WO2022107402A1 - （メタ）アクリル系共重合体、（メタ）アクリル系共重合体組成物およびインク - Google Patents

（メタ）アクリル系共重合体、（メタ）アクリル系共重合体組成物およびインク Download PDF

Info

Publication number
WO2022107402A1
WO2022107402A1 PCT/JP2021/029243 JP2021029243W WO2022107402A1 WO 2022107402 A1 WO2022107402 A1 WO 2022107402A1 JP 2021029243 W JP2021029243 W JP 2021029243W WO 2022107402 A1 WO2022107402 A1 WO 2022107402A1
Authority
WO
WIPO (PCT)
Prior art keywords
meth
acrylic copolymer
mercaptan
derived
ink
Prior art date
Application number
PCT/JP2021/029243
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
倫仁 小林
Original Assignee
三菱ケミカル株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 三菱ケミカル株式会社 filed Critical 三菱ケミカル株式会社
Priority to JP2022563580A priority Critical patent/JPWO2022107402A1/ja
Priority to CN202180067390.2A priority patent/CN116390960A/zh
Publication of WO2022107402A1 publication Critical patent/WO2022107402A1/ja

Links

Classifications

    • 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
    • C08F220/00—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
    • 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

Definitions

  • the present invention relates to (meth) acrylic copolymers, (meth) acrylic copolymer compositions and inks.
  • water-based inks can reduce the amount of volatile organic compounds (VOCs), and can reduce the risk of fire and toxicity such as mutagenicity. Therefore, water-based inks are widely used in applications such as gravure printing.
  • VOCs volatile organic compounds
  • acrylic polymers and (meth) acrylic copolymers containing (meth) acrylic acid alkyl ester-derived structural units and (meth) acrylic acid-derived structural units have high transparency and pigments. Because of its good color development, it is widely used in water-based ink applications.
  • the (meth) acrylic polymer and (meth) acrylic copolymer for water-based inks have good solubility in alkaline water, the total amount of VOC at the time of dissolution can be suppressed to a small level, and the storage stability of the ink is stable. Good properties and good concealment during film printing are required.
  • Patent Document 1 a polycarboxylic acid resin and a polyol resin produced by solution polymerization using polyfunctional mercaptan are condensed in a solvent different from the polymerization solvent, and then neutralized with an amine at 95 ° C.
  • Patent Document 2 describes a method for obtaining an aqueous pigment dispersion having high storage stability by introducing a hydrophobic moiety and a hydrophilic moiety into a polyfunctional mercaptan prepared in a solution.
  • the present invention includes a (meth) acrylic copolymer having good solubility in alkaline water, good storage stability of ink, and good concealment in film printing; the above-mentioned (meth) acrylic copolymer ( It is an object of the present invention to provide an ink containing a (meth) acrylic copolymer composition; and the (meth) acrylic copolymer composition.
  • the present invention has the following aspects.
  • It has a structural unit derived from a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms, a structural unit derived from an acid group-containing vinyl compound, and a chemical structure derived from a trifunctional or higher functional mercaptan.
  • it is a (meth) acrylic copolymer that is a solid in the form of particles.
  • It has a structural unit derived from a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms, a structural unit derived from an acid group-containing vinyl compound, and a chemical structure derived from trifunctional or higher mercaptan.
  • a (meth) acrylic copolymer further comprising one or more chemical structures selected from the group consisting of monofunctional mercaptan-derived chemical structures and bifunctional mercaptan-derived chemical structures.
  • (Meta) acrylic copolymer [6] The (meth) acrylic copolymer according to any one of [1] to [5], wherein the (meth) acrylic copolymer has a mass average particle size of 20 to 2000 ⁇ m. [7] The (meth) acrylic copolymer according to any one of [1] to [6], wherein the (meth) acrylic copolymer has a water content of 0.01 to 10% by mass.
  • the (meth) acrylic copolymer and the (meth) acrylic copolymer having good solubility in alkaline water and good storage stability of ink and good concealment in film printing can be obtained. It is possible to provide an ink containing the (meth) acrylic copolymer composition containing the (meth) acrylic copolymer composition and the (meth) acrylic copolymer composition.
  • (meth) acrylic acid is a general term for acrylic acid and methacrylic acid.
  • (Meta) acrylic is a general term for acrylic and methacrylic.
  • the "(meth) acrylic copolymer” is, for example, a copolymer having at least one of an acryloyl group and a methacryloyl group.
  • (meth) acrylate is a general term for acrylate and methacrylate.
  • the ratio of each structural unit of the (meth) acrylic copolymer and the ratio of the chemical structure derived from mercaptan mean those calculated from the mass ratio of each monomer used as the polymerization raw material and mercaptan. ..
  • the term “room temperature” means a temperature within the range of 23 ° C. ⁇ 2 ° C. unless otherwise specified.
  • the (meth) acrylic copolymer according to the first aspect of the present invention is also referred to as a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms (hereinafter, also referred to as “monomer (a)”. ), A structural unit derived from an acid group-containing vinyl compound (hereinafter, also referred to as “monomer (b)”), and a chemical structure derived from a trifunctional or higher functional mercaptan.
  • the (meth) acrylic copolymer of the first aspect further preferably has one or more chemical structures selected from the group consisting of a monofunctional mercaptan-derived chemical structure and a bifunctional mercaptan-derived chemical structure. .. Further, the (meth) acrylic copolymer has a structure derived from a monomer other than the monomer (a) and the monomer (b) (hereinafter, also referred to as “monomer (c)”). It may have more units.
  • the (meth) acrylic copolymer of the second aspect of the present invention has a structural unit derived from the monomer (a), a structural unit derived from the monomer (b), and a chemistry derived from trifunctional or higher functional mercaptan. It has a structure and further has one or more chemical structures selected from the group consisting of a monofunctional mercaptan-derived chemical structure and a bifunctional mercaptan-derived chemical structure. Further, the (meth) acrylic copolymer of the second aspect may further have a structural unit derived from the monomer (c).
  • the (meth) acrylic copolymer of the first aspect and the second aspect of the present invention is a structural unit derived from a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms, that is, a single amount. It has a structural unit derived from the body (a).
  • Examples of the monomer (a) in the (meth) acrylic copolymer of the first aspect and the second aspect include methyl (meth) acrylate, ethyl (meth) acrylate, and n- (meth) acrylate.
  • Examples thereof include hexyl, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and isooctyl (meth) acrylate.
  • methyl (meth) acrylate, n-butyl (meth) acrylate, and acrylic acid are available because the (meth) acrylic copolymer has better solubility in alkaline water and is easily available.
  • 2-Ethylhexyl is preferred. These may be used alone or in combination of two or more.
  • the proportion of the structural unit derived from the monomer (a) in the (meth) acrylic copolymer of the first aspect and the second aspect is the structural unit derived from the monomer (a) and the monomer (b).
  • the structural unit derived from the monomer (a) and the monomer (b) are the structural unit derived from the monomer (a) and the monomer (b).
  • 60 to 97% by mass is preferable, and 80 to 95% by mass is more preferable.
  • the lower and upper limits of these numerical ranges can be combined arbitrarily.
  • the ratio of the structural unit derived from the monomer (a) is within the above range, the film forming property and the water resistance of the ink are good.
