of workability.
  • the reaction can be carried out by charging the raw materials once or in a divided manner into a reactor equipped with a stirring blade and then reacting them at a predetermined temperature.
  • the reaction temperature during the polymerization is preferably 60 to 240°C, for example 80 to 220°C.
  • the reaction time is preferably 0.1 to 100 hours, for example 0.5 to 30 hours.
  • the active energy ray-curable composition of the present invention contains the above-mentioned styrene-acrylate copolymer, and optionally contains a monomer having a radical-polymerizable double bond and a polymerization initiator. It includes.
  • the content of the styrene-acrylate copolymer in the active energy ray-curable composition may be in the range of 1 to 50% by weight, preferably in the range of 1 to 40% by weight.
  • a styrene-acrylate copolymer if necessary, a monomer having a radical-polymerizable double bond, and a polymerization initiator are mixed, and the temperature is set to 25 to 120° C. It can be obtained by dissolving in an air atmosphere for 0.5 to 2 hours.
  • the content of the monomer having a radical-polymerizable double bond in the resin composition of the present invention is 40 to 90% by weight, preferably 50 to 90% by weight.
  • a compound containing a (meth)acrylate group can be exemplified, and specifically, the following can be exemplified.
  • Examples of monofunctional acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, dodecyl (meth)acrylate and stearyl (meth)acrylate.
  • alkyl (meth)acrylates having 1 to 18 carbon atoms, and further benzyl (meth)acrylate, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, tricyclodecane monomethylol (meth)acrylate, 2-hydroxyethyl ( (Meth)acrylate, 2-hydroxypropyl(meth)acrylate, 3-hydroxypropyl(meth)acrylate, 2-hydroxybutyl(meth)acrylate, 4-hydroxybutyl(meth)acrylate, hydroxypentyl(meth)acrylate, 2-hydroxy -3-phenoxypropyl (meth)acrylate, 2-hydroxy-3-butoxypropyl (meth)acrylate, 2-hydroxy-3-methoxypropyl (meth)acrylate, diethylene glycol mono(meth)acrylate, triethylene glycol mono(meth)acrylate Acrylate, polyethylene glycol mono(meth)acrylate, dipropylene glycol mono(meth)acrylate, poly
  • an alkylene oxide adduct (meth)acrylate of an aliphatic alcohol compound can be exemplified.
  • Alkylene oxide adduct of aliphatic alcohol compound (meth)acrylate Mono- or poly(1-20) alkylene (C2-C20) oxide adduct of aliphatic alcohol compound as a monomer (eg, alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide) , Pentylene oxide, hexylene oxide, etc.) mono- or poly(1-10)(meth)acrylate. More specifically, monofunctional modified acrylate, difunctional modified acrylate, trifunctional modified acrylate, tetrafunctional modified acrylate and the like can be mentioned.
  • an alkylene oxide adduct (meth)acrylate having a carbon number of 2 to 20, for example, methanol mono- or poly(1-20) alkylene (C2 to C20) oxide adduct (for example, ethylene oxide or propylene oxide as the alkylene oxide) is used.
  • poly(1-20) alkylene (C2-C20) oxide of butylphenol, octylphenol, nonylphenol or dodecylphenol examples thereof include adducts (ethylene oxide, propylene oxide, butylene oxide as alkylene oxide) (meth)acrylate and the like.
  • ethylene glycol mono- or poly(1-20) alkylene (C2-C20) oxide adduct eg, alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide) di(meth)acrylate, diethylene glycol mono- or poly( 2-20) Alkylene (C2-C20) oxide adduct (eg, alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide) di(meth)acrylate, triethylene glycol poly(2-20) alkylene (C2-C20) oxide addition Body (as alkylene oxide, for example, ethylene oxide, propylene oxide, butylene oxide) di(meth)acrylate, polyethylene glycol poly(2-20) alkylene (C2-C20) oxide adduct (for example, as alkylene oxide, ethylene oxide, propylene oxide, Butylene oxide) di(meth)acrylate, propylene glycol poly(2-20) alkylene (C2-C20) oxide adduct (for example, as
  • the oxide include ethylene oxide, propylene oxide, butylene oxide)tri(meth)acrylate, trimethylolhexane poly(2-20)alkylene (C2 to C20) oxide adduct (as the alkylene oxide, for example, ethylene oxide, propylene oxide, butylene).