  • the (meth) acrylic copolymer of the first aspect and the second aspect of the present invention has a structural unit derived from an acid group-containing vinyl compound, that is, a structural unit derived from the monomer (b).
  • the monomer (b) include vinyl compounds having an acid group such as carboxylic acid or sulfonic acid.
  • Specific examples of the vinyl compound having a carboxylic acid group in the (meth) acrylic copolymer of the first aspect and the second aspect include monobasic acids such as (meth) acrylic acid and crotonic acid; fumaric acid and malein. Bibasic acids such as acids and itaconic acids; partial esters of these dibasic acids and the like can be mentioned.
  • vinyl compound having a sulfonic acid group examples include vinyl sulfonic acid, 2-acrylamide-2-methylpropanesulfonic acid and the like.
  • a vinyl compound having a carboxylic acid group is preferable, and (meth) acrylic acid is more preferable, from the viewpoint of improving the water solubility of the (meth) acrylic copolymer.
  • These may be used alone or in combination of two or more.
  • the proportion of the structural unit derived from the monomer (b) in the (meth) acrylic copolymer of the first aspect and the second aspect is the structural unit derived from the monomer (a) and the monomer (b).
  • the structural unit derived from the monomer (a) and the monomer (b) Of the total 100% by mass of the derived constituent units, 3 to 40% by mass is preferable, and 5 to 20% by mass is more preferable.
  • the lower and upper limits of these numerical ranges can be combined arbitrarily.
  • the ratio of the structural unit derived from the monomer (b) is within the above range, the solubility of the (meth) acrylic copolymer in alkaline water and the solubility in other solvents are better.
  • the total ratio of the structural unit derived from the monomer (a) and the structural unit derived from the monomer (b) in the (meth) acrylic copolymer of the first aspect and the second aspect is the (meth) acrylic system. 70 to 99.9% by mass is preferable, 80 to 99% by mass is more preferable, and 85 to 95% by mass is further preferable with respect to the total mass of all the constituent units constituting the copolymer.
  • the lower and upper limits of these numerical ranges can be combined arbitrarily.
  • the total ratio of the structural unit derived from the monomer (a) and the structural unit derived from the monomer (b) is within the above range, the solubility in alkaline water is extremely good.
  • the total mass of all the structural units constituting the (meth) acrylic copolymer of the first aspect and the second aspect also includes the ratio of the chemical structure derived from metacaptan, which will be described later.
  • the (meth) acrylic copolymer of the first aspect and the second aspect has a chemical structure derived from a trifunctional or higher functional mercaptan.
  • a trifunctional or higher functional mercaptan as a chain transfer agent in the polymerization reaction when producing the (meth) acrylic copolymer of the first aspect and the second aspect, the trifunctional or higher functionality is used.
  • the mercaptan of the above becomes the starting point of the polymerization, and the chemical structure derived from the trifunctional or higher mercaptan is introduced into the (meth) acrylic copolymer.
  • a trifunctional or higher functional mercaptan is a compound having three or more mercapto groups in a single molecule.
  • Examples of the trifunctional or higher functional mercaptan in the (meth) acrylic copolymer of the first aspect and the second aspect include 1,2,3-trimercaptopropane and 2,2-bis (mercaptomethyl) -1-.
  • trimethylol propanthris (3-mercaptopropionate) and pentaerythritol tetrakis (3) are available because the (meth) acrylic copolymer has better solubility in alkaline water and is easily available.
  • -Mercaptopropionate pentaerythritol tetrakis (thioglycolate) are preferred. These may be used alone or in combination of two or more.
  • the proportion of the chemical structure derived from the trifunctional or higher mercaptan in the (meth) acrylic copolymer of the first aspect and the second aspect is derived from all the monomers constituting the (meth) acrylic copolymer. 0.1 to 20 parts by mass is preferable, and 1 to 6 parts by mass is more preferable with respect to a total of 100 parts by mass of the constituent units.
  • the lower and upper limits of these numerical ranges can be combined arbitrarily.
  • the proportion of the chemical structure derived from the trifunctional or higher mercaptan is at least the above lower limit, the solubility of the (meth) acrylic copolymer in alkaline water tends to be better.
  • the ratio of the chemical structure derived from the trifunctional or higher mercaptan is not more than the above upper limit value, the odor of the (meth) acrylic copolymer is suppressed.
  • the (meth) acrylic copolymer of the first aspect is selected from the group consisting of a chemical structure derived from a trifunctional or higher functional mercaptan, a chemical structure derived from a monofunctional mercaptan, and a chemical structure derived from a bifunctional mercaptan. It is preferable to further have one or more chemical structures. If the (meth) acrylic copolymer of the first aspect further has one or more chemical structures selected from the group consisting of monofunctional mercaptan-derived chemical structures and bifunctional mercaptan-derived chemical structures, alkaline water. The viscosity at the time of dissolution in is lowered, and it becomes easy to mix pigments and the like.
  • the (meth) acrylic copolymer of the second aspect has a chemical structure derived from a trifunctional or higher mercaptan, a chemical structure derived from a trifunctional or higher mercaptan, and a chemical structure derived from a monofunctional mercaptan. It further has one or more chemical structures selected from the group consisting of bifunctional mercaptan-derived chemical structures. Therefore, according to the (meth) acrylic copolymer of the second aspect, the viscosity at the time of dissolution in alkaline water becomes low, and the compounding of a pigment or the like becomes easy.
  • a monofunctional mercaptan is a compound having one mercapto group in a single molecule.
  • Examples of the monofunctional mercaptan in the (meth) acrylic copolymer of the first aspect and the second aspect include n-octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, n-butyl mercaptan, and thioglycolic acid.
  • the proportion of the chemical structure derived from the monofunctional mercaptan in the (meth) acrylic copolymer of the first aspect and the second aspect is the composition derived from all the monomers constituting the (meth) acrylic copolymer. 0.1 to 20 parts by mass is preferable, and 1 to 6 parts by mass is more preferable with respect to a total of 100 parts by mass of the unit.
  • the lower and upper limits of these numerical ranges can be combined arbitrarily.
  • the ratio of the chemical structure derived from the monofunctional mercaptan is at least the above lower limit, the solubility of the (meth) acrylic copolymer in alkaline water tends to be better.
  • the ratio of the chemical structure derived from the monofunctional mercaptan is not more than the above upper limit value, the odor of the (meth) acrylic copolymer is suppressed.
  • a bifunctional mercaptan is a compound having two mercapto groups in a single molecule.
  • the bifunctional mercaptan in the (meth) acrylic copolymer of the first aspect and the second aspect include 1,4-dimercaptobutane, 3-oxo-1,5-pentanedithiol, and 3-thia-. Examples thereof include 1,5-pentanedithiol, ethylene glycol bis (3-mercaptopropionate), and 1,4-butanediol bis (thioglycolate). These may be used alone or in combination of two or more.
  • the proportion of the chemical structure derived from the bifunctional mercaptan in the (meth) acrylic copolymer of the first aspect and the second aspect is the composition derived from all the monomers constituting the (meth) acrylic copolymer. 0.1 to 20 parts by mass is preferable, and 1 to 6 parts by mass is more preferable with respect to a total of 100 parts by mass of the unit.