  • a pentaerythritol poly(2-20) alkylene(C2-C20) oxide adduct eg, ethylene oxide, propylene oxide, butylene oxide
  • a ditrimethylolpropane poly(2 To 20) alkylene (C2 to C20) oxide adduct eg, alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide) tetra(meth)acrylate, ditrimethylolpropane poly(2-20) alkylene oxide (eg, ethylene oxide, propylene oxide) , Butylene oxide, etc.) tetra(meth)acrylate, ditrimethylolpropane tetracaprolactonate, tetra(meth)acrylate, ditrimethylolethane poly(2-20)alkylene (C2-C20) oxide adduct (for example, ethylene oxide as alkylene oxide) Oxide, propylene oxide, butylene oxide
  • Alkylene oxide eg ethylene oxide, propylene oxide, butylene oxide, etc.
  • tetra(meth)acrylate ditrimethylolhexane poly(2-20) alkylene (C2-C20) oxide adduct (eg, as alkylene oxide, ethylene oxide, propylene oxide) , Butylene oxide) tetra(meth)acrylate, ditrimethylolhexane poly(2-20) alkylene oxide (eg ethylene oxide, propylene oxide, butylene oxide, etc.) tetra(meth)acrylate, ditrimethylol octane (2-20) alkylene (C2 To C20) oxide adduct (eg, alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide) tetra(meth)acrylate, ditrimethylol octane poly(4-200) alkylene oxide (eg, ethylene oxide, propylene oxide, butylene oxide, etc.
  • Alkylene (C2 to C20) oxide adduct eg, alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide) hexa(meth)acrylate, tripentaerythritol polyalkylene oxide hepta(meth)acrylate, tripentaerythritol poly(2 to 20) Alkylene (C2-C20) oxide adducts
  • alkylene oxides include ethylene oxide, propylene oxide, butylene oxide) octa(meth)acrylate, but the present invention is not limited thereto.
  • an active energy ray-curable (meth)acrylic oligomer an active energy ray-curable (meth)acrylic oligomer, urethane (meth)acrylate, epoxy (meth)acrylate, polyester (meth)acrylate can be appropriately used.
  • oligomers examples include polyols, esterified products of polybasic acid and (meth)acrylic acid, and epoxy acrylate.
  • polyol ethylene glycol, glycerin, trimethylolpropane, pentaerythritol, etc.
  • polybasic acid phthalic anhydride, isophthalic acid, (anhydrous) succinic acid, (anhydrous) maleic acid, adipic acid, sebacic acid, etc. are used.
  • the ester reaction of the polyol, polybasic acid and (meth)acrylic acid is carried out by a conventional method.
  • urethane (meth)acrylate general aromatic or aliphatic urethane (meth)acrylate can be mentioned.
  • (meth)acrylates such as tolylene diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate.
  • epoxy (meth)acrylate examples include general aromatic or aliphatic epoxy (meth)acrylate.
  • examples thereof include (meth)acrylates such as bisphenol A epoxy, bisphenol F epoxy, novolac epoxy, and phosphoric acid type epoxy.
  • polyester (meth)acrylates examples include general polyester (meth)acrylates, fatty acid-modified types, chlorinated polyesters, and the like.
  • a bifunctional acrylate, a trifunctional acrylate, a tetrafunctional or higher acrylate, and a trifunctional modified acrylate are preferable.
  • the active energy ray-curable composition of the present invention may contain a polymerization initiator.
  • the polymerization initiator can be used without limitation. It is particularly preferable to contain a photopolymerization initiator.
  • the amount of the polymerization initiator compounded in the active energy ray-curable composition in the present invention is 0.1 to 15 parts by weight, based on 100 parts by weight of the total of the styrene-acrylate copolymer and the monomer having a radical-polymerizable double bond. It is preferably in the range of 0.5 part by weight, more preferably in the range of 0.5 to 10 parts by weight.