  • the lower and upper limits of these numerical ranges can be combined arbitrarily.
  • the ratio of the chemical structure derived from the bifunctional mercaptan is at least the above lower limit, the solubility of the (meth) acrylic copolymer in alkaline water tends to be better.
  • the ratio of the chemical structure derived from the bifunctional mercaptan is not more than the above upper limit value, the odor of the (meth) acrylic copolymer is suppressed.
  • the (meth) acrylic copolymer of the first aspect and the second aspect is a structural unit derived from the monomer (a) and a structural unit derived from the monomer (b), as well as other monomers. It may further have a structural unit derived from (monomer (c)).
  • the monomer (c) in the (meth) acrylic copolymer of the first aspect and the second aspect is also referred to as a compound having one polymerizable double bond (hereinafter, “monomer (c1)”). ), Compounds having two or more polymerizable double bonds (hereinafter, also referred to as “monomer (c2)”) and the like can be mentioned.
  • the monomer (c2) is preferable as the monomer (c). That is, the (meth) acrylic copolymer further has a structural unit derived from the monomer (c2) in addition to the structural unit derived from the monomer (a) and the structural unit derived from the monomer (b). Is preferable.
  • Examples of the monomer (c1) in the (meth) acrylic copolymer of the first aspect and the second aspect include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, and ⁇ -methylstyrene.
  • the proportion of the structural unit derived from the monomer (c1) in the (meth) acrylic copolymer of the first aspect and the second aspect is the structural unit derived from the monomer (a) and the monomer (b). 0.1 to 20 parts by mass is preferable, and 1 to 6 parts by mass is more preferable with respect to a total of 100 parts by mass of the derived constituent units.
  • the lower and upper limits of these numerical ranges can be combined arbitrarily.
  • the ratio of the structural unit derived from the monomer (c1) is at least the above lower limit value, the storage stability of the ink tends to be better.
  • the ratio of the structural unit derived from the monomer (c1) is not more than the above upper limit value, the viscosity of the ink can be lowered and the handling at the time of printing becomes good.
  • Examples of the monomer (c2) in the (meth) acrylic copolymer of the first aspect and the second aspect include ethylene glycol di (meth) acrylate, 1,2-propylene glycol di (meth) acrylate, and 1 , 4-Butandiol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,4-cyclohexanedimethanol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) ) Acrylate, 1,3-propylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropanetri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, bisphenol A-di (meth) acrylate, 2,2-
  • ethylene glycol diacrylate, 1,6-hexanediol di (meth) acrylate, and trimethylolpropane tri (meth) are low in viscosity when dissolved in alkaline water and can be easily blended with pigments.
  • Acrylate is preferred. These may be used alone or in combination of two or more.
  • the proportion of the structural unit derived from the monomer (c2) in the (meth) acrylic copolymer of the first aspect and the second aspect is the structural unit derived from the monomer (a) and the monomer (b). 0.1 to 20 parts by mass is preferable, and 1 to 6 parts by mass is more preferable with respect to a total of 100 parts by mass of the derived constituent units.
  • the lower and upper limits of these numerical ranges can be combined arbitrarily.
  • the ratio of the structural unit derived from the monomer (c2) is at least the above lower limit value, the storage stability of the ink tends to be better.
  • the ratio of the structural unit derived from the monomer (c2) is not more than the above upper limit value, the viscosity of the ink can be lowered and the handling at the time of printing becomes good.
  • the (meth) acrylic copolymer of the first aspect is solid at room temperature. Since the (meth) acrylic copolymer of the first aspect is solid at room temperature, VOC when dissolved in alkaline water can be reduced. In addition, it is suitable for transportation and storage because it can suppress the increase in volume as compared with the state of being dissolved in water (aqueous solution) and the state of being dispersed in water (dispersion liquid).
  • the (meth) acrylic copolymer of the second aspect is also preferably solid at room temperature. When the (meth) acrylic copolymer of the second aspect is solid at room temperature, VOC when dissolved in alkaline water can be reduced.
  • the solid (meth) acrylic copolymer includes powder-like, plate-like, crushed-like, spherical, particle-like, granular, and pellet-like solids. Among these, powdery, crushed, spherical, particulate, and granular solids are preferable because they are easy to handle when dissolved in a solvent or alkaline water.
  • the (meth) acrylic copolymer of the first aspect and the second aspect can be easily dissolved in water or a mixed solvent of water and an auxiliary solvent described later by neutralizing with a basic compound described later. ..
  • the secondary glass transition temperature (Tg) of the (meth) acrylic copolymer of the first aspect and the second aspect is preferably 35 ° C. or higher, more preferably 40 ° C. or higher, still more preferably 45 ° C. or higher.
  • the secondary glass transition temperature (Tg) of the (meth) acrylic copolymer of the first aspect and the second aspect is preferably 70 ° C. or lower, more preferably 60 ° C. or lower, still more preferably 55 ° C. or lower.
  • the secondary glass transition temperature (Tg) of the (meth) acrylic copolymer of the first aspect and the second aspect can be measured using a differential scanning calorimeter (DSC), and the specific measurement thereof. The method is as described in the section of Examples.
  • the mass average particle size of the (meth) acrylic copolymer of the first aspect and the second aspect is preferably 20 to 2000 ⁇ m, more preferably 50 to 850 ⁇ m, further preferably 80 to 700 ⁇ m, and particularly preferably 150 to 600 ⁇ m. preferable.
  • the lower and upper limits of these numerical ranges can be combined arbitrarily.
  • the mass average particle size of the (meth) acrylic copolymer is at least the above lower limit, the compounding work becomes easy. Further, when the mass average particle size of the (meth) acrylic copolymer is not more than the above upper limit value, the dissolution time in alkaline water is shortened.
  • the mass average particle size of the (meth) acrylic copolymer can be calculated by shaking 20 g of the granular resin for 5 minutes using a standard sieve to classify the (meth) acrylic copolymer.
  • the water content of the (meth) acrylic copolymer of the first aspect and the second aspect is preferably 0.01 to 10% by mass, and 0.02 to 8. 0% by mass is more preferable, 0.1 to 5.0% by mass is further preferable, and 0.5 to 5.0% by mass is particularly preferable.
  • the lower and upper limits of these numerical ranges can be combined arbitrarily. When the water content of the (meth) acrylic copolymer is at least the above lower limit, the solubility in alkaline water is good. Further, when the water content of the (meth) acrylic copolymer is not more than the above upper limit value, the water resistance of the printed matter is high.
  • the handleability of the copolymer when the particulate (meth) acrylic copolymer is obtained is good.
  • the specific method for measuring the water content of the (meth) acrylic copolymer is as described in the section of Examples.
  • the acid value of the (meth) acrylic copolymer of the first aspect and the second aspect is preferably 20 to 140 mgKOH / g, more preferably 50 to 100 mgKOH / g, still more preferably 55 to 90 mgKOH / g.
  • the lower and upper limits of these numerical ranges can be combined arbitrarily.
  • the acid value of the (meth) acrylic copolymer is at least the above lower limit, the solubility in alkaline water becomes better.
  • the acid value of the (meth) acrylic copolymer is not more than the above upper limit, the amount of the basic compound required for neutralization and dissolution can be reduced, and the water resistance of the printed matter is also good.
  • the acid value of the (meth) acrylic copolymer means a value expressed in milligrams of the mass of potassium hydroxide required to neutralize 1 g of the (meth) acrylic copolymer.
  • the acid value of the (meth) acrylic copolymer of the first aspect and the second aspect can be measured by neutralization titration with a potassium hydroxide solution based on the discoloration point of phenolphthalein. The specific measurement method is as described in the section of Examples.
  • the weight average molecular weight (Mw) of the (meth) acrylic copolymer of the first aspect and the second aspect is preferably 15,000 to 80,000, more preferably 15,000 to 60,000, further preferably 20,000 to 60,000, and even more preferably 25,000 to 60,000. Is particularly preferable, and 25,000 to 40,000 is most preferable.
  • the lower and upper limits of these numerical ranges can be combined arbitrarily. When the weight average molecular weight of the (meth) acrylic copolymer is at least the above lower limit, the storage stability of the ink tends to be better.
  • the weight average molecular weight (Mw) of the (meth) acrylic copolymer of the first aspect and the second aspect is the weight average molecular weight (in terms of polystyrene) measured by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • the number average molecular weight (Mn) of the (meth) acrylic copolymer of the first aspect and the second aspect is preferably 5000 to 120000, more preferably 8000 to 80000, still more preferably 12000 to 70000. 15,000 to 60,000 is particularly preferable, and 20,000 to 50,000 is most preferable.
  • the lower and upper limits of these numerical ranges can be combined arbitrarily.
  • the number average molecular weight of the (meth) acrylic copolymer is at least the above lower limit, the storage stability of the ink tends to be better.
  • the number average molecular weight of the (meth) acrylic copolymer is not more than the above upper limit, the viscosity of the ink tends to be low and the film forming property tends to be good.
  • the number average molecular weight (Mn) of the (meth) acrylic copolymer of the first aspect and the second aspect is the number average molecular weight (in terms of polystyrene) measured by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • the (meth) acrylic copolymer of the first aspect and the second aspect can be produced by a known polymerization method such as bulk polymerization, suspension polymerization and emulsion polymerization.
  • a known polymerization method such as bulk polymerization, suspension polymerization and emulsion polymerization.
  • bulk polymerization and suspension polymerization are preferable from the viewpoint that a powder-like polymer, a spherical or particle-like copolymer, which is easy to handle, can be easily obtained.
  • the method for producing the (meth) acrylic copolymer according to the first aspect and the second aspect by suspension polymerization includes a suspension polymerization step, a first dehydration step, a washing step, and a second dehydration step. , It is preferable to have a drying step.
  • suspension polymerization step In the suspension polymerization step, the above-mentioned monomers (a) and (b) and, if necessary, the monomer (c) are dispersed in water and polymerized in the presence of trifunctional or higher mercaptan. This is a step of obtaining the (meth) acrylic copolymer of the first aspect and the second aspect.
  • a known method can be adopted as the method of suspension polymerization.
  • Examples of the polymerization aid that can be used in the production of the (meth) acrylic copolymer of the first aspect and the second aspect include a polymerization initiator, a chain transfer agent, a dispersant, and a dispersion aid.
  • a polymerization initiator e.g., ethylene glycol dimethacrylate
  • a chain transfer agent e.g., ethylene glycol dimethacrylate
  • a dispersant e.g., a dispersant, and a dispersion aid.
  • Examples of the polymerization initiator that can be used in the production of the (meth) acrylic copolymer of the first aspect and the second aspect include 2,2'-azobisisobutyronitrile and 2,2'-azobis (2). -Methylbutyronitrile), benzoyl peroxide, lauroyl peroxide, tert-butylperoxy-2-ethylhexanoate, tert-amylhydroxy-2-ethylhexanoate, tert-hexylperoxy-2-ethylhexanoate , 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate and the like. These may be used alone or in combination of two or more.
  • a mercaptan having at least trifunctionality or higher is used as the chain transfer agent.
  • the chain transfer agent in addition to the trifunctional or higher functional mercaptan, at least one of the above-mentioned monofunctional mercaptan and bifunctional mercaptan may be used in combination.
  • diphenyl disulfide, dibenzyl disulfide, and ⁇ -methylstyrene dimer may be further used in combination. These may be used alone or in combination of two or more.
  • Examples of the dispersant that can be used in the production of the (meth) acrylic copolymer of the first aspect and the second aspect include a surfactant that stably disperses the monomer in water.
  • Examples thereof include copolymers, polyvinyl alcohol, polyvinylpyrrolidone, hydroxyethyl cellulose, hydroxypropyl cellulose and the like. These may be used alone or in combination of two or more.
  • Dispersing aids that can be used in the production of the (meth) acrylic copolymers of the first and second aspects include, for example, sodium sulfate, sodium carbonate, sodium dihydrogen phosphate, disodium hydrogen phosphate, potassium chloride. , Calcium acetate, magnesium sulfate, manganese sulfate and the like. These may be used alone or in combination of two or more.
  • the (meth) acrylic copolymer of the first aspect and the second aspect is obtained in the state of a slurry.
  • (meth) acrylic copolymer particles having a shape close to that of a true sphere can be obtained.
  • the first dehydration step is a step of dehydrating the slurry after suspension polymerization with a dehydrator or the like to separate the (meth) acrylic copolymer particles of the first aspect and the second aspect from the reaction solution.
  • the second dehydration step is a step of dehydrating the (meth) acrylic copolymer particles after the washing step with a dehydrator or the like to separate the (meth) acrylic copolymer particles from the washing liquid.
  • Various dehydrators can be used in each dehydration step, and for example, a centrifugal dehydrator, a device having a mechanism for sucking and removing water on a perforated belt, and the like can be appropriately selected and used.
  • a centrifugal dehydrator a device having a mechanism for sucking and removing water on a perforated belt, and the like can be appropriately selected and used.
  • One dehydrator may be used, two dehydrators of the same model may be prepared and used in each dehydration step, or a plurality of different models of dehydrators may be used. It is possible to appropriately select a model that suits the purpose in terms of product quality, capital investment cost, productivity, operating cost, and the like. When the balance between product quality and production speed is important, it is preferable to use a dedicated dehydrator in each dehydration process.
  • the washing step is to wash the (meth) acrylic copolymer particles separated from the reaction solution.
  • a cleaning method for example, a method of adding a cleaning liquid to the (meth) acrylic copolymer particles dehydrated in the first dehydration step to re-slurry the (meth) acrylic copolymer and stirring and mixing the (meth) acrylic copolymer, and a cleaning function.
  • a cleaning liquid for example, a method of adding a cleaning liquid to the (meth) acrylic copolymer particles dehydrated in the first dehydration step to re-slurry the (meth) acrylic copolymer and stirring and mixing the (meth) acrylic copolymer, and a cleaning function.
  • the type and amount of cleaning liquid may be selected so that the purpose of the cleaning process is achieved.