  • photopolymerization initiator examples include, but are not limited to, benzophenones such as benzyl, benzophenone, p-methylbenzophenone, Michler's ketone, methylbenzophenone, 4,4′-dichlorobenzophenone, 4,4′-bisdiethylaminobenzophenone, acetophenone.
  • benzophenones such as benzyl, benzophenone, p-methylbenzophenone, Michler's ketone, methylbenzophenone, 4,4′-dichlorobenzophenone, 4,4′-bisdiethylaminobenzophenone, acetophenone.
  • acetophenones, alkylphenones, acylphosphine oxides, oxyphenyls and oxime ester benzoins are preferable, and acetophenones and alkylphenones are more preferable.
  • These photopolymerization initiators may be used alone or in combination of two or more kinds. Further, it is possible to use a photopolymerization initiator and a sensitizer together.
  • Sensitizers include 2,4,6-trimethylbenzophenone, 2,3,4-trimethylbenzophenone, 4-phenylbenzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 4-(1,3-acryloyl- 1,4,7,10,13-pentaoxotridecyl)benzophenone, methyl-o-benzoylbenzoate, [4-(methylphenylthio)phenyl]phenylmethanone, (4-benzoylbenzyl)trimethylammonium chloride, 2- Hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxy-cyclohexyl-phenylketone, 2 -Hydroxy-2-methyl-1-styrylpropan-1-one polymer, diethoxyacetophenone, dibutoxyacetophenone, benzoin methyl ether, be
  • Examples of the active energy ray used for curing the active energy ray-curable composition of the present invention include ultraviolet rays, electron rays, ⁇ rays, ⁇ rays, ⁇ rays, X rays, and other polymerizable components in the composition.
  • it is not particularly limited as long as it can provide energy necessary for proceeding the polymerization reaction of the monomer having a radical-polymerizable double bond.
  • a polymerization initiator is used. The polymerization reaction can proceed even without the use of H.
  • UV-LED ultraviolet light emitting diode
  • UV-LD ultraviolet laser diode
  • the active energy ray-curable composition of the present invention contains various additives, for example, stabilizers (for example, polymerization inhibitors such as hydroquinone, metoquinone, and methylhydroquinone), and pigments such as inorganic pigments and organic pigments.
  • stabilizers for example, polymerization inhibitors such as hydroquinone, metoquinone, and methylhydroquinone
  • pigments such as inorganic pigments and organic pigments.
  • inorganic pigments include yellow lead, zinc yellow, navy blue, barium sulfate, cadmium red, titanium oxide, zinc white, rouge, alumina white, calcium carbonate, ultramarine blue, carbon black, graphite, aluminum powder, and red iron oxide.
  • Is a soluble azo pigment such as ⁇ -naphthol-based, ⁇ -oxynaphthoic acid-based, ⁇ -oxynaphthoic acid-based anilide-based, acetoacetic anilide-based, pyrazolone-based, ⁇ -naphthol-based, ⁇ -oxynaphthoic acid-based anilide-based, Insoluble azo pigments such as acetoacetic anilide monoazo, acetoacetic anilide disazo, and pyrazolone, phthalocyanine pigments such as copper phthalocyanine blue, halogenated (chlorine or brominated) copper phthalocyanine blue, sulfonated copper phthalocyanine blue, and metal-free phthalocyanine , Quinacridone, dioxazine, slene (pyrantron, anthanthrone, indanthrone, anthrapyrimidine, flavantron,
  • additives for imparting abrasion resistance, anti-blocking property, sliding property, and anti-scratch property natural waxes such as carnauba wax, wood wax, lanolin, montan wax, paraffin wax, microcrystalline wax, and Fischer-Tropsch wax.
  • natural waxes such as carnauba wax, wood wax, lanolin, montan wax, paraffin wax, microcrystalline wax, and Fischer-Tropsch wax.
  • examples thereof include polyethylene wax, polypropylene wax, polytetrafluoroethylene wax, polyamide wax, and synthetic wax such as silicone compound.