  • the cleaning liquid include water (ion-exchanged water, distilled water, purified water, etc.), an aqueous solution in which a sodium salt is dissolved, a buffer adjusted to an arbitrary pH, methanol, and the like.
  • the drying step is a step of drying the (meth) acrylic copolymer particles of the first aspect and the second aspect after the second dehydration step. Water remains on the surface of the (meth) acrylic copolymer particles after the second dehydration step. Further, the inside of the (meth) acrylic copolymer is in a state close to saturated water absorption. Therefore, in order to further reduce the water content of the (meth) acrylic copolymer of the first aspect and the second aspect, it is preferable to dry.
  • a dryer that heats under reduced pressure to dry, and (meth) acrylic copolymer particles are simultaneously dried while being air-transported in a tube using warm air.
  • a dryer that performs drying while blowing warm air from the lower side of the perforated plate and flowing the (meth) acrylic copolymer particles on the upper side.
  • the drying step is preferably performed so that the water content of the (meth) acrylic copolymer of the first aspect and the second aspect after the drying step is 0.01 to 10% by mass.
  • the method for producing a (meth) acrylic copolymer by bulk polymerization preferably includes a bulk polymerization step and a pulverization step.
  • a devolatile step may be provided between the bulk polymerization step and the pulverization step.
  • the above-mentioned monomers (a) and (b) and, if necessary, the monomer (c) are polymerized in the presence of trifunctional or higher functional mercaptan, and the first embodiment is carried out. And the step of obtaining the (meth) acrylic copolymer of the second aspect.
  • a known method can be adopted as the bulk polymerization method.
  • the monomer (a) and the monomer (b) and, if necessary, the monomer (c) are polymerized in a reactor having a polymerization temperature control function. Examples thereof include a method of polymerizing in the presence of an auxiliary agent.
  • Examples of the polymerization aid include a polymerization initiator and a chain transfer agent. However, at least the above-mentioned trifunctional or higher functional mercaptan is used as the chain transfer agent.
  • Examples of the polymerization initiator include the polymerization initiator exemplified above in the description of the suspension polymerization step.
  • Examples of the chain transfer agent include the chain transfer agents exemplified above in the description of the suspension polymerization step.
  • the shape of the reactor used in the bulk polymerization step is arbitrary.
  • a glass cell in which a rubber tube having both ends connected to form an annular shape is sandwiched between two tempered glass plates and the four corners are clipped can be used as a reactor.
  • examples of the reactor used industrially include a closed container having a stirring mechanism.
  • the polymerization temperature control function for example, when the glass cell is used as a reactor, a commercially available constant temperature water tank may be used.
  • a closed container having a stirring mechanism When a closed container having a stirring mechanism is used, the temperature can be controlled by exchanging heat with a heat medium or a refrigerant whose temperature has been adjusted from the outer surface of the reaction container.
  • the devolatile step removes volatile components (for example, unreacted monomer, water, etc.) contained in the (meth) acrylic copolymer of the first aspect and the second aspect obtained in the bulk polymerization step (for example, unreacted monomer, moisture, etc.). This is the process of devolatile).
  • a known method can be adopted as the devolatilization method.
  • Examples of the devolatile method include a method of treating a (meth) acrylic copolymer using an extruder with a vent. The set temperature of the extruder may be determined in consideration of the boiling point of the volatile component to be removed and the like.
  • the pulverization step is a step of pulverizing the (meth) acrylic copolymer of the first aspect and the second aspect, which have been devolatile-treated as necessary, so as to have a desired particle size.
  • the pulverization method any pulverization method according to the required particle size can be adopted.
  • the maximum diameter of the particles after pulverization is preferably 5 mm or less, more preferably 2 mm or less, from the viewpoint of forming a slurry with water during neutralization and dissolution in water.
  • the (meth) acrylic copolymer of the first aspect and the second aspect of the present invention described above has excellent solubility and powder properties, it has good solubility in various solvents, especially alkaline water. be. Further, the composition and the ink containing the (meth) acrylic copolymer of the first aspect and the second aspect of the present invention are excellent in coatability, storage stability and concealment in film printing. Therefore, it is unlikely that bumps or uneven printing will occur during printing. Further, the (meth) acrylic copolymer according to the first aspect and the second aspect of the present invention is also excellent in productivity.
  • the (meth) acrylic copolymer of the first aspect and the second aspect of the present invention can be used as a raw material for, for example, inks and paints. In particular, it is suitable as a raw material for water-based inks.
  • the (meth) acrylic copolymer composition of the present invention is a group consisting of the (meth) acrylic copolymer of the first aspect of the present invention and the (meth) acrylic copolymer of the second aspect described above. Containing one or more selected from; with water; with a basic compound;
  • the (meth) acrylic copolymer composition may further contain a pigment and a solvent other than water (hereinafter, also referred to as "auxiliary solvent").
  • auxiliary solvent a solvent other than water
  • the (meth) acrylic copolymer composition containing a pigment is also particularly referred to as a “pigment-containing composition”.
  • the content of the (meth) acrylic copolymer is preferably 10 to 60% by mass, more preferably 15 to 50% by mass, based on the total mass of the (meth) acrylic copolymer composition.
  • the lower and upper limits of these numerical ranges can be combined arbitrarily.
  • the content of the (meth) acrylic copolymer is at least the above lower limit value, the film-forming property is good and the texture at the time of printing on the substrate is good.
  • the content of the (meth) acrylic copolymer is not more than the above upper limit value, the film-forming property is good and good printing performance on various substrates is exhibited.
  • the water content is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, based on the total mass of the (meth) acrylic copolymer composition.
  • the lower and upper limits of these numerical ranges can be combined arbitrarily. When the water content is at least the above lower limit, the miscibility with the pigment is good. When the water content is not more than the above upper limit, the viscosity after dissolving the (meth) acrylic polymer is low, and the mixing property with other materials is good.
  • the basic compound serves to neutralize the solid (meth) acrylic copolymer and dissolve it in water or a mixed solvent of water and an auxiliary solvent.
  • the basic compound include alkali metal hydroxides, ammonia, aqueous ammonia, and amine compounds.
  • alkali metal hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide and the like.
  • the amine compound include triethylamine, 1-propylamine, diethylamine, triisopropylamine, dibutylamine, amylamine, 1-octylamine, 2- (dimethylamino) ethanol, 2- (ethylamino) ethanol and 2- (diethylamino).
  • Ethanol 1-amino-2-propanol, 2-amino-1-propanol, 3-amino-1-propanol, 1- (dimethylamino) -2-propanol, 3- (dimethylamino) -1-propanol, 2- Examples thereof include (propylamino) ethanol, bis (3-ethoxypropyl) amine, aminobenzyl alcohol, morpholin, N-methylmorpholin, tetrabutylammonium hydroxide and the like.
  • the amine valence per usage amount is high, the amount of amine required for neutralization can be reduced, the ink can be made low in VOC, and the printed matter is easily volatilized after drying and does not easily remain in the printed matter.
  • Triethylamine, 2- (dimethylamino) ethanol are preferred. These may be used alone or in combination of two or more.
  • the content of the basic compound is preferably 0.1 to 10% by mass, more preferably 2 to 5% by mass, based on the total mass of the (meth) acrylic copolymer composition.
  • the lower and upper limits of these numerical ranges can be combined arbitrarily.
  • the content of the basic compound is at least the above lower limit, the solubility of the (meth) acrylic polymer composition is good.
  • the content of the basic compound is not more than the above upper limit value, the water resistance after printing is good.
  • pigment examples include titanium oxide, carbon black, phthalocyanine blue, phthalocyanine green, chrome yellow, cadmium yellow, chrome yellow, cobalt blue, chrome green, cobalt green, benzidine yellow, and zinc white.
  • any commercially available pigment can also be used. These may be used alone or in combination of two or more.
  • the content of the pigment is preferably 20 to 60% by mass, preferably 20 to 50% by mass, based on the total mass of the (meth) acrylic copolymer composition. % Is more preferable.
  • the lower and upper limits of these numerical ranges can be combined arbitrarily.
  • the content of the pigment is at least the above lower limit value, the concealment property to the substrate is improved and the color development of the coating film is improved.
  • the content of the pigment is not more than the above upper limit value, the ink in which the pigment is uniformly dispersed can be adjusted, and the coating film has less lumps.
  • the (meth) acrylic copolymer composition of the present invention contains water as a solvent, but may contain a solvent other than water as an auxiliary solvent, if necessary.
  • auxiliary solvent include water-soluble organic solvents among alcohols, glycols, ethers, ketones, esters, and carbitols. These may be used alone or in combination of two or more.
  • the content of the auxiliary solvent is preferably 1 to 40% by mass, preferably 2 to 40% by mass, based on the total mass of the (meth) acrylic copolymer composition. 30% by mass is more preferable.
  • the lower and upper limits of these numerical ranges can be combined arbitrarily.
  • the content of the auxiliary solvent is at least the above lower limit value, the leveling property in the (meth) acrylic copolymer composition can be further improved.
  • the content of the auxiliary solvent is not more than the above upper limit value, the amount of the volatile organic compound (VOC) contained in the (meth) acrylic copolymer composition can be reduced.
  • the (meth) acrylic copolymer composition is obtained by dissolving the (meth) acrylic copolymer together with a basic compound in, for example, water or a mixed solvent of water and an auxiliary solvent. At that time, a pigment may be blended if necessary.
  • Specific examples of the production method include a method of mixing and stirring the components constituting the (meth) acrylic copolymer composition using a normally used stirrer.
  • the (meth) acrylic copolymer composition of the present invention described above is excellent in coatability, storage stability and concealment in film printing, and thus is less likely to cause bumps and uneven printing during printing.
  • the ink of the present invention contains the above-mentioned (meth) acrylic copolymer composition.
  • the ink further contains a pigment in addition to the (meth) acrylic copolymer composition.
  • the pigment-containing composition itself may be used as an ink, or may be further diluted with water or an auxiliary solvent.
  • the ink may further contain an auxiliary solvent, a binder, other auxiliary agents and the like, if necessary, for various purposes.
  • the content of the (meth) acrylic copolymer of the first aspect and the second aspect of the present invention contained in the ink is preferably 5 to 30% by mass, preferably 10 to 25% by mass, based on the total mass of the ink. Is more preferable.
  • the lower and upper limits of these numerical ranges can be combined arbitrarily.
  • the content of the (meth) acrylic copolymer is at least the above lower limit value, aggregation of the primary particles of the pigment can be suppressed.
  • the content of the (meth) acrylic copolymer is not more than the above upper limit value, the ink has a low viscosity and is easy to handle.
  • the content of water contained in the ink is preferably 20 to 60% by mass, more preferably 25 to 50% by mass, based on the total mass of the ink.
  • the lower and upper limits of these numerical ranges can be combined arbitrarily.
  • the water content is at least the above lower limit value, the ink has a low viscosity and is easy to print.
  • the water content is not more than the above upper limit value, the dryness of the printed matter is good.
  • the content of the basic compound contained in the ink is preferably 0.1 to 10% by mass, more preferably 2 to 5% by mass, based on the total mass of the ink.
  • the lower and upper limits of these numerical ranges can be combined arbitrarily.
  • the content of the basic compound is at least the above lower limit value, the film forming property of the ink is good.
  • the content of the basic compound is not more than the above upper limit value, an image having good water resistance can be formed.
  • the pigment examples include the pigments exemplified above in the description of the (meth) acrylic copolymer composition.
  • the content of the pigment contained in the ink is preferably 10 to 50% by mass, more preferably 20 to 40% by mass, based on the total mass of the ink.
  • the lower and upper limits of these numerical ranges can be combined arbitrarily.
  • the content of the pigment is at least the above lower limit value, the ink has excellent hiding power of the base material.
  • the content of the pigment is not more than the above upper limit value, the generation of agglomerates during printing is suppressed, and the ink has less color unevenness.
  • the ink of the present invention contains water as a solvent, but may contain a solvent other than water as an auxiliary solvent, if necessary.
  • the auxiliary solvent include the auxiliary solvent exemplified above in the description of the (meth) acrylic copolymer composition.
  • the content of the auxiliary solvent is preferably 0.1 to 30% by mass, more preferably 1 to 25% by mass, based on the total mass of the ink. The lower and upper limits of these numerical ranges can be combined arbitrarily.
  • the content of the auxiliary solvent is at least the above lower limit value, the leveling property in the water-based ink can be further improved.
  • the content of the auxiliary solvent is not more than the above upper limit value, the amount of the volatile organic compound (VOC) contained in the ink can be reduced.
  • the ink of the present invention may contain a binder for the purpose of supplementing the substrate adhesion of the ink.
  • a binder for the purpose of supplementing the substrate adhesion of the ink.
  • the binder include urethane dispersion (PUD), urethane-acrylic composite dispersion (PUA), acrylic emulsion, polyester dispersion, polyolefin dispersion, polyolefin-acrylic composite dispersion, polyolefin-polyester dispersion and the like. These may be used alone or in combination of two or more.
  • auxiliaries examples include defoaming agents, leveling agents, pigment dispersants, film-forming auxiliaries, and adhesion-imparting agents. These may be used alone or in combination of two or more.
  • the ink is obtained, for example, by adding a pigment and, if necessary, one or more of an auxiliary solvent, a binder and other auxiliary agents to a (meth) acrylic copolymer composition and mixing them. At that time, if necessary, a pigment dispersion treatment may be performed. Further, it may be further diluted with water if necessary.