  • additives such as ultraviolet absorbers, infrared absorbers, antibacterial agents, etc. can be added depending on the required performance.
  • a pigment which is a colorant is not contained, and a transparent constitution results in an overprint varnish.
  • a color printing ink is formed.
  • a binder resin other than the styrene-acrylate copolymer can be used if necessary.
  • binder resin other than the styrene-acrylate copolymer diallyl phthalate resin, polyester, polyvinyl chloride, poly(meth)acrylic acid ester, epoxy resin, polyurethane resin, petroleum (based) resin, cellulose derivative (eg, ethyl cellulose, Cellulose acetate, nitrocellulose), vinyl chloride/vinyl acetate copolymers, polyamide resins, polyvinyl acetal resins, synthetic rubbers such as butadiene-acrylonitrile copolymers. These resins may be used alone or in combination of two or more.
  • the method for producing the active energy ray-curable composition of the present invention may be carried out in the same manner as in the conventional active energy ray-curable composition.
  • the styrene-acrylate copolymer of the present invention can be used at room temperature to 100°C.
  • Polymer if necessary, a monomer having a radical-polymerizable double bond, a composition component such as a polymerization initiator and a sensitizer, and other additives, a kneader, a triple roll, an attritor, a sand mill, a gate mixer, etc.
  • Examples of the printing method using the active energy ray-curable composition of the present invention include lithographic printing (normal lithographic printing using dampening water and waterless lithographic printing not using dampening water), letterpress printing, intaglio printing, Examples include stencil printing, preferably lithographic printing.
  • the base material for the printed matter is not particularly limited, and examples thereof include printing on various materials such as paper, plastics, stickers, labels and metals, and printing on paper is preferable.
  • part represents a “weight part”
  • % represents the “weight%.”
  • Mw weight average molecular weight
  • Mn number average molecular weight
  • Mw/Mn molecular weight distribution
  • Iodine value measurement The iodine value of the styrene-acrylate copolymer used for production was measured according to the method specified in JIS K6235.
  • Example 1 shows the copolymers 1 and 2 obtained in Synthesis Example 1 and Synthesis Example 2, a monomer having a radical-polymerizable double bond, and a polymerization inhibitor. Each composition amount described was added, and heated and mixed at 90° C. for 2 hours to prepare an active energy ray-curable composition. After cooling each composition to room temperature (25° C.), it was allowed to stand overnight, and the solubility was confirmed by its transparent appearance. Those that had a transparent appearance even after cooling were evaluated as ⁇ , and those that became cloudy: as ⁇ . The results of Example 1 are shown in Table 1. The results of Comparative Example 1 are shown in Table 2.
  • the components other than the copolymer 1 shown in Table 1 are as follows. Further, the composition amounts shown in Table 1 are expressed in parts by weight. *1: DTMPTA: MIWON MIRAMER M410 ditrimethylolpropane tetraacrylate *2: 3PO-TMPTA: Sartomer Co., Ltd. SR492TFN propylene oxide modified trimethylolpropane triacrylate *3: TPGDA: Sartomer Co., Ltd.
  • SR306H tripropylene glycol diacrylate * 4 TMPTA: manufactured by MIWON MIRAMER M300 trimethylolpropane triacrylate *5: 3EO-TMPTA: manufactured by MIWON MIRAMER M3130 ethylene oxide-modified trimethylolpropane triacrylate *6: methylhydroquinone: manufactured by Wako Pure Chemical Industries, Ltd.
  • the components other than the copolymer 2 shown in Table 2 are the same as those in Table 1. Further, the composition amounts shown in Table 2 are expressed in parts by weight.
  • Example 2 and Comparative Example 2 1) Dryability test An active energy ray-curable composition prepared from each component listed in Table 3 was coated on a piece of art paper (art paper manufactured by Oji Paper Co., Ltd.) using an RI tester, and the output was 80 W/cm. It was cured with a metal halide lamp (lamp distance 11 cm, conveyor speed 100 m/min).
  • a metal halide lamp lamp distance 11 cm, conveyor speed 100 m/min.