  • a method for the pigment dispersion treatment an arbitrary dispersion treatment method using a commercially available rocking shaker, a planetary bead mill, a batch type stirring type bead mill, a continuous stirring type bead mill, or the like can be adopted.
  • the ink of the present invention described above is excellent in coatability, storage stability and concealment in film printing, and thus is less likely to cause bumps or uneven printing during printing.
  • the temperature (° C) corresponding to the intersection of the tangent line drawn for the point on the low temperature side and the tangent line of the point (conversion point) where the rate of change in the slope of the graph is maximum is set.
  • the next glass transition temperature (Tg) was used.
  • the water content of the (meth) acrylic copolymer is 0% when the (meth) acrylic copolymer is dried at 105 ° C. for 2 hours, and before and after drying when the (meth) acrylic copolymer is dried at 105 ° C. for 2 hours. It was calculated from the dry weight loss of the (meth) acrylic copolymer.
  • A After stirring for the first 3 hours, no precipitate was visually confirmed and the solubility was excellent.
  • methyl methacrylate was continuously added dropwise at a rate of 0.24 g / min for 75 minutes using a dropping pump, maintained at a polymerization temperature of 60 ° C. for 6 hours, and then cooled to room temperature.
  • the dispersant (1) was obtained.
  • the solid content of the obtained dispersant (1) was 7.5%.
  • Example 1 In a polymerization apparatus equipped with a stirrer, a cooling tube, and a thermometer, 40 parts of methyl methacrylate, 40 parts of n-butyl methacrylate, 5 parts of n-butyl acrylate, 15 parts of methacrylic acid, and trimethylolpropane trimethacrylate 1.2. A monomer mixture in which parts are uniformly dissolved, 0.4 parts of 2,2'-azobis (2-methylbutyronitrile), 2 parts of 2-ethylhexyl 3-mercaptopropionic acid, and trimethyl propanthris (3-parts).
  • the inside of the kettle was cooled to room temperature, and the generated slurry was dehydrated by a centrifugal dehydrator (first dehydration step).
  • the obtained (meth) acrylic copolymer and pure water as a cleaning liquid are put into a cleaning tank so that the mass ratio ((meth) acrylic copolymer: cleaning liquid) is 1: 2, and the mixture is stirred for 20 minutes.
  • dehydration was performed with a centrifugal dehydrator (second dehydration step).
  • the dehydrated (meth) acrylic copolymer is put into a flow tank type dryer whose internal temperature is set to 40 ° C., and the water content of the (meth) acrylic copolymer particles becomes 10% or less. Dry (drying process).
  • Tg secondary glass transition temperature
  • Mw weight average molecular weight
  • Mn number average molecular weight
  • Solubility in was evaluated.
  • water-based ink was prepared by the above-mentioned method, and the storage stability of the ink and the hiding property of the printed matter were evaluated. The results are shown in Table 1.
  • Examples 2, 3, 5, 6, Comparative Examples 1 to 7 Particle-like solid (meth) acrylic copolymer particles were produced in the same manner as in Example 1 except for the compounding compositions shown in Tables 1 and 2, and various measurements and evaluations were performed. The results are shown in Table 1.
  • Example 4 In a glass cell equipped with a thermometer, 70 parts of methyl methacrylate, 5 parts of n-butyl acrylate, 12 parts of 2-ethylhexyl acrylate, 13 parts of methacrylic acid, 1.2 parts of trimethylolpropane triacrylate, and tert-butyl. Uniform mixture of 0.4 part of peroxy-2-ethylhexanoate (manufactured by Nichiyu Co., Ltd., "Perbutyl O”), 4 parts of 2-ethylhexyl 3-mercaptopropionate, and 2 parts of pentaerythritol tetrakis (thioglycolate).
  • the temperature inside the glass cell was controlled to 83 ° C. in a water tank to start bulk polymerization, and after detecting the peak of polymerization heat generation, the bulk polymerization was treated at 90 ° C. for 30 minutes.
  • a (meth) acrylic copolymer was obtained (bulk polymerization step).
  • the inside of the glass cell was cooled to room temperature.
  • the lumpy solid (meth) acrylic copolymer is removed from the cell, crushed with a sanitary crusher SC-01 (manufactured by Misho Industry Co., Ltd.), and then shaken on a mesh with an opening of 2 mm to pass the passage.
  • Example 5 The particulate solid (meth) acrylic copolymer obtained in Example 4 was shaken on a mesh having an opening of 1 mm for 5 minutes, and the passage was collected to collect the particulate solid (meth) acrylic. A system copolymer was obtained.
  • Example 6 The particulate (meth) acrylic copolymer obtained in Example 4 was shaken on a mesh having an opening of 750 ⁇ m for 5 minutes, and the passage was collected to collect the particulate (meth) acrylic copolymer. A polymer was obtained.
  • -MMA Methyl methacrylate.
  • -N-BMA n-butyl methacrylate.
  • -N-BA n-butyl acrylate.
  • 2-EHA 2-ethylhexyl acrylate.
  • IBXMA Isobornyl methacrylate.
  • -MAA Methacrylic acid.
  • -TMPTMA Trimethylolpropane Trimethacrylate.
  • HDDA 1,6-hexanediol diacrylate.
  • -TMPTA Trimethylolpropane triacrylate.
  • EHMP 2-ethylhexyl 3-mercaptopropionate.
  • -EGMP Ethylene glycol bis (3-mercaptopropionate).
  • TMPMP Trimethylolpropanetris (3-mercaptopropionate).
  • -PEMP Pentaerythritol tetrakis (3-mercaptopropionate).
  • -PETG Pentaerythritol tetrakis (thioglycolate).
  • -AMBN 2,2'-azobis (2-methylbutyronitrile).
  • -Perbutyl O tert-butylperoxy-2-ethylhexanoate.
  • IBXMA is a substitute for the monomer (a) (monomer (a')).
  • the (meth) acrylic copolymer obtained in each example had good solubility in alkaline water.
  • the ink containing these (meth) acrylic copolymers has good storage stability and excellent concealment of printed matter in film printing.
  • the (meth) acrylic copolymer of Comparative Example 3 having a constituent unit of origin had poor solubility in alkaline water. Further, in the case of Comparative Example 3, although the (meth) acrylic copolymer composition was obtained, the viscosity was very high and the pigment could not be dispersed, so that the ink storage stability and the concealment of the printed matter were concealed. The sex could not be evaluated. It does not have a chemical structure derived from a trifunctional or higher functional mercaptan, but instead has a chemical structure derived from a monofunctional mercaptan or a chemical structure derived from a bifunctional mercaptan, but the ratio thereof is higher than that in Comparative Examples 1 and 2.
  • the few (meth) acrylic copolymers of Comparative Examples 4 and 5 did not dissolve in the eluent, and GPC measurement could not be performed. Moreover, the solubility in alkaline water was poor. Further, in the cases of Comparative Examples 4 and 5, although the (meth) acrylic copolymer composition was obtained, the viscosity was very high and the pigment could not be dispersed, so that the ink storage stability and the printed matter were printed. could not evaluate the concealment of.
  • the (meth) acrylic copolymers of Comparative Examples 6 and 7 having no structural unit derived from the monomer (a) or the structural unit derived from the monomer (b) had poor solubility in alkaline water. ..
  • the (meth) acrylic copolymer and the (meth) acrylic copolymer having good solubility in alkaline water and good storage stability of ink and good concealment in film printing can be obtained. It is possible to provide an ink containing the (meth) acrylic copolymer composition containing the (meth) acrylic copolymer composition and the (meth) acrylic copolymer composition. Therefore, the (meth) acrylic copolymer of the present invention can be suitably used in the field of resin compositions that can be developed with an alkaline aqueous solution, and is extremely important in industry.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (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)
  • Compositions Of Macromolecular Compounds (AREA)
PCT/JP2021/029243 2020-11-18 2021-08-06 （メタ）アクリル系共重合体、（メタ）アクリル系共重合体組成物およびインク WO2022107402A1 (ja)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2022563580A JPWO2022107402A1 (ko) 2020-11-18 2021-08-06
CN202180067390.2A CN116390960A (zh) 2020-11-18 2021-08-06 (甲基)丙烯酸类共聚物、(甲基)丙烯酸类共聚物组合物及油墨

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2020-192003 2020-11-18
JP2020192003 2020-11-18

Publications (1)

Publication Number Publication Date
WO2022107402A1 true WO2022107402A1 (ja) 2022-05-27

Family

ID=81708772

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2021/029243 WO2022107402A1 (ja) 2020-11-18 2021-08-06 （メタ）アクリル系共重合体、（メタ）アクリル系共重合体組成物およびインク

Country Status (3)

Country Link
JP (1) JPWO2022107402A1 (ko)
CN (1) CN116390960A (ko)
WO (1) WO2022107402A1 (ko)

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04304277A (ja) * 1990-12-27 1992-10-27 Vianova Kunstharz Ag アクリル酸エステル共重合体系の水で希釈できる塗料結合剤
JP2005097406A (ja) * 2003-09-24 2005-04-14 Nippon Shokubai Co Ltd 紫外線硬化型ホットメルト粘着剤組成物
US20140179823A1 (en) * 2012-12-21 2014-06-26 Rohm And Haas Company Acrylic dispersions with multi-functional acrylates for uv-cure coatings
JP2016196626A (ja) * 2015-04-02 2016-11-24 アイカ工業株式会社 自動車灯具用反応性ホットメルト組成物及び自動車灯具
WO2019065604A1 (ja) * 2017-09-29 2019-04-04 富士フイルム株式会社 水性組成物及び高分子化合物
JP2019163417A (ja) * 2018-03-20 2019-09-26 富士フイルム株式会社 インク、インクセット、インクジェット記録方法、及びインクの製造方法
JP2019207143A (ja) * 2018-05-29 2019-12-05 東洋インキＳｃホールディングス株式会社 生化学分析用ブロッキング剤
EP3587459A1 (en) * 2018-06-23 2020-01-01 Helios, Tovarna Barv lakov in umetnih smol Kolicevo, d.o.o. Synthetic resin for preparation of protective coatings and process for preparation of coatings on the basis of such resin
JP2020041071A (ja) * 2018-09-12 2020-03-19 住友化学株式会社 組成物、硬化膜および表示装置

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04304277A (ja) * 1990-12-27 1992-10-27 Vianova Kunstharz Ag アクリル酸エステル共重合体系の水で希釈できる塗料結合剤
JP2005097406A (ja) * 2003-09-24 2005-04-14 Nippon Shokubai Co Ltd 紫外線硬化型ホットメルト粘着剤組成物
US20140179823A1 (en) * 2012-12-21 2014-06-26 Rohm And Haas Company Acrylic dispersions with multi-functional acrylates for uv-cure coatings
JP2016196626A (ja) * 2015-04-02 2016-11-24 アイカ工業株式会社 自動車灯具用反応性ホットメルト組成物及び自動車灯具
WO2019065604A1 (ja) * 2017-09-29 2019-04-04 富士フイルム株式会社 水性組成物及び高分子化合物
JP2019163417A (ja) * 2018-03-20 2019-09-26 富士フイルム株式会社 インク、インクセット、インクジェット記録方法、及びインクの製造方法
JP2019207143A (ja) * 2018-05-29 2019-12-05 東洋インキＳｃホールディングス株式会社 生化学分析用ブロッキング剤
EP3587459A1 (en) * 2018-06-23 2020-01-01 Helios, Tovarna Barv lakov in umetnih smol Kolicevo, d.o.o. Synthetic resin for preparation of protective coatings and process for preparation of coatings on the basis of such resin
JP2020041071A (ja) * 2018-09-12 2020-03-19 住友化学株式会社 組成物、硬化膜および表示装置

Also Published As

Publication number Publication date
JPWO2022107402A1 (ko) 2022-05-27
CN116390960A (zh) 2023-07-04

Similar Documents

Publication Publication Date Title
EP1710284B1 (en) Aqueous polymer dispersions
JP5507245B2 (ja) リン酸アルミニウム又はポリリン酸アルミニウム粒子の製造
JP5683263B2 (ja) 非イオン性水溶性添加剤
AU2013364228B2 (en) Grafted pigment dispersing polymeric additive and paint employing the same with improved hiding
KR101200124B1 (ko) 무기 안료용 고분자 분산제
US9574105B2 (en) Coating composition comprising autoxidisable component
JPH01213371A (ja) アニオン性種の掃除機構を有する水性被覆組成物
EP3523381B1 (en) Latex paint containing titanium dioxide pigment
WO2022107402A1 (ja) （メタ）アクリル系共重合体、（メタ）アクリル系共重合体組成物およびインク
AU2017339556B2 (en) Latex paint containing titanium dioxide pigment
CN113661189A (zh) 树脂颗粒及其制备方法和含有该树脂颗粒的亲水性赋予剂
CN111234093A (zh) 丙烯酸系聚合物颗粒及其制造方法、油墨组合物以及涂料组合物
WO2023276708A1 (ja) 増粘剤および接着剤組成物
US20140194585A1 (en) Bulk polymerization of (meth)acrylate copolymers soluble under aqueous-alkaline conditions
JPH0649131A (ja) 高酸価（メタ）アクリル系重合体の製造方法
JPH0258285B2 (ko)
CN107109088B (zh) 用于提高的遮盖的添加剂及包含其的漆组合物
JPH06211942A (ja) 顔料分散樹脂用ビニル系重合体の製造法
EP3130617B1 (en) Polymer nanoparticle preparation by miniemulsion polymerization
WO2017022423A1 (ja) （メタ）アクリル系架橋粒子およびその製造方法
JP5063182B2 (ja) ビニル系重合体及びその製造方法

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: 21894277

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2022563580

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 21894277

Country of ref document: EP

Kind code of ref document: A1