  • As the UV curing device a conveyor type ultraviolet curing device manufactured by Eye Graphics Co., Ltd. was used. The coating film was touched with a finger and passed multiple times until no fingerprints were left on the surface (tack free). When the coating film was touched with a finger after UV irradiation was performed 5 times, the surface was not fingerprinted: ⁇ , the surface was fingerprinted: x.
  • Table 3 The evaluation results are shown in Table 3.
  • the components other than the copolymers 1 and 2 shown in Table 3 are as follows.
  • the composition amounts shown in Table 3 are expressed in parts by weight.
  • the active energy ray-curable composition containing the styrene-acrylate copolymer of the present invention was shown to have excellent drying property, scratch property and adhesiveness.
  • Example 3 Evaluation of physical properties when using an active energy ray-curable composition as an ink 30 parts by weight of the copolymer 1 produced in Synthesis Example 1, 70 parts by weight of DTMPTA, and 0.1 parts by weight of methylhydroquinone were mixed to obtain an active energy. A line-curable composition was prepared. Furthermore, an ink was prepared with the compounding amounts of the respective components shown in Table 4. Various physical properties of the obtained ink were acquired by the evaluation methods described below.
  • the active energy ray-curable composition containing the styrene-acrylate copolymer of the present invention has excellent adhesion to a substrate such as paper, and when used as an ink, the curability and the adhesion are excellent. Since it is excellent in physical properties such as scratch resistance, it is useful for various printing inks, paints, coating agents, photoresists and the like.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Polymerisation Methods In General (AREA)
  • Paints Or Removers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

L'objet de la présente invention est de fournir : un copolymère de styrène-acrylate qui permet d'obtenir d'excellentes propriétés physiques lorsqu'il est utilisé dans une encre ; et une composition durcissable par rayonnement d'énergie active contenant le copolymère.　La présente invention concerne un copolymère de styrène-acrylate caractérisé en ce que la proportion d'un motif constitutif (A) dérivé d'un composé styrène est de 10 à 90 % en moles, la proportion d'un motif constitutif (B) dérivé d'un composé acrylate est de 10 à 90 % en moles et le motif constitutif (B) dérivé d'un composé acrylate comprend un motif constitutif (b-1) dérivé d'un composé comprenant au moins trois groupes acryloyle par molécule associée.
PCT/JP2018/046190 2018-12-14 2018-12-14 Copolymère de styrène-acrylate Ceased WO2020121534A1 (fr)

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PCT/JP2018/046190 WO2020121534A1 (fr) 2018-12-14 2018-12-14 Copolymère de styrène-acrylate

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JP2022099528A (ja) * 2020-12-23 2022-07-05 Ｋｊケミカルズ株式会社 活性エネルギー線硬化性樹脂組成物

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CN116589640A (zh) * 2019-01-30 2023-08-15 株式会社大阪曹達 光固化性树脂组合物、油墨及涂料

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JPH05307102A (ja) * 1992-04-30 1993-11-19 Kureha Chem Ind Co Ltd 光学レンズ
JP2006274266A (ja) * 1995-04-12 2006-10-12 Eastman Chem Co 水性コーティング組成物
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JPH04252214A (ja) * 1990-12-26 1992-09-08 Akira Matsumoto （メタ）アクリロイル基を側鎖に有するビニル重合体
JPH05307102A (ja) * 1992-04-30 1993-11-19 Kureha Chem Ind Co Ltd 光学レンズ
JP2006274266A (ja) * 1995-04-12 2006-10-12 Eastman Chem Co 水性コーティング組成物
JP2007199207A (ja) * 2006-01-24 2007-08-09 Mitsubishi Rayon Co Ltd 粉砕トナー用スチレン−アクリル樹脂および粉砕トナー。

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2022099528A (ja) * 2020-12-23 2022-07-05 Ｋｊケミカルズ株式会社 活性エネルギー線硬化性樹脂組成物
JP7683906B2 (ja) 2020-12-23 2025-05-27 Ｋｊケミカルズ株式会社 活性エネルギー線硬化性樹脂組成物

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